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Sample records for electrolyte li doped

  1. Li-Doped Ionic Liquid Electrolytes: From Bulk Phase to Interfacial Behavior

    NASA Technical Reports Server (NTRS)

    Haskins, Justin B.; Lawson, John W.

    2016-01-01

    Ionic liquids have been proposed as candidate electrolytes for high-energy density, rechargeable batteries. We present an extensive computational analysis supported by experimental comparisons of the bulk and interfacial properties of a representative set of these electrolytes as a function of Li-salt doping. We begin by investigating the bulk electrolyte using quantum chemistry and ab initio molecular dynamics to elucidate the solvation structure of Li(+). MD simulations using the polarizable force field of Borodin and coworkers were then performed, from which we obtain an array of thermodynamic and transport properties. Excellent agreement is found with experiments for diffusion, ionic conductivity, and viscosity. Combining MD simulations with electronic structure computations, we computed the electrochemical window of the electrolytes across a range of Li(+)-doping levels and comment on the role of the liquid environment. Finally, we performed a suite of simulations of these Li-doped electrolytes at ideal electrified interfaces to evaluate the differential capacitance and the equilibrium Li(+) distribution in the double layer. The magnitude of differential capacitance is in good agreement with our experiments and exhibits the characteristic camel-shaped profile. In addition, the simulations reveal Li(+) to be highly localized to the second molecular layer of the double layer, which is supported by additional computations that find this layer to be a free energy minimum with respect to Li(+) translation.

  2. Electrical analysis of amorphous corn starch-based polymer electrolyte membranes doped with LiI

    NASA Astrophysics Data System (ADS)

    Shukur, M. F.; Ibrahim, F. M.; Majid, N. A.; Ithnin, R.; Kadir, M. F. Z.

    2013-08-01

    In this work, polymer electrolytes have been prepared by doping starch with lithium iodide (LiI). The incorporation of 30 wt% LiI optimizes the room temperature conductivity of the electrolyte at (1.83 ± 0.47) × 10-4 S cm-1. Further conductivity enhancement to (9.56 ± 1.19) × 10-4 S cm-1 is obtained with the addition of 30 wt% glycerol. X-ray diffraction analysis indicates that the conductivity enhancement is due to the increase in amorphous content. The activation energy, Ea, of 70 wt% starch-30 wt% LiI electrolyte is 0.26 eV, while 49 wt% starch-21 wt% LiI-30 wt% glycerol electrolyte exhibits an Ea of 0.16 eV. Dielectric studies show that all the electrolytes obey non-Debye behavior. The power law exponent s is obtained from the variation of dielectric loss, ɛi, with frequency at different temperatures. The conduction mechanism of 70 wt% starch-30 wt% LiI electrolyte can be explained by the correlated barrier hopping model, while the conduction mechanism for 49 wt% starch-21 wt% LiI-30 wt% glycerol electrolyte can be represented by the quantum mechanical tunneling model.

  3. Defect Structure of Li-Doped BPO 4: A Nanostructured Ceramic Electrolyte for Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Jak, M. J. G.; Kelder, E. M.; Schoonman, J.

    1999-01-01

    In this paper the defect chemistry of Li-doped BPO4(BPO4-xLi2O, 0≤x≤0.1) is studied. This nanostructured ceramic electrolyte is used in all-solid-state Li-ion batteries. By changing the Li-doping level the influence on the crystal structure is studied and related to t he properties of the material. X-ray diffraction, Fourier-transformed infra-red spectroscopy (FT-IR),31P,11B, and7Li magic-angle-spinning solid state nuclear magnetic resonance, neutron diffraction, and inductively coupled plasma optical-emission spectroscopy measurements are used in order to study the structure. The electrical properties are studied with AC-impedance spectroscopy (AC-IS). The experimental data show that the defect structure of Li-doped BPO4can be described with two defect models, Li″B+2Li·iand V‴B+3Li·i, suggesting that the ionic conductivity takes place via interstitial Li ions.

  4. Li(+)- and Eu(³+)-doped poly(ε-caprolactone)/siloxane biohybrid electrolytes for electrochromic devices.

    PubMed

    Fernandes, M; Nobre, S S; Rodrigues, L C; Gonçalves, A; Rego, R; Oliveira, M C; Ferreira, R A S; Fortunato, E; Silva, M M; Carlos, L D; Bermudez, V de Zea

    2011-08-01

    The sol-gel process has been successfully combined with the "mixed cation" effect to produce novel luminescent and ion conducting biohybrids composed of a diurethane cross-linked poly(ε-caprolactone) (PCL530)/siloxane hybrid network (PCL stands for the poly(ε-caprolactone) biopolymer and 530 is the average molecular weight in gmol(-1)) doped with a wide range of concentrations of lithium and europium triflates (LiCF(3)SO(3) and Eu(CF(3)SO(3))(3), respectively) (molar ratio of ca. 50:50). The hybrid samples are all semicrystalline: whereas at n = 52.6 and 27.0 (n, composition, corresponds to the number of (C(═O)(CH(2))(5)O) repeat units of PCL(530) per mixture of Li(+) and Eu(3+) ions) a minor proportion of crystalline PCL(530) chains is present, at n = 6.1, a new crystalline phase emerges. The latter electrolyte is thermally stable up to 220 °C and exhibits the highest conductivity over the entire range of temperatures studied (3.7 × 10(-7) and 1.71 × 10(-4) S cm(-1) at 20 and 102 °C, respectively). According to infrared spectroscopic data, major modifications occur in terms of hydrogen bonding interactions at this composition. The electrochemical stability domain of the biohybrid sample with n = 27 spans more than 7 V versus Li/Li(+). This sample is a room temperature white light emitter. Its emission color can be easily tuned across the Commission Internationale d'Éclairage (CIE) chromaticity diagram upon simply changing the excitation wavelength. Preliminary tests performed with a prototype electrochromic device (ECD) comprising the sample with n = 6.1 as electrolyte and WO(3) as cathodically coloring layer are extremely encouraging. The device exhibits switching time around 50 s, an optical density change of 0.15, good open circuit memory under atmospheric conditions (ca. 1 month) and high coloration efficiency (577 cm(2) C(-1) in the second cycle). PMID:21774498

  5. Identification and inspection of the vacancy site in Li doped BPO 4 ceramic electrolyte by NMR

    NASA Astrophysics Data System (ADS)

    Dodd, A. J.; van Eck, E. R. H.

    2002-10-01

    A study of the properties of the high temperature ceramic electrolyte Li xB 1- x/3 PO 4 (lithium boron phosphate) is reported. XRD and NMR are used to investigate changes of the material as a function of heat treatment. It was found that after synthesis at 450 °C the material contains a phase of Li 4P 2O 7 in addition to the BPO 4 phase. This second phase is removed by heat treatment at temperatures higher than 600 °C. Boron vacancies are present, REDOR and CPMAS techniques are used to investigate this defect site and show that for the heat treated material Li ions are present at the vacancy site.

  6. The effects of lithium doping level on the structural, electrical properties of Li{sup +}-doped BPO{sub 4} solid electrolyte

    SciTech Connect

    Gao, Shan; Shui, Miao Zheng, Weidong; Yang, Tianci; Shu, Jie; Cheng, Liangliang; Feng, Lin; Ren, Yuanlong

    2013-08-01

    Graphical abstract: - Highlights: • Better ionic conductivities when 0.05 ≤ x ≤ 0.13. • V{sup ‴}{sub B}+3Li{sub i} model was preferred. • Grain size, lattice strain and Li{sup +}conductivity are closely related. - Abstract: A series of lithium ion conducting solid electrolytes Li{sub x}B{sub 1−x/3}PO{sub 4}(x = 0.01, 0.05, 0.09, 0.13, 0.17, 0.20) is synthesized by a soft-chemistry route. FTIR and XRD measurements reveal that the electrolyte is pure phase of tetragonal structure. AC-impedance spectroscopy (AC-IS) at room temperature shows that Li{sub x}B{sub 1−x/3}PO{sub 4} exhibits higher ionic conductivities in the range 0.05 ≤ x ≤ 0.13, beyond which, the ionic conductivities decrease quickly. Maximum ionic conductivity of the Li{sub x}B{sub 1−x/3}PO{sub 4} reaches 3.35 × 10{sup −5} S cm{sup −1} at room temperature for x = 0.05. Direct current polarizing (DCP) measurement indicates that the decomposition voltage for the solid electrolyte reaches up to 3.7 V. Micro-structure parameters of synthesized Li{sub x}B{sub 1−x/3}PO{sub 4} samples are calculated by Rietveld refinement of X-ray diffraction spectra. The unit-cell parameters, lattice strain, crystal grain size and ionic conductivities of the samples are correlated with the lithium ion doping level x.

  7. Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI], [EMIM][BF4

    NASA Technical Reports Server (NTRS)

    Haskins, Justin Bradley; Bennett, William Raymond; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W., Jr.; Watson, John W.

    2014-01-01

    Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

  8. Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI] and [EMIM][BF4

    NASA Technical Reports Server (NTRS)

    Haskins, Justin B.; Bennett, William R.; Hernandez-Lugo, Dione M.; Wu, James; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

    2014-01-01

    Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-Nbutylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-Npropylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of x(sub Li) we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing x(sub Li), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of x(sub Li) is approximately 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 - 0.3 mS/cm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

  9. Enhancement of lithium ion conductivity by doping Li3BO3 in Li2S-P2S5 glass-ceramics electrolytes for all-solid-state batteries

    NASA Astrophysics Data System (ADS)

    Eom, Minyong; Choi, Sunho; Son, Seunghyeon; Choi, Lakyoung; Park, Chanhwi; Shin, Dongwook

    2016-11-01

    (100-x) (0.78Li2S·0.22P2S5)·xLi3BO3 (0 ≤ x ≤ 5) solid electrolytes are prepared via mechanical milling and a post heat-treatment process, and the resulting electrochemical properties are investigated in conjunction with structural analysis. Adding of Li3BO3 into the (100-x) (0.78Li2S·0.22P2S5)·xLi3BO3 solid electrolyte is expected to enhance the conductivity and lower the activation energy as a consequence of changing the structural unit in the glass network. It turned out that the doping of Li3BO3 enhances the conductivity by enlarging the glass forming region and promoting precipitation of high lithium ion conductive thio-LISICON II analog. 97 (0.78Li2S·0.22P2S5)·3Li3BO3 (x = 3) glass-ceramics exhibits the highest conductivity (1.03 × 10-3 S cm-1). Structural analysis shows that the samples with Li3BO3 added to the electrolyte are composed of the main structural unit of PS43- with partially-modified structural unit of PO43-, which are believed to effectively enhance the conductivity and decrease the activation energy. In glass-ceramics produced from these materials, the thio-LISICON II phase with higher ionic conductivity tends to be stabilized by the addition of Li3BO3. Additionally, the formation of space-charge layer is relaxed by Li3BO3 doping. As a result, the all-solid-state cell shows high initial discharge capacity of 156 mAh g-1, and the capacity is retained to be 149 mAh g-1 for 40 cycles.

  10. Li3PO4-doped Li7P3S11 glass-ceramic electrolytes with enhanced lithium ion conductivities and application in all-solid-state batteries

    NASA Astrophysics Data System (ADS)

    Huang, Bingxin; Yao, Xiayin; Huang, Zhen; Guan, Yibiao; Jin, Yi; Xu, Xiaoxiong

    2015-06-01

    70Li2S·(30-x)P2S5·xLi3PO4 (mol%) amorphous powders are prepared by a high-energy ball milling technique, and the glass-ceramics are obtained by the crystallization of as-prepared amorphous samples. The XRD patterns show that a crystalline phase with a Li7P3S11 structure is obtained for x ≤ 3, while a structure change is observed for x = 5. The Li+-ion conductivity is enhanced by the substitution of Li3PO4 for P2S5, and the 70Li2S·29P2S5·1Li3PO4 glass-ceramics exhibit the highest total conductivity of 1.87 × 10-3 S cm-1 at 25 °C and the lowest activation energy of 18 kJ mol-1. The LiCoO2 in the all-solid-state cell of In-Li/70Li2S·29P2S5·1Li3PO4/LiCoO2 exhibits a discharge capacity of 108 mAh g-1, which is 20% higher than that in the In-Li/70Li2S·30P2S5/LiCoO2 cell. The higher discharge capacity of the LiCoO2 electrode is attributed to the higher Li+-ion conductivity of the solid electrolyte and lower interface resistance of electrode-electrolyte.

  11. A New Sealed Lithium-Peroxide Battery with a Co-Doped Li2O Cathode in a Superconcentrated Lithium Bis(fluorosulfonyl)amide Electrolyte

    PubMed Central

    Okuoka, Shin-ichi; Ogasawara, Yoshiyuki; Suga, Yosuke; Hibino, Mitsuhiro; Kudo, Tetsuichi; Ono, Hironobu; Yonehara, Koji; Sumida, Yasutaka; Yamada, Yuki; Yamada, Atsuo; Oshima, Masaharu; Tochigi, Eita; Shibata, Naoya; Ikuhara, Yuichi; Mizuno, Noritaka

    2014-01-01

    We propose a new sealed battery operating on a redox reaction between an oxide (O2−) and a peroxide (O22−) with its theoretical specific energy of 2570 Wh kg−1 (897 mAh g−1, 2.87 V) and demonstrate that a Co-doped Li2O cathode exhibits a reversible capacity over 190 mAh g−1, a high rate capability, and a good cyclability with a superconcentrated lithium bis(fluorosulfonyl)amide electrolyte in acetonitrile. The reversible capacity is largely dominated by the O2−/O22− redox reaction between oxide and peroxide with some contribution of the Co2+/Co3+ redox reaction. PMID:25023009

  12. Synergistic multi-doping effects on the Li7La3Zr2O12 solid electrolyte for fast lithium ion conduction

    PubMed Central

    Shin, Dong Ok; Oh, Kyungbae; Kim, Kwang Man; Park, Kyu-Young; Lee, Byungju; Lee, Young-Gi; Kang, Kisuk

    2015-01-01

    Here, we investigate the doping effects on the lithium ion transport behavior in garnet Li7La3Zr2O12 (LLZO) from the combined experimental and theoretical approach. The concentration of Li ion vacancy generated by the inclusion of aliovalent dopants such as Al3+ plays a key role in stabilizing the cubic LLZO. However, it is found that the site preference of Al in 24d position hinders the three dimensionally connected Li ion movement when heavily doped according to the structural refinement and the DFT calculations. In this report, we demonstrate that the multi-doping using additional Ta dopants into the Al-doped LLZO shifts the most energetically favorable sites of Al in the crystal structure from 24d to 96 h Li site, thereby providing more open space for Li ion transport. As a result of these synergistic effects, the multi-doped LLZO shows about three times higher ionic conductivity of 6.14 × 10−4 S cm−1 than that of the singly-doped LLZO with a much less efforts in stabilizing cubic phases in the synthetic condition. PMID:26666197

  13. Computational and Experimental Investigation of Li-doped Ionic Liquid Electrolytes: [pyr14][tfsi], [pyr13][fsi], and [EMIM][BF4

    NASA Technical Reports Server (NTRS)

    Haskins, Justin B.; Bennett, William R.; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

    2014-01-01

    We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of

  14. Fluorine-Doped Antiperovskite Electrolyte for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Li, Yutao; Zhou, Weidong; Xin, Sen; Li, Shuai; Zhu, Jinlong; Lü, Xujie; Cui, Zhiming; Jia, Quanxi; Zhou, Jianshi; Zhao, Yusheng; Goodenough, John B

    2016-08-16

    A fluorine-doped antiperovskite Li-ion conductor Li2 (OH)X (X=Cl, Br) is shown to be a promising candidate for a solid electrolyte in an all-solid-state Li-ion rechargeable battery. Substitution of F(-) for OH(-) transforms orthorhombic Li2 OHCl to a room-temperature cubic phase, which shows electrochemical stability to 9 V versus Li(+) /Li and two orders of magnitude higher Li-ion conductivity than that of orthorhombic Li2 OHCl. An all-solid-state Li/LiFePO4 with F-doped Li2 OHCl as the solid electrolyte showed good cyclability and a high coulombic efficiency over 40 charge/discharge cycles. PMID:27356953

  15. Fluorine-Doped Antiperovskite Electrolyte for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Li, Yutao; Zhou, Weidong; Xin, Sen; Li, Shuai; Zhu, Jinlong; Lü, Xujie; Cui, Zhiming; Jia, Quanxi; Zhou, Jianshi; Zhao, Yusheng; Goodenough, John B

    2016-08-16

    A fluorine-doped antiperovskite Li-ion conductor Li2 (OH)X (X=Cl, Br) is shown to be a promising candidate for a solid electrolyte in an all-solid-state Li-ion rechargeable battery. Substitution of F(-) for OH(-) transforms orthorhombic Li2 OHCl to a room-temperature cubic phase, which shows electrochemical stability to 9 V versus Li(+) /Li and two orders of magnitude higher Li-ion conductivity than that of orthorhombic Li2 OHCl. An all-solid-state Li/LiFePO4 with F-doped Li2 OHCl as the solid electrolyte showed good cyclability and a high coulombic efficiency over 40 charge/discharge cycles.

  16. Rheological Studies of PMMA–PVC Based Polymer Blend Electrolytes with LiTFSI as Doping Salt

    PubMed Central

    Liew, Chiam–Wen; Durairaj, R.; Ramesh, S.

    2014-01-01

    In this research, two systems are studied. In the first system, the ratio of poly (methyl methacrylate) (PMMA) and poly (vinyl chloride) (PVC) is varied, whereas in the second system, the composition of PMMA–PVC polymer blends is varied with dopant salt, lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) with a fixed ratio of 70 wt% of PMMA to 30 wt% of PVC. Oscillation tests such as amplitude sweep and frequency sweep are discussed in order to study the viscoelastic properties of samples. Elastic properties are much higher than viscous properties within the range in the amplitude sweep and oscillatory shear sweep studies. The crossover of and is absent. Linear viscoelastic (LVE) range was further determined in order to perform the frequency sweep. However, the absence of viscous behavior in the frequency sweep indicates the solid-like characteristic within the frequency regime. The viscosity of all samples is found to decrease as shear rate increases. PMID:25051241

  17. Composite Solid Electrolyte Containing Li+- Conducting Fibers

    NASA Technical Reports Server (NTRS)

    Appleby, A. John; Wang, Chunsheng; Zhang, Xiangwu

    2006-01-01

    Improved composite solid polymer electrolytes (CSPEs) are being developed for use in lithium-ion power cells. The matrix components of these composites, like those of some prior CSPEs, are high-molecular-weight dielectric polymers [generally based on polyethylene oxide (PEO)]. The filler components of these composites are continuous, highly-Li(+)-conductive, inorganic fibers. PEO-based polymers alone would be suitable for use as solid electrolytes, were it not for the fact that their room-temperature Li(+)-ion conductivities lie in the range between 10(exp -6) and 10(exp -8) S/cm, too low for practical applications. In a prior approach to formulating a CSPE, one utilizes nonconductive nanoscale inorganic filler particles to increase the interfacial stability of the conductive phase. The filler particles also trap some electrolyte impurities. The achievable increase in conductivity is limited by the nonconductive nature of the filler particles.

  18. Composite Solid Electrolyte for Li Battery Applications

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Attia, A. I.; Halpert, G.; Peled, E.

    1993-01-01

    The electrochemical, bulk and interfacial properties of the polyethylene oxide (PEO) based composite solid electrolyte (CSE) comprising LiI, PEO, and Al2O3 have been evaluated for Li battery applications. The bulk interfacial and transport properties of the CSEs seem to strongly depend on the alumina particle size. For the CSE films with 0.05 micron alumina while the bulk conductivity is around 10(exp -4) (mho/cm) at 103 C, the Li ion transport number seems to be close to unity at the same temperature. Compared to the PEO electrolyte this polymer composite electrolyte seems to exhibit robust mechanical and interfacial properties. We have studied three different films with three different alumina sizes in the range 0.01-0.3 micron. Effects of Al2O3 particle size on the electrochemical performance of polymer composite electrolyte is discussed. With TiS2 as cathode a 10 mAh small capacity cell was charged and discharged at C/40 and C/20 rates respectively.

  19. Stability of the Solid Electrolyte Interface on the Li Electrode in Li-S Batteries.

    PubMed

    Zheng, Dong; Yang, Xiao-Qing; Qu, Deyang

    2016-04-27

    By means of high performance liquid chromatography-mass spectroscopy, the concentration of sulfur and polysulfides was determined in nonaqueous electrolytes. The stability of sulfur and Li in eight electrolytes was studied quantitatively. It was found that sulfur reacted with Li in most of the commonly used electrolytes for lithium-sulfur batteries. The reaction products between sulfur and Li were qualitatively identified. In some cases, the solid electrolyte interface on the Li can successfully prevent the interaction between S and Li; however, it was found that the solid electrolyte interface was damaged by polysulfide ions. PMID:27045986

  20. Endurance testing with Li/Na electrolyte

    SciTech Connect

    Ong, E.T.; Remick, R.J.; Sishtla, C.I.

    1996-12-31

    The Institute of Gas Technology (IGT), under subcontract to M-C Power Corporation under DOE funding, has been operating bench-scale fuel cells to investigate the performance and endurance issues of the Li/Na electrolyte because it offers higher ionic conductivity, higher exchange current densities, lower vapor pressures, and lower cathode dissolution rates than the Li/K electrolyte. These cells have continued to show higher performance and lower decay rates than the Li/K cells since the publication of our two previous papers in 1994. In this paper, test results of two long-term 100-cm{sup 2} bench scale cells are discussed. One cell operated continuously at 160 mA/cm{sup 2} for 17,000 hours with reference gases (60H{sub 2}/20CO{sub 2}/20H{sub 2}O fuel at 75% utilization and 30CO{sub 2}/70 air oxidant humidified at room temperature at 50% utilization). The other cell operated at 160 mA/cm{sup 2} for 6900 hours at 3 atm with system gases (64H{sub 2}/16CO{sub 2}/20H{sub 2}O at 75% utilization and an M-C Power system-defined oxidant at 40% utilization). Both cells have shown the highest performance and longest endurance among IGT cells operated to date.

  1. High performance MCFC using Li/Na electrolyte

    SciTech Connect

    Donado, R.A.; Ong, E.T.; Sishtla, C.I.

    1995-08-01

    The substitution of a lithium/ sodium carbonate (Li/Na) mixture for the lithium/potassium carbonate (Li/K) electrolyte used in MCFCs holds the promise of higher ionic conductivity, higher exchange current density at both electrodes, lower vapor pressure, and lower cathode dissolution rates. However, when the substitution is made in cells optimized for use with the Li/K electrolyte, the promised increase in performance is not realized. As a consequence the literature contains conflicting data with regard to the performance, compositional stability, and chemical reactivity of the Li/Na electrolyte. Experiments conducted at the Institute of Gas Technology (IGT) concluded that the source of the problem is the different wetting characteristics of the two electrolytes. Electrode pore structures optimized for use with Li/K do not work well with Li/Na. Using proprietary methods and materials, IGT was able to optimize a set of electrodes for the Li/Na electrolyte. Experiments conducted in bench-scale cells have confirmed the superior performance of the Li/Na electrolyte compared to the Li/K electrolyte. The Li/Na cells exhibited a 5 to 8 percent improvement in overall performance, a substantial decrease in the rate of cathode dissolution, and a decreased decay rate. The longest running cell has logged over 13,000 hours of operation with a decay rate of less than 2 mV/1000 hours.

  2. Li2OHCl crystalline electrolyte for stable metallic lithium anodes

    DOE PAGESBeta

    Hood, Zachary D.; Wang, Hui; Samuthira Pandian, Amaresh; Keum, Jong Kahk; Liang, Chengdu

    2016-01-22

    In a classic example of stability from instability, we show that Li2OHCl solid electrolyte forms a stable solid electrolyte interface (SEI) with metallic lithium anode. The Li2OHCl solid electrolyte can be readily achieved through simple mixing of air-stable LiOH and LiCl precursors with a mild processing temperature under 400 °C. Additionally, we show that continuous, dense Li2OHCl membranes can be fabricated at temperatures less than 400 °C, standing in great contrast to current processing temperatures of over 1600 °C for most oxide-based solid electrolytes. The ionic conductivity and Arrhenius activation energy were explored for the LiOH-LiCl system of crystalline solidmore » electrolytes where Li2OHCl with increased crystal defects was found to have the highest ionic conductivity and reasonable Arrhenius activation energy. The Li2OHCl solid electrolyte displays stability against metallic lithium, even in extreme conditions past the melting point of lithium metal. Furthermore, to understand this excellent stability, we show that SEI formation is critical in stabilizing the interface between metallic lithium and the Li2OHCl solid electrolyte.« less

  3. Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

    SciTech Connect

    Yu, Seungho; Schmidt, Robert D.; Garcia-mendez, Regina; Herbert, Erik G.; Dudney, Nancy J.; Wolfenstine, Jeff; Sakamoto, Jeff; Seigel, Donald

    2015-12-16

    The oxide known as LLZO, with nominal composition Li7La3Zr2O12, is a promising solid electrolyte for Li-based batteries due to its high Li-ion conductivity and chemical stability with respect to lithium. Solid electrolytes may also enable the use of metallic Li anodes by serving as a physical barrier that suppresses dendrite initiation and propagation during cycling. Prior linear elasticity models of the Li electrode/solid electrolyte interface suggest that the stability of this interface is highly dependent on the elastic properties of the solid separator. For example, dendritic suppression is predicted to be enhanced as the electrolyte s shear modulus increases. In the present study a combination of first-principles calculations, acoustic impulse excitation measurements, and nanoindentation experiments are used to determine the elastic constants and moduli for highconductivity LLZO compositions based on Al and Ta doping. The calculated and measured isotropic shear moduli are in good agreement and fall within the range of 56-61 GPa. These values are an order of magnitude larger than that for Li metal and far exceed the minimum value ( 8.5 GPa) believed to be necessary to suppress dendrite initiation. These data suggest that LLZO exhibits sufficient stiffness to warrant additional development as a solid electrolyte for Li batteries.

  4. Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

    DOE PAGESBeta

    Yu, Seungho; Schmidt, Robert D.; Garcia-mendez, Regina; Herbert, Erik G.; Dudney, Nancy J.; Wolfenstine, Jeff; Sakamoto, Jeff; Seigel, Donald

    2015-12-16

    The oxide known as LLZO, with nominal composition Li7La3Zr2O12, is a promising solid electrolyte for Li-based batteries due to its high Li-ion conductivity and chemical stability with respect to lithium. Solid electrolytes may also enable the use of metallic Li anodes by serving as a physical barrier that suppresses dendrite initiation and propagation during cycling. Prior linear elasticity models of the Li electrode/solid electrolyte interface suggest that the stability of this interface is highly dependent on the elastic properties of the solid separator. For example, dendritic suppression is predicted to be enhanced as the electrolyte s shear modulus increases. Inmore » the present study a combination of first-principles calculations, acoustic impulse excitation measurements, and nanoindentation experiments are used to determine the elastic constants and moduli for highconductivity LLZO compositions based on Al and Ta doping. The calculated and measured isotropic shear moduli are in good agreement and fall within the range of 56-61 GPa. These values are an order of magnitude larger than that for Li metal and far exceed the minimum value ( 8.5 GPa) believed to be necessary to suppress dendrite initiation. These data suggest that LLZO exhibits sufficient stiffness to warrant additional development as a solid electrolyte for Li batteries.« less

  5. Self-doped molecular composite battery electrolytes

    DOEpatents

    Harrup, Mason K.; Wertsching, Alan K.; Stewart, Frederick F.

    2003-04-08

    This invention is in solid polymer-based electrolytes for battery applications. It uses molecular composite technology, coupled with unique preparation techniques to render a self-doped, stabilized electrolyte material suitable for inclusion in both primary and secondary batteries. In particular, a salt is incorporated in a nano-composite material formed by the in situ catalyzed condensation of a ceramic precursor in the presence of a solvated polymer material, utilizing a condensation agent comprised of at least one cation amenable to SPE applications. As such, the counterion in the condensation agent used in the formation of the molecular composite is already present as the electrolyte matrix develops. This procedure effectively decouples the cation loading levels required for maximum ionic conductivity from electrolyte physical properties associated with condensation agent loading levels by utilizing the inverse relationship discovered between condensation agent loading and the time domain of the aging step.

  6. Polymer electrolytes for a rechargeable li-Ion battery

    SciTech Connect

    Argade, S.D.; Saraswat, A.K.; Rao, B.M.L.; Lee, H.S.; Xiang, C.L.; McBreen, J.

    1996-10-01

    Lithium-ion polymer electrolyte battery technology is attractive for many consumer and military applications. A Li{sub x}C/Li{sub y}Mn{sub 2}O{sub 4} battery system incorporating a polymer electrolyte separator base on novel Li-imide salts is being developed under sponsorship of US Army Research Laboratory (Fort Monmouth NJ). This paper reports on work currently in progress on synthesis of Li-imide salts, polymer electrolyte films incorporating these salts, and development of electrodes and cells. A number of Li salts have been synthesized and characterized. These salts appear to have good voltaic stability. PVDF polymer gel electrolytes based on these salts have exhibited conductivities in the range 10{sup -4} to 10{sub -3} S/cm.

  7. Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

    NASA Technical Reports Server (NTRS)

    West, William; Whitacre, Jay; Lim, James

    2008-01-01

    Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

  8. Evaluation of LiCl-LiBr-KBr electrolyte for Li-alloy/metal disulfide cells

    SciTech Connect

    Kaun, T.D.

    1987-01-01

    The physical properties of a new molten salt electrolyte for lithium-alloy/metal disulfide cells, 25 mol % LiCl-37 mol % LiBr-38 mol % KBr, were investigated. Cyclic voltammetry of FeS/sub 2/ in the new molten salt at 375 to 425/sup 0/C indicated improved electrochemistry and stability of the reaction on the upper voltage plateau (1.75 V vs. LiAl). The new electrolyte provides an opportunity to operate an upper-plateau (UP) FeS/sub 2/ electrode at a lower temperature, 400/sup 0/C, and with a higher activity of lithium ion in the electrolyte. The broad liquidus of this molten salt at 400/sup 0/C also supports operation at high current density. Testing of 24- to 48-Ah cells indicated greater than 50% improved energy and power density over the conventional two-plateau FeS/sub 2/ cell with LiCl-KCl electrolyte. The conventional FeS/sub 2/ cells would lose 50% of their upper-plateau capacity within 200 cycles. The elimination of this capacity decline problem was demonstrated by 400 cycles and 5400 h of stable operation with a dense UP FeS/sub 2/ electrode cell, which maintained 89% utilization of theoretical capacity throughout the test.

  9. Acid and alkali doped PBI electrolyte in electrochemical system

    NASA Astrophysics Data System (ADS)

    Xing, Baozhong

    In this work the conductivity of blank PBI membrane, acid doped PBI and alkaline doped PBI was systematically studied. A new methodology for sorption kinetics study in electrolyte solution has been established by monitoring the conductivity change during the sorption process. The model of the doping process and mechanism of conductivity are proposed. The performance of PBI (doped under optimum conditions) in fuel cell as PEM was evaluated. The experimental results show that the blank PBI in acid solution is an ionic insulator. It clarified the long time confusion in this area. The acid doped PBI membrane is an ionic conductor. The conductivity increases with the concentration of the acid solution. In high concentration acid solution, the conductivity increases with the type of acid in the order: H2SO 4 > H3PO4 > HClO4 > HNO3 > HCl. The kinetics of the doping process was studied, by a continuous method. The ionic conductivity mechanism was established. The PBI membranes doped with H2SO4 and H3PO4 exhibit better performance than NafionRTM. The doped FBI has more resistance to CO poison. 3% CO in H2 has little effect on the H3PO 4 doped PBI membrane at 185°C. The conductivity of the alkali doped PBI membrane changes with the concentration of the alkaline solution and the type of the alkalis. The conductivity has a maximum in KOH and NaOH solution. The maximum conductivity in KOH is higher than in NaOH and LiOH. It is about 5 times of that of NafionRTM in alkaline solution. The two-step sorption process in alkaline solution was observed. The first step is the permeation process of the alkalis in the PBI membrane. The permeation is the results of diffusion and interaction. It is concluded that the permeation process is controlled by the rate of interaction between the alkali and PBI molecule. The second step is the relaxation process in the membrane. This step contributes more to the conductivity for the membrane than the first step. The ionic conductivity mechanism

  10. Self-doped microphase separated block copolymer electrolyte

    DOEpatents

    Mayes, Anne M.; Sadoway, Donald R.; Banerjee, Pallab; Soo, Philip; Huang, Biying

    2002-01-01

    A polymer electrolyte includes a self-doped microphase separated block copolymer including at least one ionically conductive block and at least one second block that is immiscible in the ionically conductive block, an anion immobilized on the polymer electrolyte and a cationic species. The ionically conductive block provides a continuous ionically conductive pathway through the electrolyte. The electrolyte may be used as an electrolyte in an electrochemical cell.

  11. Physico- and electrochemistry of composite electrolytes based on PEODME-LiTFSI with TiO 2

    NASA Astrophysics Data System (ADS)

    Moskwiak, M.; Giska, I.; Borkowska, R.; Zalewska, A.; Marczewski, M.; Marczewska, H.; Wieczorek, W.

    The effect of fumed TiO 2 fillers (pure and modified by H 2SO 4) on ionic conductivity of composite electrolytes based on poly(ethylene oxide) dimethyl ether (PEODME) oligomer (M w = 500) doped with lithium bis-(trifluoromethanesulfonyl)imide LiN(CF 3SO 2) 2 (LiTFSI) are studied by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR) and complex impedance methods. The electrochemical stability of the electrolytes in the potential range of 4 V versus Li electrode has been confirmed by voltammetric measurements. Li electrode reactions have been followed by means of impedance spectroscopy. The growth in time of the resistance of the interfacial (Li electrode-polymer electrolyte) layers was inhibited upon the addition of fillers.

  12. Modification of LiCl-LiBr-KBr electrolyte for LiAl/FeS{sub 2} batteries

    SciTech Connect

    Kaun, T.D.; Jansen, A.N.; Henriksen, G.L.; Vissers, D.R.

    1996-06-01

    The bipolar LiAl/FeS{sub 2} battery is being developed to achieve the high performance and long cycle life needed for electric vehicle application. The molten-salt (400 to 440 C operation) electrolyte composition for this battery has evolved to support these objectives. An earlier change to LiCl-LiBr-KBr electrolyte is responsible for significantly increased cycle life (up to 1,000 cycles). Recent electrolyte modification has significantly improved cell performance; approximately 50% increased power, with increased high rate capacity utilization. Results are based on power-demanding EV driving profile test at 600 W/kg. The effects of adding small amounts (1--5 mol%) of LiF and LiI to LiCl-LiBr-KBr electrolyte are discussed. By cyclic voltammetry, the modified electrolytes exhibit improved FeS{sub 2} electrochemistry. Electrolyte conductivity is little changed, but high current density (200 mA/cm{sup 2}) performance improved by approximately 50%. A specific feature of the LiI addition is an enhanced cell overcharge tolerance rate from 2.5 to 5 mA/cm{sup 2}. The rate of overcharge tolerance is related to electrolyte properties and negative electrode lithium activity. As a result, the charge balancing of a bipolar battery configuration with molten-salt electrolyte is improved to accept greater cell-to-cell deviations.

  13. Improving sulfolane-based electrolyte for high voltage Li-ion cells with electrolyte additives

    NASA Astrophysics Data System (ADS)

    Xia, Jian; Dahn, J. R.

    2016-08-01

    An electrolyte mixture containing 1 M LiPF6 in sulfolane:ethylmethyl carbonate 3:7 with vinylene carbonate and other electrolyte additives exhibited promising cycling and storage performance in high voltage Li(Ni0·4Mn0·4Co0.2)O2/graphite pouch type Li-ion cells tested to 4.5 V. Voltage drop during storage, coulombic efficiency, charge endpoint capacity slippage during ultra high precision cycling, charge-transfer resistance after storage or cycling, gas evolution during storage and cycling as well as capacity retention during long-term cycling were examined. The results for cells with sulfolane-based electrolytes were compared with those for cells with ethylene carbonate-based electrolytes containing state-of-the-art electrolyte additives. This survey showed that the combination of vinylene carbonate and triallyl phosphate as electrolyte additives in sulfolane:ethylmethyl carbonate electrolyte yielded cells capable of better performance during tests to 4.5 V than cells with ethylene carbonate-based electrolytes. These results suggest that sulfolane-based electrolytes may be promising for high voltage Li-ion cells.

  14. Improving sulfolane-based electrolyte for high voltage Li-ion cells with electrolyte additives

    NASA Astrophysics Data System (ADS)

    Xia, Jian; Dahn, J. R.

    2016-08-01

    An electrolyte mixture containing 1 M LiPF6 in sulfolane:ethylmethyl carbonate 3:7 with vinylene carbonate and other electrolyte additives exhibited promising cycling and storage performance in high voltage Li(Ni0·4Mn0·4Co0.2)O2/graphite pouch type Li-ion cells tested to 4.5 V. Voltage drop during storage, coulombic efficiency, charge endpoint capacity slippage during ultra high precision cycling, charge-transfer resistance after storage or cycling, gas evolution during storage and cycling as well as capacity retention during long-term cycling were examined. The results for cells with sulfolane-based electrolytes were compared with those for cells with ethylene carbonate-based electrolytes containing state-of-the-art electrolyte additives. This survey showed that the combination of vinylene carbonate and triallyl phosphate as electrolyte additives in sulfolane:ethylmethyl carbonate electrolyte yielded cells capable of better performance during tests to 4.5 V than cells with ethylene carbonate-based electrolytes. These results suggest that sulfolane-based electrolytes may be promising for high voltage Li-ion cells.

  15. Developing New Electrolytes for Advanced Li-ion Batteries

    NASA Astrophysics Data System (ADS)

    McOwen, Dennis Wayne

    The use of renewable energy sources is on the rise, as new energy generating technologies continue to become more efficient and economical. Furthermore, the advantages of an energy infrastructure which relies more on sustainable and renewable energy sources are becoming increasingly apparent. The most readily available of these renewable energy sources, wind and solar energy in particular, are naturally intermittent. Thus, to enable the continued expansion and widespread adoption of renewable energy generating technology, a cost-effective energy storage system is essential. Additionally, the market for electric/hybrid electric vehicles, which both require efficient energy storage, continues to grow as more consumers seek to reduce their consumption of gasoline. These vehicles, however, remain quite expensive, due primarily to costs associated with storing the electrical energy. High-voltage and thermally stable Li-ion battery technology is a promising solution for both grid-level and electric vehicle energy storage. Current limitations in materials, however, limit the energy density and safe operating temperature window of the battery. Specifically, the state-of-the-art electrolyte used in Li-ion batteries is not compatible with recently developed high-voltage positive electrodes, which are one of the most effectual ways of increasing the energy density. The electrolyte is also thermally unstable above 50 °C, and prone to thermal runaway reaction if exposed to prolonged heating. The lithium salt used in such electrolytes, LiPF6, is a primary contributor to both of these issues. Unfortunately, an improved lithium salt which meets the myriad property requirements for Li-ion battery electrolytes has eluded researchers for decades. In this study, a renewed effort to find such a lithium salt was begun, using a recently developed methodology to rapidly screen for desirable properties. Four new lithium salts and one relatively new but uncharacterized lithium salt were

  16. Electrolytic LiCl precipitation from LiCl-KCl melt in porous Li-Al anodes

    SciTech Connect

    Vallet, C.E.; Heatherly, D.E.; Heatherly, L. Jr.; Braunstein, J.

    1983-12-01

    Composition gradients such as those predicted to occur during discharge of porous Li-Al negative electrodes of Li/S batteries with LiCl-KCl eutectic electrolyte were generated and measured in the LiCl-KCl anolyte of an electrolysis cell with Li-Al electrodes. Precipitation of lithium chloride during electrolysis was observed by two-dimensional scanning of electrolyte composition in the front part of quenched porous Li-Al anode sections using SEM/EDX. The distribution of sites of increased or decreased LiCl concentration, LiCl saturation and precipitation was mapped. Cathodic regions were observed near the cell walls. Preliminary results of analysis by Auger spectroscopy confirm LiCl precipitation in the porous anode. 16 references, 7 figures, 1 table.

  17. Electrolytic LiCl precipitation from LiCl-KCl melt in porous Li-Al anodes

    NASA Astrophysics Data System (ADS)

    Vallet, C. E.; Heatherly, D. E.; Heatherly, L., Jr.; Braunstein, J.

    1983-12-01

    Composition gradients such as those predicted to occur during discharge of porous Li-Al negative electrodes of Li/S batteries with LiCl-KCl eutectic electrolyte were generated and measured in the LiCl-KCl anolyte of an electrolysis cell with Li-Al electrodes. Precipitation of lithium chloride during electrolysis was observed by two-dimensional scanning of electrolyte composition in the front part of quenched porous Li-Al anode sections using SEM/EDX. The distribution of sites of increased or decreased LiCl concentration, LiCl saturation and precipitation was mapped. Cathodic regions were observed near the cell walls. Preliminary results of analysis by Auger spectroscopy confirm LiCl precipitation in the porous anode.

  18. Photocured Gelled Electrolytes For Secondary Li Cells

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesan

    1994-01-01

    Class of photocured polymers exhibiting lithium-ion conductivities greater than those of well-studied polymers based on polyethylene oxide (PEO) show promise as polymeric electrolytes in rechargeable lithium cells. Increase in conductivity occasioned by use of electrolytes, coupled with amenability of electrolytes to formation into uniform thin (less than 25 micrometers thick), wide films, expected to result in cells with power densities greater than 100 W h/kg and charge/discharge rates exceeding currents equal, in amperes, to ampere-hour ratings. All-solid-state lithium batteries containing these electrolytes used as high-power, high-rate rechargeable power sources in commercial and aerospace applications.

  19. LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Reddy, V. Prakash; Prakash, G. K. Syria; Hu, Jinbo; Yan, Ping; Smart, Marshall; Bugga, ratnakumar; Chin, Keith; Surampudi, Subarao

    2008-01-01

    Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic

  20. Electrolytes for Li-Ion Cells in Low Temperature Applications

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Surampudi, S.

    2000-01-01

    Prototype AA-size lithium-ion cells have been demonstrated to operate effectively at temperatures as low as -30 to -40 C. These improvements in low temperature cell performance have been realized by the incorporation of ethylene carbonate-based electrolytes which possess low melting, low viscosity cosolvents, such as methyl acetate, ethyl acetate, gamma-butyrolactone, and ethyl methyl carbonate. The cells containing a 0.75M LiPF6 EC+DEC+DMC+EMC (1:1:1:1) electrolyte displayed the best performance at -30 C (> 90% of the room temperature capacity at approximately C/15 rate), whereas, at -40 C the cells with the 0.75M LiPF6 EC+DEC+DMC+MA (1:1:1:1) and 0.75M LiPF6 EC+DEC+DMC+EA (1:1:1:1) electrolytes showed superior performance.

  1. Electronic Properties of LiFePO4 and Li doped LiFePO4

    SciTech Connect

    Zhuang, G.V.; Allen, J.L.; Ross, P.N.; Guo, J.-H.; Jow, T.R.

    2005-06-28

    The potential use of different iron phosphates as cathodematerials in lithium-ion batteries has recently been investigated.1 Oneof the promising candidates is LiFePO4. This compound has severaladvantages in comparison to the state-of-the-art cathode material incommercial rechargeable lithium batteries. Firstly, it has a hightheoretical capacity (170 mAh/g). Secondly, it occurs as mineraltriphylite in nature and is inexpensive, thermally stable, non-toxic andnon-hygroscopic. However, its low electronic conductivity (~;10-9 S/cm)results in low power capability. There has been intense worldwideresearch activity to find methods to increase the electronic conductivityof LiFePO4, including supervalent ion doping,2 introducingnon-carbonaceous network conduction3 and carbon coating, and theoptimization of the carbon coating on LiFePO4 particle surfaces.4Recently, the Li doped LiFePO4 (Li1+xFe1-xPO4) synthesized at ARL hasyield electronic conductivity increase up to 106.5 We studied electronicstructure of LiFePO4 and Li doped LiFePO4 by synchrotron based soft X-rayemission (XES) and X-ray absorption (XAS) spectroscopies. XAS probes theunoccupied partial density of states, while XES the occupied partialdensity of states. By combining XAS and XES measurements, we obtainedinformation on band gap and orbital character of both LiFePO4 and Lidoped LiFePO4. The occupied and unoccupied oxygen partial density ofstates (DOS) of LiFePO4 and 5 percent Li doped LiFePO4 are presented inFig. 1. Our experimental results clearly indicate that LiFePO4 has wideband gap (~; 4 eV). This value is much larger than what is predicted byDFT calculation. For 5 percent Li doped LiFePO4, a new doping state wascreated closer to the Fermi level, imparting p-type conductivity,consistent with thermopower measurement. Such observation substantiatesthe suggestion that high electronic conductivity in Li1.05Fe0.95 PO4 isdue to available number of charge carriers in the material. Furthermore,Hall effect

  2. Power capability improvement of LiBOB/PC electrolyte for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Kaneko, Hiroaki; Sekine, Kyoichi; Takamura, Tsutomu

    Lithium bis(oxalto)borate (LiBOB) is quite effective to prevent vigorous decomposition of propylene carbonate (PC) at the graphite anode of a Li-ion battery during Li insertion. PC is a very good solvent that is inexpensive, has high conductivity and a low melting point; however, the power capability of PC electrolyte containing LiBOB is unsatisfactory. In an attempt to improve the power capability of the LiBOB/PC electrolyte, mixed electrolytes containing both LiBOB and LiClO 4 were examined. An integrated fiber felt of highly graphitized carbon was used as the working electrode and the performance was evaluated by cyclic voltammetry (CV), constant current followed by constant voltage charge (CCCV) and constant current discharge. The CV produced a stable peak for Li extraction, but the peak height was as low as half that obtained in a conventional electrolyte such as a 1:1 mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) containing 1 M LiClO 4. However, the peak height in PC, containing 1/49 M LiBOB and 1 M LiClO 4, became 1.5 times higher than that in PC containing 1 M LiBOB. The peak height was increased further using a 1:1 mixture of PC and acetonitrile (AN) containing 1/49 M LiBOB and 1 M LiClO 4, although the cycleability was poor. A similar tendency was observed with the CCCV test. The CV peak height was plotted against the ionic conductivity of several solvents and showed no linear relationship, implying that the reaction activity was influenced by the solid electrolyte interphase (SEI) formed. The charge transfer resistance was evaluated by impedance spectroscopy. The results revealed that not only the surface film resistance but also the charge transfer resistance was markedly increased in the electrolyte containing LiBOB; however, they were reduced by the addition of LiClO 4.

  3. Conductivity and properties of polysiloxane-polyether cluster-LiTFSI networks as hybrid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Boaretto, Nicola; Joost, Christine; Seyfried, Mona; Vezzù, Keti; Di Noto, Vito

    2016-09-01

    This report describes the synthesis and the properties of a series of polymer electrolytes, composed of a hybrid inorganic-organic matrix doped with LiTFSI. The matrix is based on ring-like oligo-siloxane clusters, bearing pendant, partially cross-linked, polyether chains. The dependency of the thermo-mechanic and of the transport properties on several structural parameters, such as polyether chains' length, cross-linkers' concentration, and salt concentration is studied. Altogether, the materials show good thermo-mechanical and electrochemical stabilities, with conductivities reaching, at best, 8·10-5 S cm-1 at 30 °C. In conclusion, the cell performances of one representative sample are shown. The scope of this report is to analyze the correlations between structure and properties in networked and hybrid polymer electrolytes. This could help the design of optimized polymer electrolytes for application in lithium metal batteries.

  4. Electronic Properties of LiFePO4 and Li doped LiFePO4

    SciTech Connect

    Allen, J.L.; Zhuang, G.V.; Ross, P.N.; Guo, J.-H.; Jow, T.R.

    2006-05-31

    LiFePO{sub 4} has several potential advantages in comparison to the transition metal oxide cathode materials used in commercial lithium-ion batteries. However, its low intrinsic electronic conductivity ({approx} 10{sup -9} S/cm) is problematic. We report here a study by soft x-ray absorption/emission spectroscopy of the electronic properties of undoped LiFePO{sub 4} and Li-doped LiFePO{sub 4} in which Li{sup +} ions are substituted for Fe{sup 2+} ions in an attempt to increase the intrinsic electronic conductivity. The conductivities of the Li{sub 1+x}Fe{sub 1-x}PO{sub 4} samples were, however, essentially unchanged from that of the undoped LiFePO{sub 4}. Nonetheless, evidence for changing the electronic properties of LiFePO{sub 4} by doping with excess Li+ was observed by the XAS/XES spectroscopy. New pre-edge features the O-1s XAS spectrum of Li{sub 1.05}Fe{sub 0.95}PO4 is a direct indication that the charge compensation for substitution of Fe{sup 2+} by Li{sup +} resides in the unoccupied O-2p orbitals. A charge transfer (CT) excitation was also observed in the doped material implying that the unoccupied O-2p orbitals created by doping are strongly hybridized with unoccupied Fe-3d orbitals of neighboring sites. However, the strong covalent bonding within the (PO{sub 4}){sup 3-} anions and the large separation of the Fe cations means that the charge created by doping is not delocalized in the manner of electrons or holes in a semiconductor.

  5. On the structural and impedance characteristics of Li- doped PEO, using n-butyl lithium in hexane as dopant

    SciTech Connect

    Anand, P. B. E-mail: jayalekshmi@cusat.ac.in; Jayalekshmi, S. E-mail: jayalekshmi@cusat.ac.in

    2014-01-28

    Nowadays polymer based solid state electrolytes for applications in rechargeable battery systems are highly sought after materials, pursued extensively by various research groups worldwide. Numerous methods are discussed in literature to improve the fundamental properties like electrical conductivity, mechanical stability and interfacial stability of polymer based electrolytes. The application of these electrolytes in Li-ion cells is still in the amateur state, due to low ionic conductivity, low lithium transport number and the processing difficulties. The present work is an attempt to study the effects of Li doping on the structural and transport properties of the polymer electrolyte, poly-ethelene oxide (PEO) (Molecular weight: 200,000). Li doped PEO was obtained by treating PEO with n-Butyllithium in hexane for different doping concentrations. Structural characterization of the samples was done by XRD and FTIR techniques. Impedance measurements were carried out to estimate the ionic conductivity of Li doped PEO samples. It is seen that, the crystallinity of the doped PEO decreases on increasing the doping concentration. XRD and FTIR studies support this observation. It is inferred that, ionic conductivity of the sample is increasing on increasing the doping concentration since less crystallinity permits more ionic transport. Impedance measurements confirm the results quantitatively.

  6. Chemical stability enhancement of lithium conducting solid electrolyte plates using sputtered LiPON thin film

    NASA Technical Reports Server (NTRS)

    West, W. C.; Whitacre, J. F.; Lim, J. R.

    2004-01-01

    Sputter deposition of LiPON films directly onto high Li+ conductivity solid electrolyte plates has been investigated as a means to minimize the reactivity of the plates to metallic Li. The LiPON films were shown to effectively passivate the plates in contact with metallic Li, in contrast to unpassivated plates that reacted immediately in contact with Li metal.

  7. Electrolyte effects in Li(Si)/FeS{sub 2} thermal batteries

    SciTech Connect

    Guidotti, R.A.; Reinhardt, F.W.

    1994-10-01

    The most common electrochemical couple for thermally activated (``thermal``) batteries is the Li-alloy/FeS{sub 2} system. The most common Li-alloys used for anodes are 20% Li-80% Al and 44% Li-56% Si (by weight); liquid Li immobilized with iron powder has also been used. The standard electrolyte that has been used in thermal batteries over the years is the LiCl-KCl eutectic that melts at 352{degrees}C. The LiCl-LiBr-LiF eutectic had the best rate and power characteristics. This electrolyte melts at 436{degrees}C and shows very low polarization because of the absence of Li+ gradients common with the LiCl-KCl eutectic. The low-melting electrolytes examined included a KBr-LiBr-LiCl eutectic (melting at 321{degrees}C), a LiBr-KBr-LiF eutectic (melting at 313{degrees}C), and a CsBr-LiBr-KBr eutectic (melting at 238{degrees}C). The CsBr-based salt had poor conductivity and was not studied further. The LiBr-KBr-LiF eutectic outperformed the KBr-LiBr-LiCl eutectic and was selected for more extensive testing. Because of their lower melting points and larger liquidi relative to the LiCl-KCl eutectic, the low-melting electrolytes are prime candidates for long-life applications (i.e., for activated lives of one hour or more). This paper will detail the relative performance of the Li(Si)/FeS{sub 2} couple using primarily the LiCl-KCl (standard) eutectic, the LiCl-LiBr-LiF (all-Li) eutectic, and the LiBr-KBr-LiF (low-melting) eutectic electrolytes. Most of the tests were conducted with 5-cell batteries; validation tests were also carried out with appropriate full-sized batteries.

  8. Electrolyte effects in Li(Si)/FeS2 thermal batteries

    NASA Astrophysics Data System (ADS)

    Guidotti, Ronald A.; Reinhardt, Frederick W.

    The most common electrochemical couple for thermally activated ('thermal') batteries is the Li-alloy/FeS2 system. The most common Li-alloys used for anodes are 20% Li-80% Al and 44% Li-56% Si (by weight); liquid Li immobilized with iron powder has also been used. The standard electrolyte that has been used in thermal batteries over the years is the LiCl-KCl eutectic that melts at 352 C. The LiCl-LiBr-LiF eutectic had the best rate and power characteristics. This electrolyte melts at 436(degrees)C and shows very low polarization because of the absence of Li(+) gradients common with the LiCl-KCl eutectic. The low-melting electrolytes examined included a KBr-LiBr-LiCl eutectic (melting at 321 C), a LiBr-KBr-LiF eutectic (melting at 313 C), and a CsBr-LiBr-KBr eutectic (melting at 238 C). The CsBr-based salt had poor conductivity and was not studied further. The LiBr-KBr-LiF eutectic outperformed the KBr-LiBr-LiCl eutectic and was selected for more extensive testing. Because of their lower melting points and larger liquidi relative to the LiCl-KCl eutectic, the low-melting electrolytes are prime candidates for long-life applications (i.e., for activated lives of one hour or more). This paper will detail the relative performance of the Li(Si)/FeS2 couple using primarily the LiCl-KCl (standard) eutectic, the LiCl-LiBr-LiF (all-Li) eutectic, and the LiBr-KBr-LiF (low-melting) eutectic electrolytes. Most of the tests were conducted with 5-cell batteries; validation tests were also carried out with appropriate full-sized batteries.

  9. Simulated electrolyte-metal interfaces -- Li3PO4 and Li

    NASA Astrophysics Data System (ADS)

    Xu, Xiao; Du, Yaojun A.; Holzwarth, N. A. W.

    2007-03-01

    There has recently been a lot of interest in solid electrolyte materials such as LiPON developed at Oak Ridge National Laboratory for use in Li-ion batteries and other technologies. We report on the results of our model calculations on idealized interfaces between Li3PO4 and Li metal, studying the structural stability and the ion mobility, using first-principles density functional techniques with the PWscf and pwpaw codes. Starting with a supercell constructed from Li3PO4 in its crystalline γ-phase structure and several layers of Li metal, we used optimization and molecular dynamics techniques to find several meta-stable configurations. The qualitative features of the results are consistent with experimental evidence that the electrolyte is quite stable with respect to Li metal. In addition to stability analyses, we plan to study Li-ion diffusion across the interface. J. B. Bates, N. J. Dudney, and co-workers, Solid State Ionics, 53-56, 647-654 (1992). http://www.pwscf.org and http://pwpaw.wfu.edu. N. J. Dudney in Gholam-Abbas Nazri and Gianfranco Pistoia, Eds., Lithium Batteries: Science and Technology, Chapt. 20, pp. 623-642, Kluwer Academic Publishers, 2004. ISBN 1-4020-7628-2.

  10. Effect of a pyrrolidinium zwitterion on charge/discharge cycle properties of Li/LiCoO2 and graphite/Li cells containing an ionic liquid electrolyte

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Seitaro; Yoshizawa-Fujita, Masahiro; Takeoka, Yuko; Rikukawa, Masahiro

    2016-11-01

    Ionic liquids (ILs) containing zwitterions have been studied as electrolytes for lithium-ion batteries (LIBs). The effects of addition of a pyrrolidinium zwitterion in an IL electrolyte on the thermal and electrochemical stability and charge/discharge properties of Li/LiCoO2 and graphite/Li cells were investigated. The thermal decomposition temperature of the IL electrolyte composed of N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)amide ([P13][FSA])/lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) with 3-(1-butylpyrrolidinium)propane-1-sulfonate (Bpyps) as the zwitterionic additive, the thermal decomposition temperature was about 300 °C. The electrochemical window of [P13][FSA]/LiTFSA/Bpyps was 0-+5.4 V vs. Li/Li+, which was almost identical to that of [P13][FSA]/LiTFSA. Li|electrolyte|LiCoO2 cells containing the IL/Bpyps electrolyte system exhibited high capacities in the cut-off voltage range of 3.0-4.6 V, even after 50 cycles. The increase in the interfacial resistance between the electrolyte and cathode with cycling was suppressed. In the cyclic voltammograms of cells employing a graphite electrode, the intercalation/deintercalation of lithium ions were observed in the range of 0 and + 0.4 V vs. Li/Li+. Further, graphite|electrolyte|Li cells containing [P13][FSA]/LiTFSA/Bpyps exhibited stable charge/discharge cycle behaviour over 50 cycles.

  11. Optimized Carbonate and Ester-Based Li-Ion Electrolytes

    NASA Technical Reports Server (NTRS)

    Smart, Marshall; Bugga, Ratnakumar

    2008-01-01

    To maintain high conductivity in low temperatures, electrolyte co-solvents have been designed to have a high dielectric constant, low viscosity, adequate coordination behavior, and appropriate liquid ranges and salt solubilities. Electrolytes that contain ester-based co-solvents in large proportion (greater than 50 percent) and ethylene carbonate (EC) in small proportion (less than 20 percent) improve low-temperature performance in MCMB carbon-LiNiCoO2 lithium-ion cells. These co-solvents have been demonstrated to enhance performance, especially at temperatures down to 70 C. Low-viscosity, ester-based co-solvents were incorporated into multi-component electrolytes of the following composition: 1.0 M LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + X (1:1:8 volume percent) [where X = methyl butyrate (MB), ethyl butyrate EB, methyl propionate (MP), or ethyl valerate (EV)]. These electrolyte formulations result in improved low-temperature performance of lithium-ion cells, with dramatic results at temperatures below 40 C.

  12. Plasma electrochemistry: potential measured at boron doped diamond and platinum in gaseous electrolyte.

    PubMed

    Hadzifejzovic, E; Sanchez Galiani, J A; Caruana, D J

    2006-06-28

    Premixed hydrogen/oxygen flame doped with ionisable alkali metals was considered as a dilute electrolyte. Two identical premixed flames which were in physical contact, served as a two compartment flame electrolyte cell. Five different electrochemical cells were studied, each containing a different combination of three alkali metals, Li, K and Cs. Pairs of boron doped diamond (BDD) and platinum electrodes were used to measure the overall zero current cell potential. The total potential measured across the cell was shown to be the sum of the mixed potential, dependent on the identity of ionised species present in the flame, and the diffusion potential originating at the junction between the two flames. Classical kinetic molecular theory and electrochemical theory of mixed potentials have been applied to account for the potential difference measured across these gas phase electrochemical cells. The relative merits of both models are discussed in the context of the experimental results obtained.

  13. Superconductivity in Li-doped {alpha}-rhombohedral boron

    SciTech Connect

    Nagatochi, T.; Sumiyoshi, A.; Kimura, K.; Hyodo, H.; Soga, K.; Sato, Y.; Terauchi, M.; Esaka, F.

    2011-05-01

    Metal transition and superconductivity were observed in Li-doped {alpha}-rhombohedral boron ({alpha}-B{sub 12}). The authors have established a purification method and obtained a large amount of high-purity {alpha}-B{sub 12} powder. Li doping into purified {alpha}-B{sub 12} was attempted by vapor diffusion processing (VDP) in a Mo or Ta tube. Li-doped {alpha}-B{sub 12} contained metallic glittering particles. Meissner effects were observed in such a compound with the nominal composition Li{sub x}B{sub 12} (x = 1.0, 1.4, 1.5, 1.7, or 2.5) (T{sub c} = 3.2-7 K). As for Li{sub 2.5}B{sub 12}, the temperature dependence of its electrical conductivity indicates a metallic character and its electrical resistivity drop is detected near the Meissner temperature. The existence of Li and Fermi edges in Li-doped {alpha}-B{sub 12} crystals was verified by transmission electron microscopy-electron energy loss spectroscopy (TEM-EELS). Lattice expansion, which is a well-known indicator of metal doping into a crystal, was also observed. Thus, Li doping into {alpha}-B{sub 12} was successfully achieved. Our work also suggests that it is possible to dope a larger amount of Li into {alpha}-B{sub 12} and to increase its T{sub c}.

  14. Effects of electrolyte salts on the performance of Li-O2 batteries

    SciTech Connect

    Nasybulin, Eduard N.; Xu, Wu; Engelhard, Mark H.; Nie, Zimin; Burton, Sarah D.; Cosimbescu, Lelia; Gross, Mark E.; Zhang, Jiguang

    2013-02-05

    It is well known that the stability of nonaqueous electrolyte is critical for the rechargeable Li-O2 batteries. Although stability of many solvents used in the electrolytes has been investigated, considerably less attention has been paid to the stability of electrolyte salt which is the second major component. Herein, we report the systematic investigation of the stability of seven common lithium salts in tetraglyme used as electrolytes for Li-O2 batteries. The discharge products of Li-O2 reaction were analyzed by X-ray diffraction, X-ray photoelectron spectroscopy and nuclear magnetic resonance spectroscopy. The performance of Li-O2 batteries was strongly affected by the salt used in the electrolyte. Lithium tetrafluoroborate (LiBF4) and lithium bis(oxalato)borate (LiBOB) decompose and form LiF and lithium borates, respectively during the discharge of Li-O2 batteries. Several other salts, including lithium bis(trifluoromethane)sulfonamide (LiTFSI), lithium trifluoromethanesulfonate (LiTf), lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4) , and lithium bromide (LiBr) led to the discharge products which mainly consisted of Li2O2 and only minor signs of decomposition of LiTFSI, LiTf, LPF6 and LiClO4 were detected. LiBr showed the best stability during the discharge process. As for the cycling performance, LiTf and LiTFSI were the best among the studied salts. In addition to the instability of lithium salts, decomposition of tetraglyme solvent was a more significant factor contributing to the limited cycling stability. Thus a more stable nonaqueous electrolyte including organic solvent and lithium salt still need to be further developed to reach a fully reversible Li-O2 battery.

  15. Method for treating electrolyte to remove Li{sub 2}O

    DOEpatents

    Tomczuk, Z.; Miller, W.E.; Johnson, G.K.; Willit, J.L.

    1998-01-20

    A method is described for removing Li{sub 2}O present in an electrolyte predominantly of LiCl and KCl. The electrolyte is heated to a temperature not less than about 500 C and then Al is introduced into the electrolyte in an amount in excess of the stoichiometric amount needed to convert the Li{sub 2}O to a Li-Al alloy and lithium aluminate salt. The salt and aluminum are maintained in contact with agitation for a time sufficient to convert the Li{sub 2}O.

  16. Method for treating electrolyte to remove Li.sub.2 O

    DOEpatents

    Tomczuk, Zygmunt; Miller, William E.; Johnson, Gerald K.; Willit, James L.

    1998-01-01

    A method of removing Li.sub.2 O present in an electrolyte predominantly of LiCl and KCl. The electrolyte is heated to a temperature not less than about 500.degree. C. and then Al is introduced into the electrolyte in an amount in excess of the stoichiometric amount needed to convert the Li.sub.2 O to a Li-Al alloy and lithium aluminate salt. The salt and aluminum are maintained in contact with agitation for a time sufficient to convert the Li.sub.2 O.

  17. First Principles Prediction of Nitrogen-doped Carbon Nanotubes as a High-Performance Cathode for Li-S Batteries

    SciTech Connect

    Wang, Zhiguo; Niu, Xinyue; Xiao, Jie; Wang, Chong M.; Liu, Jun; Gao, Fei

    2013-07-16

    The insulating nature of sulfur and the solubility of the polysulfide in organic electrolyte are two main factors that limit the application of lithium sulfur (Li-S) battery systems. Enhancement of Li conductivity, identification of a strong adsorption agent of polysulfides and the improvement of the whole sulfur-based electrode are of great technological importance. The diffusion of Li atoms on the outer-wall, inner-wall and inter-wall spaces in nitrogen-doped double-walled carbon nanotubes (CNTs) and penetrations of Li and S atoms through the walls are studied using density functional theory. We find that N-doping does not alternate the diffusion behaviors of Li atoms throughout the CNTs, but the energy barrier for Li atoms to penetrate the wall is greatly decreased by N-doping (from ~9.0 eV to ~ 1.0 eV). On the other hand, the energy barrier for S atoms to penetrate the wall remains very high, which is caused by the formation of the chemical bonds between the S and nearby N atoms. The results indicate that Li atoms are able to diffuse freely, whereas S atoms can be encapsulated inside the N-doped CNTs, suggesting that the N-doped CNTs can be potentially used in high performance Li-S batteries.

  18. Improved electrolytes for Li-ion batteries: Mixtures of ionic liquid and organic electrolyte with enhanced safety and electrochemical performance

    NASA Astrophysics Data System (ADS)

    Guerfi, A.; Dontigny, M.; Charest, P.; Petitclerc, M.; Lagacé, M.; Vijh, A.; Zaghib, K.

    Physical and electrochemical characteristics of Li-ion battery systems based on LiFePO 4 cathodes and graphite anodes with mixture electrolytes were investigated. The mixed electrolytes are based on an ionic liquid (IL), and organic solvents used in commercial batteries. We investigated a range of compositions to determine an optimum conductivity and non-flammability of the mixed electrolyte. This led us to examine mixtures of ILs with the organic electrolyte usually employed in commercial Li-ion batteries, i.e., ethylene carbonate (EC) and diethylene carbonate (DEC). The IL electrolyte consisted of (trifluoromethyl sulfonylimide) (TFSI) as anion and 1-ethyl-3-methyleimidazolium (EMI) as the cation. The physical and electrochemical properties of some of these mixtures showed an improvement characteristics compared to the constituents alone. The safety was improved with electrolyte mixtures; when IL content in the mixture is ≥40%, no flammability is observed. A stable SEI layer was obtained on the MCMB graphite anode in these mixed electrolytes, which is not obtained with IL containing the TFSI-anion. The high-rate capability of LiFePO 4 is similar in the organic electrolyte and the mixture with a composition of 1:1. The interface resistance of the LiFePO 4 cathode is stabilized when the IL is added to the electrolyte. A reversible capacity of 155 mAh g -1 at C/12 is obtained with cells having at least some organic electrolyte compared to only 124 mAh g -1 with pure IL. With increasing discharge rate, the capacity is maintained close to that in the organic solvent up to 2 C rate. At higher rates, the results with mixture electrolytes start to deviate from the pure organic electrolyte cell. The evaluation of the Li-ion cells; LiFePO 4//Li 4Ti 5O 12 with organic and, 40% mixture electrolytes showed good 1st CE at 98.7 and 93.0%, respectively. The power performance of both cell configurations is comparable up to 2 C rate. This study indicates that safety and

  19. Li Ion Conducting Polymer Gel Electrolytes Based on Ionic Liquid/PVDF-HFP Blends

    PubMed Central

    Ye, Hui; Huang, Jian; Xu, Jun John; Khalfan, Amish; Greenbaum, Steve G.

    2009-01-01

    Ionic liquids thermodynamically compatible with Li metal are very promising for applications to rechargeable lithium batteries. 1-methyl-3-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P13TFSI) is screened out as a particularly promising ionic liquid in this study. Dimensionally stable, elastic, flexible, nonvolatile polymer gel electrolytes (PGEs) with high electrochemical stabilities, high ionic conductivities and other desirable properties have been synthesized by dissolving Li imide salt (LiTFSI) in P13TFSI ionic liquid and then mixing the electrolyte solution with poly(vinylidene-co-hexafluoropropylene) (PVDF-HFP) copolymer. Adding small amounts of ethylene carbonate to the polymer gel electrolytes dramatically improves the ionic conductivity, net Li ion transport concentration, and Li ion transport kinetics of these electrolytes. They are thus favorable and offer good prospects in the application to rechargeable Li batteries including open systems like Li/air batteries, as well as more “conventional” rechargeable lithium and lithium ion batteries. PMID:20354587

  20. Defect complexes in Li-doped MgO

    NASA Astrophysics Data System (ADS)

    Richter, N. A.; Stavale, F.; Levchenko, S. V.; Nilius, N.; Freund, H.-J.; Scheffler, M.

    2015-05-01

    Magnesium oxide (MgO) is used in a variety of industrial applications due to its low cost and structural stability. In heterogeneous catalysis, MgO and Li-doped MgO have been studied as catalysts for the oxidative coupling of methane. In this work, we analyze the structure and stability of defect complexes comprising Li dopants and oxygen vacancies in MgO, combining scanning tunneling microscopy, photon-emission experiments, and density-functional theory computations. The experimental results strongly indicate that after annealing Li-doped MgO to temperatures of 600 K and higher, Li evaporates from the surface, but Li defects, such as substitutional defects, interstitials, or defect complexes comprising Li remain in the bulk. Our calculations show that bulk defect complexes containing F2 + color centers, that have donated their two electrons to two adjacent Li defects, are the most stable configurations at realistic pressure and temperature conditions.

  1. Interfacial stability and electrochemical behavior of Li/LiFePO4 batteries using novel soft and weakly adhesive photo-ionogel electrolytes

    NASA Astrophysics Data System (ADS)

    Aidoud, D.; Etiemble, A.; Guy-Bouyssou, D.; Maire, E.; Le Bideau, J.; Guyomard, D.; Lestriez, B.

    2016-10-01

    We have developed flexible polymer-gel electrolytes based on a polyacrylate cross-linked matrix that confines an ionic liquid doped with a lithium salt. Free-standing solid electrolyte membrane is obtained after UV photo-polymerization of acrylic monomers dissolved inside the ionic liquid/lithium salt mixture. The liquid precursor of the photo-ionogel may also be directly deposited onto porous composite electrode, which results in all-solid state electrode/electrolyte stacking after UV illumination. Minor variations in the polymer component of the electrolyte formulation significantly affect the electrochemical behavior in LiFePO4/lithium and lithium/lithium cells. The rate performance increases with an increase of the ionic conductivity, which decreases with the polymer content and decreases with increasing oxygen content in the polyacrylate matrix. Their fairly low modulus endow them weak and beneficial pressure-sensitive-adhesive character. X-Rays Tomography shows that the solid-state photo-ionogel electrolytes keep their integrity upon cycling and that their surface remains smooth. The coulombic efficiency of LiFePO4/lithium cells increases with an increase of the adhesive strength of the photo-ionogel, suggesting a relationship between the contact intimacy at the lithium/photo-ionogel interface and the efficiency of the lithium striping/plating. In lithium/lithium cells, only the photo-ionogels with the higher adhesion strength are able to allow the reversible striping/plating of lithium.

  2. Electrochemical properties of dual phase neodymium-doped ceria alkali carbonate composite electrolytes in intermediate temperature

    NASA Astrophysics Data System (ADS)

    Kim, Ji-Tae; Lee, Tae-Hee; Park, Ka-Young; Seo, Yongho; Kim, Ki Buem; Song, Sun-Ju; Park, Byoungnam; Park, Jun-Young

    2015-02-01

    Composite electrolyte materials composed of neodymium-doped ceria (Nd0.2Ce0.8O1.9; NDC) and (Li-0.5Na)2CO3 are investigated to understand the unique behaviors of their multi-ionic conduction. In the intermediate temperature, the NDC-based carbonate composite electrolytes exhibit a much higher conductivity compared to pure NDC. It has been claimed that the oxide ions are transported in the doped-ceria phase via oxygen vacancies and the protons are conducted through the second carbonate phase, thereby resulting in an enhanced ionic conductivity. However, it has not been experimentally demonstrated if the proton conduction within the carbonate phase aided in improving the conductivity of oxygen ions in the composite system. Hence, the primary objective of this work is to cultivate a deeper insight into the conduction property of these composites as an attempt to clarify the ionic transport phenomenon responsible for enhanced conductivity. Electrical conductivities of NDC and NDC/carbonate materials are investigated as a function of oxygen partial pressure and vapor pressure of water to understand transport properties of composite electrolytes. The ionic and electronic transference numbers of composite electrolytes are measured by the oxygen- and hydrogen-concentration cells containing water. The dominant charge carriers are identified quantitatively through the analysis of the partial conductivity of proton, oxygen ions, and electrons (holes). Understanding the transport properties and transference numbers of composite electrolytes can contribute to the development of commercial solid oxide fuel cells, which can be done by reducing the operating temperature using a highly ionic conductive NDC/carbonate composite electrolyte at the intermediate temperature.

  3. Novel Stable Gel Polymer Electrolyte: Toward a High Safety and Long Life Li-Air Battery.

    PubMed

    Yi, Jin; Liu, Xizheng; Guo, Shaohua; Zhu, Kai; Xue, Hailong; Zhou, Haoshen

    2015-10-28

    Nonaqueous Li-air battery, as a promising electrochemical energy storage device, has attracted substantial interest, while the safety issues derived from the intrinsic instability of organic liquid electrolytes may become a possible bottleneck for the future application of Li-air battery. Herein, through elaborate design, a novel stable composite gel polymer electrolyte is first proposed and explored for Li-air battery. By use of the composite gel polymer electrolyte, the Li-air polymer batteries composed of a lithium foil anode and Super P cathode are assembled and operated in ambient air and their cycling performance is evaluated. The batteries exhibit enhanced cycling stability and safety, where 100 cycles are achieved in ambient air at room temperature. The feasibility study demonstrates that the gel polymer electrolyte-based polymer Li-air battery is highly advantageous and could be used as a useful alternative strategy for the development of Li-air battery upon further application.

  4. Novel Stable Gel Polymer Electrolyte: Toward a High Safety and Long Life Li-Air Battery.

    PubMed

    Yi, Jin; Liu, Xizheng; Guo, Shaohua; Zhu, Kai; Xue, Hailong; Zhou, Haoshen

    2015-10-28

    Nonaqueous Li-air battery, as a promising electrochemical energy storage device, has attracted substantial interest, while the safety issues derived from the intrinsic instability of organic liquid electrolytes may become a possible bottleneck for the future application of Li-air battery. Herein, through elaborate design, a novel stable composite gel polymer electrolyte is first proposed and explored for Li-air battery. By use of the composite gel polymer electrolyte, the Li-air polymer batteries composed of a lithium foil anode and Super P cathode are assembled and operated in ambient air and their cycling performance is evaluated. The batteries exhibit enhanced cycling stability and safety, where 100 cycles are achieved in ambient air at room temperature. The feasibility study demonstrates that the gel polymer electrolyte-based polymer Li-air battery is highly advantageous and could be used as a useful alternative strategy for the development of Li-air battery upon further application. PMID:26452054

  5. Enhanced performance of Li|LiFePO4 cells using CsPF6 as an electrolyte additive

    NASA Astrophysics Data System (ADS)

    Xiao, Liang; Chen, Xilin; Cao, Ruiguo; Qian, Jiangfeng; Xiang, Hongfa; Zheng, Jianming; Zhang, Ji-Guang; Xu, Wu

    2015-10-01

    The practical application of lithium (Li) metal anode in rechargeable Li batteries is hindered by both the growth of Li dendrites and the low Coulombic efficiency (CE) during repeated charge/discharge cycles. Recently, we have discovered that CsPF6 as an electrolyte additive can significantly suppress Li dendrite growth and lead to highly compacted and well aligned Li nanorod structures during Li deposition on copper substrates. In this paper, the effect of CsPF6 additive on the performance of rechargeable Li metal batteries with lithium iron phosphate (LFP) cathode is further studied. Li|LFP coin cells with CsPF6 additive in electrolytes show well protected Li anode surface, decreased resistance, enhanced rate capability and extended cycling stability. In Li|LFP cells, the electrolyte with CsPF6 additive shows excellent long-term cycling stability (at least 500 cycles) at a charge current density of 0.5 mA cm-2 without internal short circuit. At high charge current densities, the effect of CsPF6 additive becomes less significant. Future work needs to be done to protect Li metal anode, especially at high charge current densities and for long cycle life.

  6. Enhanced Performance of Li|LiFePO4 Cells Using CsPF6 as an Electrolyte Additive

    SciTech Connect

    Xiao, Liang; Chen, Xilin; Cao, Ruiguo; Qian, Jiangfeng; Xiang, Hongfa; Zheng, Jianming; Zhang, Jiguang; Xu, Wu

    2015-10-20

    The practical application of lithium (Li) metal anode in rechargeable Li batteries is hindered by both the growth of Li dendrites and the low Coulombic efficiency (CE) during repeated charge/discharge cycles. Recently, we have discovered that CsPF6 as an electrolyte additive can significantly suppress Li dendrite growth and lead to highly compacted and well aligned Li nanorod structure during Li deposition on copper substrates. In this paper, the effect of CsPF6 additive on the performance of rechargeable Li metal batteries with lithium iron phosphate (LFP) cathode was further studied. Li|LFP coin cells with CsPF6 additive in electrolytes show well protected Li anode surface, decreased resistance, enhanced rate capability and extended cycling stability. In Li|LFP cells, the electrolyte with CsPF6 additive shows excellent long-term cycling stability (at least 500 cycles) at a charge current density of 0.5 mA cm-2 without internal short circuit. At high charge current densities, the effect of CsPF6 additive becomes less significant. Future work needs to be done to protect Li metal anode, especially at high charge current densities and for long cycle life.

  7. Direct observation of Li diffusion in Li-doped ZnO nanowires

    NASA Astrophysics Data System (ADS)

    Li, Guohua; Yu, Lei; Hudak, Bethany M.; Chang, Yao-Jen; Baek, Hyeonjun; Sundararajan, Abhishek; Strachan, Douglas R.; Yi, Gyu-Chul; Guiton, Beth S.

    2016-05-01

    The direct observation of Li diffusion in Li-doped zinc oxide nanowires (NWs) was realized by using in situ heating in the scanning transmission electron microscope (STEM). A continuous increase of low atomic mass regions within a single NW was observed between 200 °C and 600 °C when heated in vacuum, which was explained by the conversion of interstitial to substitutional Li in the ZnO NW host lattice. A kick-out mechanism is introduced to explain the migration and conversion of the interstitial Li (Lii) to Zn-site substitutional Li (LiZn), and this mechanism is verified with low-temperature (11 K) photoluminescence measurements on as-grown and annealed Li-doped zinc oxide NWs, as well as the observation of an increase of NW surface roughing with applied bias.

  8. Performance of new 10 kW class MCFC using Li/K and Li/Na electrolyte

    SciTech Connect

    Mugikura, Yoshihiro; Yoshiba, Fumihiko; Izaki, Yoshiyuki; Watanabe, Takao

    1996-12-31

    The molten carbonate fuel cell (MCFC) uses generally mixture of lithium carbonate and potassium carbonate (Li/K) as the electrolyte. NiO cathode dissolution is one of serious problems for MCFC life. The NiO cathode has been found to dissolve into the electrolyte as Ni{sup 2+} ion which is reduced to metallic Ni by H{sub 2} in the fuel gas and bridges the anode and the cathode. The bridges short circuit and degrade cell performance and shorten cell life. Since solubility of NiO in mixture of lithium carbonate and sodium carbonate (Li/Na) is lower than in Li/K, it takes longer time to take place slowing by NiO cathode dissolution in Li/Na compared with in Li/K. The ionic conductivity of Li/Na is higher than of Li/K, however, oxygen solubility in Li/Na is lower 9 than in Li/K. A new 10 kW class MCFC stack composed of Li/K cells and Li/Na cells, was tested. Basic performance of the Li/K cells and Li/Na cells of the stack was reported.

  9. Electronic properties of Li-doped zigzag graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Narin, P.; Kutlu, E.; Sarikavak-Lisesivdin, B.; Lisesivdin, S. B.; Özbay, E.

    2016-10-01

    Zigzag graphene nanoribbons (ZGNRs) are known to exhibit metallic behavior. Depending on structural properties such as edge status, doping and width of nanoribbons, the electronic properties of these structures may vary. In this study, changes in electronic properties of crystal by doping Lithium (Li) atom to ZGNR structure are analyzed. In spin polarized calculations are made using Density Functional Theory (DFT) with generalized gradient approximation (GGA) as exchange correlation. As a result of calculations, it has been determined that Li atom affects electronic properties of ZGNR structure significantly. It is observed that ZGNR structure exhibiting metallic behavior in pure state shows half-metal and semiconductor behavior with Li atom.

  10. Enabling linear alkyl carbonate electrolytes for high voltage Li-ion cells

    NASA Astrophysics Data System (ADS)

    Xia, Jian; Petibon, Remi; Xiong, Deijun; Ma, Lin; Dahn, J. R.

    2016-10-01

    Some of the problems of current electrolytes for high voltage Li-ion cells originate from ethylene carbonate (EC) which is thought to be an essential electrolyte component for Li-ion cells. Ethylene carbonate-free electrolytes containing 1 M LiPF6 in ethylmethyl carbonate (EMC) with small loadings of vinylene carbonate, fluoroethylene carbonate, or (4R,5S)-4,5-Difluoro-1,3-dioxolan-2-one acting as "enablers" were developed. These electrolytes used in Li(Ni0.4Mn0.4Co0.2)O2/graphite pouch type Li-ion cells tested at 4.2 V and 4.5 V yielded excellent charge-discharge cycling and storage properties. The results for cells containing linear alkyl carbonate electrolytes with no EC were compared to those of cells with EC-containing electrolytes incorporating additives proven to enhance cyclability of cells. The combination of EMC with appropriate amounts of these enablers yields cells with better performance than cells with EC-containing electrolytes incorporating additives tested to 4.5 V. Further optimizing these linear alkyl carbonate electrolytes with appropriate co-additives may represent a viable path to the successful commercial utilization of NMC/graphite Li-ion cells operated to 4.5 V and above.

  11. An experimental study for Li recycling in an electrolytic reduction process for UO2 with a Li2O-LiCl molten salt

    NASA Astrophysics Data System (ADS)

    Park, Wooshin; Hur, Jin-Mok; Hong, Sun-Seok; Choi, Eun-Young; Im, Hun Suk; Oh, Seung-Chul; Lee, Jae-Won

    2013-10-01

    If Li is excessively produced in an electrolytic reduction process for UO2 with a Li2O-LiCl molten salt, a part of Li2O will be lost in the form of Li as deposited on the cathode, and the Li can cause negative effects on a post process. To solve these problems, a method for Li recycling was investigated in this study. A series of experiments were carried out consisting of four runs. In the first run, UO2 fragments were electrochemically reduced at 3.2 V of cell voltage. The excess Li was then recovered by transferring to another electrode at 0.3 V of cell voltage. The recovered Li was then utilized as the source for the reduction of fresh UO2 fragments. Finally, the remaining UO2 was electrochemically reduced at 3.2 V of cell voltage. The concentration of Li2O was reasonably maintained as a result of the Li recycling without a significant loss. Consequently, the potential problems by Li could be disregarded using the recycling method. The electrolytic reduction process for UO2 will be more efficient and sustainable by combining the technology for Li recycling and the conventional electrolytic reduction process.

  12. The use of Electrolyte Additives to Improve the High Temperature Resilience of Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Lucht, B. L.; Ratnakumar, Bugga V.

    2007-01-01

    This viewgraph presentation reviews the use of electrolyte additves to improve the resillience of Lithium ion cells. The objective of this work is to identify lithium-ion electrolytes, which will lead to Li-ion cells with a wide operational temperature range (+60 to -60 C), and to develop Li-ion electrolytes which result in cells that display improved high temperature resilience. Significant improvement in the high temperature resilience of Li-ion cells containing these additives was observed, with the most dramatic benefit being displayed by addition of DMAc. When the electrochemical properties of the individual electrodes were analyzed, the degradation of the anode kinetics was slowed most dramatically by the incorporation of DMAc into the electrolytes. Whereas, the greatest retention in the cathode kinetics was observed in the cell containing the electrolyte with VC added.

  13. Studies on the thermal behavior of CS:LiTFSI:[Amim] Cl polymer electrolytes exerted by different [Amim] Cl content

    NASA Astrophysics Data System (ADS)

    Ramesh, S.; Shanti, R.; Morris, Ezra

    2012-01-01

    The principle motivation of this research work is to develop environmental-friendly polymer electrolytes utilizing corn starch (CS), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1-allyl-3-methylimidazolium chloride ([Amim] Cl) by solution casting technique. The highest ionic conductivity value was achieved for the composition CS:LiTFSI:[Amim] Cl (14 wt. %:6 wt. %:80 wt. %) which exhibits the ionic conductivity value of 5.68 × 10 -2 S cm -1 at 40 °C with the activation energy of 4.86 kJ mol -1. This sample possess high concentration of amorphous phase coupled with greater presence of conducting cations (lithium, Li + and imidazolium, [Amim] +) as depicted by the dielectric loss tangent plot. The conductivity-temperature plots were found to obey Arrhenius rule in which the conductivity mechanism is thermally assisted. The melting temperature of polymer electrolyte decreases with increase in [Amim] Cl content. This is attributed to the good miscibility of [Amim] Cl in CS:LiTFSI matrix inducing structural disorderliness. Reference to the TGA results it is found that the addition of [Amim] Cl diminishes the heat-resistivity whereas enhancement in the thermal stability occurred at the initial addition and declines with further doping of [Amim] Cl.

  14. Thermal reactions of mesocarbon microbead (MCMB) particles in LiPF 6-based electrolyte

    NASA Astrophysics Data System (ADS)

    Xiao, Ang; Li, Wentao; Lucht, Brett L.

    The thermal reaction of ternary electrolyte (1.0 M LiPF 6 in 1:1:1 ethylene carbonate/dimethyl carbonate/diethyl carbonate) with mesocarbon microbeads (MCMB) particles was investigated by the combined use of NMR, GC-MS, FTIR-ATR, TGA, XPS and SEM/EDS-element map. The thermal decomposition of ternary electrolyte is not inhibited by the presence of MCMB particles. The chemical composition and morphology of the surface of MCMB particles changes significantly upon storage in the presence of ternary electrolyte. Electrolyte decomposition products including oligocarbonates, oligoethylene oxides, polyethylene oxide (PEO), lithium fluorophosphates (Li xPO yF z), and lithium fluoride are deposited on the surface of MCMB particles. The concentration of decomposition products on the surface of MCMB increases with increased storage time and temperature. The addition of dimethyl acetamide (DMAc) impedes the thermal decomposition of the electrolyte and deposition of electrolyte decomposition products on the surface of MCMB.

  15. Pushing the Theoretical Limit of Li-CFx Batteries: A Tale of Bi-functional Electrolyte

    SciTech Connect

    Rangasamy, Ezhiylmurugan; Li, Juchuan; Sahu, Gayatri; Dudney, Nancy J; Liang, Chengdu

    2014-01-01

    In a typical battery, electrodes deliver capacities less or equal the theoretical maxima of the electrode materials.1 The inert electrolyte functions solely as the ionic conductor without contribution to the cell capacity because of its distinct mono-function in the concept of conventional batteries. Here we demonstrate that the most energy-dense Li-CFx battery2 delivers a capacity exceeding the theoretical maximum of CFx with a solid electrolyte of Li3PS4 (LPS) that has dual functions: as the inert electrolyte at the anode and the active component at the cathode. Such a bi-functional electrolyte reconciles both inert and active characteristics through a synergistic discharge mechanism of CFx and LPS. Li3PS4 is known as an inactive solid electrolyte with a broad electrochemical window over 5 V.3 The synergy at the cathode is through LiF, the discharge product of CFx, which activates the electrochemical discharge of LPS at a close electrochemical potential of CFx. Therefore, the solid-state Li-CFx batteries output 126.6% energy beyond their theoretic limits without compromising the stability of the cell voltage. The extra energy comes from the electrochemical discharge of LPS, the inert electrolyte. This bi-functional electrolyte revolutionizes the concept of conventional batteries and opens a new avenue for the design of batteries with an unprecedentedly high energy density.

  16. Characterization of low-melting electrolytes for potential geothermal borehole power supplies: The LiBr-KBr-LiF eutectic

    SciTech Connect

    Guidotti, R.A.; Reinhardt, F.W.

    1998-05-01

    The suitability of modified thermal-battery technology for use as a potential power source for geothermal borehole applications is under investigation. As a first step, the discharge processes that take place in LiSi/LiBr-KBr-LiF/FeS{sub 2} thermal cells were studied at temperatures of 350 C and 400 C using pelletized cells with immobilized electrolyte. Incorporation of a reference electrode allowed the relative contribution of each electrode to the overall cell polarization to be determined. The results of single-cell tests are presented, along with preliminary data for cells based on a lower-melting CsBr-LiBr-KBr eutectic salt.

  17. Stability of the solid electrolyte Li{sub 3}OBr to common battery solvents

    SciTech Connect

    Schroeder, D.J.; Hubaud, A.A.; Vaughey, J.T.

    2014-01-01

    Graphical abstract: The stability of the anti-perovskite phase Li{sub 3}OBr has been assessed in a variety of battery solvents. - Highlights: • Lithium stable solid electrolyte Li{sub 3}OBr unstable to polar organic solvents. • Solvation with no dissolution destroys long-range structure. • Ion exchange with protons observed. - Abstract: Recently a new class of solid lithium ion conductors was reported based on the anti-perovskite structure, notably Li{sub 3}OCl and Li{sub 3}OBr. For many beyond lithium-ion battery uses, the solid electrolyte is envisioned to be in direct contact with liquid electrolytes and lithium metal. In this study we evaluated the stability of the Li{sub 3}OBr phase against common battery solvents electrolytes, including diethylcarbonate (DEC) and dimethylcarbonate (DMC), as well as a LiPF{sub 6} containing commercial electrolyte. In contact with battery-grade organic solvents, Li{sub 3}OBr was typically found to be insoluble but lost its crystallinity and reacted with available protons and in some cases with the solvent. A low temperature heat treatment was able to restore crystallinity of the samples; however evidence of proton ion exchange was conserved.

  18. Preparation of Li3BO3-Li2SO4 glass-ceramic electrolytes for all-oxide lithium batteries

    NASA Astrophysics Data System (ADS)

    Tatsumisago, Masahiro; Takano, Ryohei; Tadanaga, Kiyoharu; Hayashi, Akitoshi

    2014-12-01

    Newly designed oxide glass-ceramic electrolyte of Li2.9B0.9S0.1O3.1 with high Li+ ion conductivity and low melting property was prepared by mechanical milling and subsequent heat treatment at 290 °C. This material showed 1.4 × 10-5 S cm-1 at room temperature and excellent deformation properties to obtain powder-compressed pellets with low interfacial resistance like in the case of sulfide solid electrolytes. The glass-ceramic exhibited favorable mechanical properties to form favorable solid-solid contacts in solid-state batteries by pressing without high temperature heat treatments. All-solid-state In/LiCoO2 cells using these oxide glass-ceramic electrolytes operated as secondary batteries at room temperature.

  19. Structure and Stoichiometry in Supervalent Doped Li7La3 Zr2O12

    DOE PAGESBeta

    Mukhopadhyay, Saikat; Thompson, Travis; Sakamoto, Jeff; Huq, Ashfia; Wolfenstine, Jeff; Allen, Jan L.; Bernstein, Noam; Stewart, Derek A.; Johannes, M. D.

    2015-04-20

    The oxide garnet material Li7La3 Zr2O12 shows remarkably high ionic conductivity when doped with supervalent ions that are charge compensated by Li vacancies and is currently one of the best candidates for development of a technologically relevant solid electrolyte. Determination of optimal dopant concentration, however, has remained a persistent problem due to the extreme difficulty of establishing the actual (as compared to nominal) stoichiometry of intentionally doped materials and by the fact that it is still not entirely clear what level of lattice expansion/contraction best promotes. ionic diffusion. By combining careful synthesis, neutron diffraction, high-resolution X-ray diffraction (XRD), Raman measurements,more » and density functional theory calculations, we show that structure and stoichiometry are intimately related such that the former can in many cases be used as a gauge of the latter. We show that different Li-vacancy creating supervalent ions (Al3+ vs Ta5+) affect the structure very differently, both in terms of the lattice constant, which is easily measurable, and hi terms of the local structure, which can be difficult or impossible to access experimentally but may have important ramifications for conduction. We carefully correlate the lattice constant to dopant type/concentration via Vegard's law and then further correlate these quantities to relevant local structural parameters. In conclusion, our work opens the possibility of developing a codopant scheme that optimizes the Li vacancy concentration and the lattice size simultaneously.« less

  20. Reversibility of electrochemical reactions of sulfur supported on inverse opal carbon in glyme-Li salt molten complex electrolytes.

    PubMed

    Tachikawa, Naoki; Yamauchi, Kento; Takashima, Eriko; Park, Jun-Woo; Dokko, Kaoru; Watanabe, Masayoshi

    2011-07-28

    Electrochemical reactions of sulfur supported on three-dimensionally ordered macroporous carbon in glyme-Li salt molten complex electrolytes exhibit good reversibility and large capacity based on the mass of sulfur, which suggests that glyme-Li salt molten complexes are suitable electrolytes for Li-S batteries.

  1. Oxygen-driven transition from two-dimensional to three-dimensional transport behaviour in β-Li3PS4 electrolyte.

    PubMed

    Wang, Xuelong; Xiao, Ruijuan; Li, Hong; Chen, Liquan

    2016-08-01

    Solid state electrolytes with high Li ion conduction are vital to the development of all-solid-state lithium batteries. Lithium thiophosphate Li3PS4 is the parent material of a series of Li superionic conductors Li10MX2S12 (M = Ge, Sn,…; X = P, Si,…), and β-Li3PS4 shows relatively high ionic conductivity itself, though it is not room-temperature stable. The positive effects of introducing O dopants into β-Li3PS4 to stabilize the crystal phase and improve the ionic conducting behaviour are revealed in this study. With the aid of first-principles density functional theory (DFT) computations and quasi-empirical bond-valence calculations, the effects of O doping at different concentrations on the properties of β-Li3PS4 is thoroughly investigated from the aspects of lattice structures, electronic structures, ionic transport properties, the interface stability against Li and the thermodynamic stability. An oxygen-driven transition from two-dimensional to three-dimensional transport behaviour is found and the oxygen dopants play the role as a connector of 2D paths. Based on all these simulation results, hopefully our research can provide a new strategy for the modification of lithium thiophosphate solid electrolytes. PMID:27432279

  2. Oxygen-driven transition from two-dimensional to three-dimensional transport behaviour in β-Li3PS4 electrolyte.

    PubMed

    Wang, Xuelong; Xiao, Ruijuan; Li, Hong; Chen, Liquan

    2016-08-01

    Solid state electrolytes with high Li ion conduction are vital to the development of all-solid-state lithium batteries. Lithium thiophosphate Li3PS4 is the parent material of a series of Li superionic conductors Li10MX2S12 (M = Ge, Sn,…; X = P, Si,…), and β-Li3PS4 shows relatively high ionic conductivity itself, though it is not room-temperature stable. The positive effects of introducing O dopants into β-Li3PS4 to stabilize the crystal phase and improve the ionic conducting behaviour are revealed in this study. With the aid of first-principles density functional theory (DFT) computations and quasi-empirical bond-valence calculations, the effects of O doping at different concentrations on the properties of β-Li3PS4 is thoroughly investigated from the aspects of lattice structures, electronic structures, ionic transport properties, the interface stability against Li and the thermodynamic stability. An oxygen-driven transition from two-dimensional to three-dimensional transport behaviour is found and the oxygen dopants play the role as a connector of 2D paths. Based on all these simulation results, hopefully our research can provide a new strategy for the modification of lithium thiophosphate solid electrolytes.

  3. Current-induced composition gradients in molten LiCl-KCl battery electrolytes

    SciTech Connect

    Braustein, J.; Cantor, S.; Vallet, C.E.

    1981-01-01

    Current induced composition gradients were demonstrated in molten LiCl-KCl eutectic mixture, the electrolyte of a LiAl/LiCl-KCl/FeS/sub x/ battery. Analysis of composition profiles in quenched samples was by atomic absorption spectroscopy (AA), which gave good precision, and by x-ray fluorescence spectroscopy in a scanning electron microscope (SEM/EDX), which gave good distance resolution. 5 refs.

  4. Improved Li/TiS2 cell cycling in ether-based electrolytes with synergistic additives

    NASA Technical Reports Server (NTRS)

    Dominey, L. A.; Goldman, J. L.; Koch, V. R.; Shen, D.; Subbarao, S.; Huang, C.-K.; Halpert, G.; Deligiannis, F.

    1991-01-01

    Based on an extensive series of normalized full cell Li/TiS2 cycling studies, open-circuit storage tests, microcalorimetry and AC impedance studies, and chemical precedent, we propose an integrated chemical model consistent with experimental observations concerning the behavior of numerous LiAsF6/cyclic ether electrolytes. The particularly striking potency of certain additives such as 2-methylfuran and the hydroxide action resides in their ability to intercept several different adverse catalytic processes concurrently in the bulk electrolyte as well as the Li anode and TiS2 cathode.

  5. Alkyl Pyrocarbonate Electrolyte Additives for Performance Enhancement of Li Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Surampudi, S.

    2000-01-01

    Lithium ion rechargeable batteries are being developed for various aerospace applications under a NASA-DoD Interagency program. These applications require further improvements in several areas, specifically in the cycle life for LEO and GEO satellites and in the low temperature performance for the Mars Lander and Rover missions. Accordingly, we have been pursuing research studies to achieve improvement in the low temperature performance, long cycle life and active life of Li ion cells. The studies are mainly focused on electrolytes, to identify newer formulations of new electrolyte additives to enhance Li permeability (at low temperatures) and stability towards the electrode. The latter approach is particularly aimed at the formation suitable SEI (solid electrolyte interphase) on carbon electrodes. In this paper, we report the beneficial effect of using alkyl pyrocarbonates as electrolyte additives to improve the low temperature performance of Li ion cells.

  6. Diphenyloctyl phosphate as a flame-retardant additive in electrolyte for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Shim, Eun-Gi; Nam, Tae-Heum; Kim, Jung-Gu; Kim, Hyun-Soo; Moon, Seong-In

    The use of diphenyloctyl phosphate (DPOF) as a flame-retardant additive in liquid electrolyte for Li-ion batteries is investigated. Mesocarbon microbeads (MCMB) and LiCoO 2 are used as the anode and cathode materials, respectively. Cyclic voltammetry (CV), differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) are used for the analyses. The cell with DPOF shows better electrochemical cell performance than that without DPOF in initial charge/discharge and rate performance tests. In cycling tests, a cell with DPOF-containing electrolyte exhibited better discharge capacity and capacity retention than that of the DPOF-free electrolyte after cycling. These results confirm the viability of using DPOF as a flame-retardant additive for improving the cell performance and thermal stability of electrolytes for Li-ion batteries.

  7. A flexible Li polymer primary cell with a novel gel electrolyte based on poly(acrylonitrile)

    NASA Astrophysics Data System (ADS)

    Akashi, Hiroyuki; Tanaka, Ko-ichi; Sekai, Koji

    The performance of a Li polymer primary cell with fire-retardant poly(acrylonitrile) (PAN)-based gel electrolytes is reported. By optimizing electrodes, electrolytes, the packaging material, and the structural design of the polymer cell, we succeeded in developing a "film-like" Li polymer primary cell with sufficient performance for practical use. The cell is flexible and less than 0.5 mm thick, which makes it suitable for a power source for some smart devices, such as an IC card. Fast cation conduction in the gel electrolyte minimizes the drop of the discharge capacity even at -20 °C. The high chemical stability of the gel electrolytes and the new packaging material allow the self-discharge rate to be limited to under 4.3%, which is equivalent to that of conventional coin-shaped or cylindrical Li-MnO 2 cells.

  8. Enhanced ionic conductivity with Li7O2Br3 phase in Li3OBr anti-perovskite solid electrolyte

    NASA Astrophysics Data System (ADS)

    Zhu, Jinlong; Li, Shuai; Zhang, Yi; Howard, John W.; Lü, Xujie; Li, Yutao; Wang, Yonggang; Kumar, Ravhi S.; Wang, Liping; Zhao, Yusheng

    2016-09-01

    Cubic anti-perovskites with general formula Li3OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li3OBr and layered Li7O2Br3, by solid state reaction routes. The results indicate that with the phase fraction of Li7O2Br3 increasing to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li3OBr. Formation energy calculations revealed the meta-stable nature of Li7O2Br3, which supports the great difficulty in producing phase-pure Li7O2Br3 at ambient pressure. Methods of obtaining phase-pure Li7O2Br3 will continue to be explored, including both high pressure and metathesis techniques.

  9. Wide Operating Temperature Range Electrolytes for High Voltage and High Specific Energy Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Hwang, C.; Krause, F. C.; Soler, J.; West, W. C.; Ratnakumar, B. V.; Amine, K.

    2012-01-01

    A number of electrolyte formulations that have been designed to operate over a wide temperature range have been investigated in conjunction with layered-layered metal oxide cathode materials developed at Argonne. In this study, we have evaluated a number of electrolytes in Li-ion cells consisting of Conoco Phillips A12 graphite anodes and Toda HE5050 Li(1.2)Ni(0.15)Co(0.10)Mn(0.55)O2 cathodes. The electrolytes studied consisted of LiPF6 in carbonate-based electrolytes that contain ester co-solvents with various solid electrolyte interphase (SEI) promoting additives, many of which have been demonstrated to perform well in 4V systems. More specifically, we have investigated the performance of a number of methyl butyrate (MB) containing electrolytes (i.e., LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + MB (20:20:60 v/v %) that contain various additives, including vinylene carbonate, lithium oxalate, and lithium bis(oxalato)borate (LiBOB). When these systems were evaluated at various rates at low temperatures, the methyl butyrate-based electrolytes resulted in improved rate capability compared to cells with all carbonate-based formulations. It was also ascertained that the slow cathode kinetics govern the generally poor rate capability at low temperature in contrast to traditionally used LiNi(0.80)Co(0.15)Al(0.05)O2-based systems, rather than being influenced strongly by the electrolyte type.

  10. Role of the solid electrolyte interphase on a Li metal anode in a dimethylsulfoxide-based electrolyte for a lithium-oxygen battery

    NASA Astrophysics Data System (ADS)

    Togasaki, Norihiro; Momma, Toshiyuki; Osaka, Tetsuya

    2015-10-01

    The effect of the solid electrolyte interphase (SEI) on a Li anode on the charge-discharge cycling performance in 1 M LiTFSI/dimethylsulfoxide electrolyte solution is examined by using charge-discharge cycling. The chemical structure of the surface and interior of the SEI strongly affects the cycling performance of the anode. The observed coulombic efficiency is low (<45%) when organic compounds such as lithium alkyl carbonates and polycarbonate form predominantly on the surface and interior. However, when inorganic compounds such as Li2CO3, Li2O, and LiF form instead, the coulombic efficiency increases to >85%. This enhanced efficiency remains constant regardless of the O2 content and despite <1000 ppm concentration of the contaminant H2O in the electrolyte. Thus, the lithium surface should be protected by inorganic compounds prior to cycling to prevent it from undergoing side reactions with the electrolyte during cycling in the electrolyte.

  11. Lithium Ion Pathway within Li7 La3 Zr2 O12 -Polyethylene Oxide Composite Electrolytes.

    PubMed

    Zheng, Jin; Tang, Mingxue; Hu, Yan-Yan

    2016-09-26

    Polymer-ceramic composite electrolytes are emerging as a promising solution to deliver high ionic conductivity, optimal mechanical properties, and good safety for developing high-performance all-solid-state rechargeable batteries. Composite electrolytes have been prepared with cubic-phase Li7 La3 Zr2 O12 (LLZO) garnet and polyethylene oxide (PEO) and employed in symmetric lithium battery cells. By combining selective isotope labeling and high-resolution solid-state Li NMR, we are able to track Li ion pathways within LLZO-PEO composite electrolytes by monitoring the replacement of (7) Li in the composite electrolyte by (6) Li from the (6) Li metal electrodes during battery cycling. We have provided the first experimental evidence to show that Li ions favor the pathway through the LLZO ceramic phase instead of the PEO-LLZO interface or PEO. This approach can be widely applied to study ion pathways in ionic conductors and to provide useful insights for developing composite materials for energy storage and harvesting. PMID:27611222

  12. Lithium Ion Pathway within Li7 La3 Zr2 O12 -Polyethylene Oxide Composite Electrolytes.

    PubMed

    Zheng, Jin; Tang, Mingxue; Hu, Yan-Yan

    2016-09-26

    Polymer-ceramic composite electrolytes are emerging as a promising solution to deliver high ionic conductivity, optimal mechanical properties, and good safety for developing high-performance all-solid-state rechargeable batteries. Composite electrolytes have been prepared with cubic-phase Li7 La3 Zr2 O12 (LLZO) garnet and polyethylene oxide (PEO) and employed in symmetric lithium battery cells. By combining selective isotope labeling and high-resolution solid-state Li NMR, we are able to track Li ion pathways within LLZO-PEO composite electrolytes by monitoring the replacement of (7) Li in the composite electrolyte by (6) Li from the (6) Li metal electrodes during battery cycling. We have provided the first experimental evidence to show that Li ions favor the pathway through the LLZO ceramic phase instead of the PEO-LLZO interface or PEO. This approach can be widely applied to study ion pathways in ionic conductors and to provide useful insights for developing composite materials for energy storage and harvesting.

  13. Synthesis and characterisation of copper doped Ca-Li hydroxyapatite

    NASA Astrophysics Data System (ADS)

    Pogosova, M. A.; Kazin, P. E.; Tretyakov, Y. D.

    2012-08-01

    Hydroxyapapites M10(PO4)6(OH)2 (MHAP), where M is an alkaline earth metal, colored by incorporation of copper ions substituting protons, were discovered recently [1]. Now this kind of apatite-type materials can be used as inorganic pigments. Until now blue (BaHAP), violet (SrHAP) and wine-red (CaHAP) colors were achieved by the copper ions introduction [2]. The task of the present work was to study possibility of further M-ion substitution to affect the color and shift it toward the red-orange tint. Polycrystalline hydroxyapatites Ca10-xLix+yCuz(PO4)6O2H2-y-z-σ (Ca-LiHAP) were synthesized by solid state reaction at 1150 °C (ceramic method) and studied by X-ray powder diffraction (XRD), infrared absorption and diffuse-reflectance spectroscopy. Refinement of the X-ray diffraction patterns by the Rietveld method shows that CaHAP unit cell parameters are a little bigger, than Ca-LiHAP ones. Small difference between unit cell parameters could be caused by two ways of the Li+ ions introduction: (1) at the Ca2+ sites (Ca-Li substitution); (2) into hexagonal channels (H-Li substitution). The Li ions doping changes the color of the copper doped CaHAP from wine-red to pink and red.

  14. Dendrite-Free Li Deposition Using Trace-Amounts of Water as an Electrolyte Additive

    SciTech Connect

    Qian, Jiangfeng; Xu, Wu; Bhattacharya, Priyanka; Engelhard, Mark H.; Henderson, Wesley A.; Zhang, Yaohui; Zhang, Jiguang

    2015-07-01

    Residual water presents in nonaqueous electrolytes has been widely regarded as a detrimental factor for lithium (Li) batteries. This is because water is highly reactive with the commonly used LiPF6 salt and leads to the formation of HF that corrodes battery materials. In this work, we demonstrate that a controlled trace-amount of water (25-100 ppm) can be an effective electrolyte additive for achieving dendrite-free Li metal deposition in LiPF6-based electrolytes and avoid its detrimental effect at the same time. Detailed analyses reveal that the trace amount of HF formed by the decomposition reaction of LiPF6 with water will be electrochemically reduced during initial Li deposition process to form a uniform and dense LiF-rich SEI layer on the surface of the substrate. This LiF-rich SEI layer leads to a uniform distribution of the electric field on the substrate surface and enables uniform and dendrite-free Li deposition. Meanwhile the detrimental effect of HF is diminished due to the consumption of HF in the LiF formation process. Microscopic analysis reveals that the as-deposited dendrite-free Li films exhibit a self-aligned and highly-compacted Li nanorods structure which is consistent with their charming blue color or known as structure color. These findings clearly demonstrate a novel approach to control the nucleation and grow process of Li metal films using well-controlled trace-amount of water. They also shine the light on the effect of water on other electrodeposition processes.

  15. Mixed-Salt/Ester Electrolytes for Low-Temperature Li+ Cells

    NASA Technical Reports Server (NTRS)

    Smart, Marshall; Bugga, Ratnakumar

    2006-01-01

    Electrolytes comprising, variously, LiPF6 or LiPF6 plus LiBF4 dissolved at various concentrations in mixtures of alkyl carbonates and alkyl esters have been found to afford improved low-temperature performance in rechargeable lithium-ion electrochemical cells. These and other electrolytes have been investigated in a continuing effort to extend the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles, the most recent being Ester-Based Electrolytes for Low-Temperature Li-Ion Cells (NPO-41097), NASA Tech Briefs, Vol. 29, No. 12 (December 2005), page 59. The ingredients of the solvent mixtures include ethylene carbonate (EC), ethyl methyl carbonate (EMC), methyl butyrate (MB), and methyl propionate (MP). The electrolytes were placed in Li-ion cells containing carbon anodes and LiNi0.8Co0.2O2 cathodes, and the electrical performances of the cells were measured over a range of temperatures down to 60 C. The electrolytes that yielded the best low-temperature performances were found to consist, variously, of 1.0 M LiPF6 + 0.4 M LiBF4 or 1.4 LiPF6 in 1EC + 1EMC + 8MP or 1EC + 1EMC + 8MB, where the concentrations of the salts are given in molar units and the proportions of the solvents are by relative volume.

  16. First-Principles Characterization of the Unknown Crystal Structure and Ionic Conductivity of Li7P2S8I as a Solid Electrolyte for High-Voltage Li Ion Batteries.

    PubMed

    Kang, Joonhee; Han, Byungchan

    2016-07-21

    Using first-principles density functional theory calculations and ab initio molecular dynamics (AIMD) simulations, we demonstrate the crystal structure of the Li7P2S8I (LPSI) and Li ionic conductivity at room temperature with its atomic-level mechanism. By successively applying three rigorous conceptual approaches, we identify that the LPSI has a similar symmetry class as Li10GeP2S12 (LGPS) material and estimate the Li ionic conductivity to be 0.3 mS cm(-1) with an activation energy of 0.20 eV, similar to the experimental value of 0.63 mS cm(-1). Iodine ions provide an additional path for Li ion diffusion, but a strong Li-I attractive interaction degrades the Li ionic transport. Calculated density of states (DOS) for LPSI indicate that electrochemical instability can be substantially improved by incorporating iodine at the Li metallic anode via forming a LiI compound. Our methods propose the computational design concept for a sulfide-based solid electrolyte with heteroatom doping for high-voltage Li ion batteries.

  17. First-Principles Characterization of the Unknown Crystal Structure and Ionic Conductivity of Li7P2S8I as a Solid Electrolyte for High-Voltage Li Ion Batteries.

    PubMed

    Kang, Joonhee; Han, Byungchan

    2016-07-21

    Using first-principles density functional theory calculations and ab initio molecular dynamics (AIMD) simulations, we demonstrate the crystal structure of the Li7P2S8I (LPSI) and Li ionic conductivity at room temperature with its atomic-level mechanism. By successively applying three rigorous conceptual approaches, we identify that the LPSI has a similar symmetry class as Li10GeP2S12 (LGPS) material and estimate the Li ionic conductivity to be 0.3 mS cm(-1) with an activation energy of 0.20 eV, similar to the experimental value of 0.63 mS cm(-1). Iodine ions provide an additional path for Li ion diffusion, but a strong Li-I attractive interaction degrades the Li ionic transport. Calculated density of states (DOS) for LPSI indicate that electrochemical instability can be substantially improved by incorporating iodine at the Li metallic anode via forming a LiI compound. Our methods propose the computational design concept for a sulfide-based solid electrolyte with heteroatom doping for high-voltage Li ion batteries. PMID:27345207

  18. Studies on the enhancement of solid electrolyte interphase formation on graphitized anodes in LiX-carbonate based electrolytes using Lewis acid additives for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Li, L. F.; Xie, B.; Lee, H. S.; Li, H.; Yang, X. Q.; McBreen, J.; Huang, X. J.

    The new electrolyte systems utilizing one type of Lewis acids, the boron based anion receptors (BBARs) with LiF, Li 2O, or Li 2O 2 in carbonate solutions have been developed and reported by us. These systems open up a new approach in developing non-aqueous electrolytes with higher operating voltage and less moisture sensitivity for lithium-ion batteries. However, the formation of a stable solid electrolyte interphase (SEI) layer on the graphitized anodes is a serious problem needs to be solved for these new electrolyte systems, especially when propylene carbonate (PC) is used as a co-solvent. Using lithium bis(oxalato)borate (LiBOB) as an additives, the SEI layer formation on mesophase carbon microbeads (MCMB) anode is significantly enhanced in these new electrolytes containing boron-based anion receptors, such as tris(pentafluorophenyl) borane, and lithium salt such as LiF, or lithium oxides such as Li 2O or Li 2O 2 in PC and dimethyl carbonate (DMC) solvents. The cells using these electrolytes and MCMB anodes cycled very well and the PC co-intercalation was suppressed. Fourier transform infrared spectroscopy (FTIR) studies show that one of the electrochemical decomposition products of LiBOB, lithium carbonate (Li 2CO 3), plays a quite important role in the stablizing SEI layer formation.

  19. Reaction Mechanisms for the Limited Reversibility of Li-O2 Chemistry in Organic Carbonate Electrolytes

    SciTech Connect

    Xu, Wu; Xu, Kang; Viswanathan, Vilayanur V.; Towne, Silas A.; Hardy, John S.; Xiao, Jie; Nie, Zimin; Hu, Dehong; Wang, Deyu; Zhang, Jiguang

    2011-11-15

    The Li-O2 chemistry in nonaqueous carbonate electrolytes and the underneath reason of its limited reversibility was exhaustively investigated. The discharge products collected from the air cathode in a Li-O2 battery at different depth of discharge (DOD) were systematically analyzed with X-ray diffraction. It is revealed that, independent of the discharge depth, lithium alkylcarbonate (either lithium propylenedicarbonate - LPDC, or lithium ethylenedicarbonate - LEDC, with other related derivatives) and lithium carbonate (Li2CO3) are always the main products, obviously originated from the electrolyte solvents propylene carbonate (PC) and ethylene carbonate (EC). These lithium alkylcarbonates are obviously generated from the single-electron reductive decomposition of the corresponding carbonate solvents initiated by the attack of superoxide radical anions. On the other hand, neither lithium peroxide (Li2O2) nor lithium oxide (Li2O) is detected. More significantly, from in situ gas chromatography/mass spectroscopy it is found that Li2CO3 and Li2O cannot be oxidized even when charged up to 4.6 V vs. Li/Li+, while LPDC, LEDC and Li2O2 are readily able to, with CO2 and CO released with the re-oxidation of LPDC and LEDC. It is therefore concluded that the quasi-reversibility of Li-O2 chemistry observed hitherto in an organic carbonate-based electrolyte is actually reliant on the formation of lithium alkylcarbonates through the reductive decomposition of carbonate solvents during discharge process and the subsequent oxidation of these same alkylcarbonates during charge process. It is the poor oxidizability of these alkylcarbonate species that constitutes the obstruction to an ideal rechargeable Li-O2 battery.

  20. Interaction of High Flash Point Electrolytes and PE-Based Separators for Li-Ion Batteries.

    PubMed

    Hofmann, Andreas; Kaufmann, Christoph; Müller, Marcus; Hanemann, Thomas

    2015-01-01

    In this study, promising electrolytes for use in Li-ion batteries are studied in terms of interacting and wetting polyethylene (PE) and particle-coated PE separators. The electrolytes are characterized according to their physicochemical properties, where the flow characteristics and the surface tension are of particular interest for electrolyte-separator interactions. The viscosity of the electrolytes is determined to be in a range of η = 4-400 mPa∙s and surface tension is finely graduated in a range of γL = 23.3-38.1 mN∙m(-1). It is verified that the technique of drop shape analysis can only be used in a limited matter to prove the interaction, uptake and penetration of electrolytes by separators. Cell testing of Li|NMC half cells reveals that those cell results cannot be inevitably deduced from physicochemical electrolyte properties as well as contact angle analysis. On the other hand, techniques are more suitable which detect liquid penetration into the interior of the separator. It is expected that the results can help fundamental researchers as well as users of novel electrolytes in current-day Li-ion battery technologies for developing and using novel material combinations. PMID:26343636

  1. Interaction of High Flash Point Electrolytes and PE-Based Separators for Li-Ion Batteries.

    PubMed

    Hofmann, Andreas; Kaufmann, Christoph; Müller, Marcus; Hanemann, Thomas

    2015-08-27

    In this study, promising electrolytes for use in Li-ion batteries are studied in terms of interacting and wetting polyethylene (PE) and particle-coated PE separators. The electrolytes are characterized according to their physicochemical properties, where the flow characteristics and the surface tension are of particular interest for electrolyte-separator interactions. The viscosity of the electrolytes is determined to be in a range of η = 4-400 mPa∙s and surface tension is finely graduated in a range of γL = 23.3-38.1 mN∙m(-1). It is verified that the technique of drop shape analysis can only be used in a limited matter to prove the interaction, uptake and penetration of electrolytes by separators. Cell testing of Li|NMC half cells reveals that those cell results cannot be inevitably deduced from physicochemical electrolyte properties as well as contact angle analysis. On the other hand, techniques are more suitable which detect liquid penetration into the interior of the separator. It is expected that the results can help fundamental researchers as well as users of novel electrolytes in current-day Li-ion battery technologies for developing and using novel material combinations.

  2. Impact of electrolyte solvent and additive choices on high voltage Li-ion pouch cells

    NASA Astrophysics Data System (ADS)

    Xia, Jian; Nelson, K. J.; Lu, Zhonghua; Dahn, J. R.

    2016-10-01

    The effects that various electrolyte solvents and electrolyte additives had on both LaPO4-coated LiNi0.4Mn0.4Co0.2O2 and uncoated LiNi0.4Mn0.4Co0.2O2/graphite pouch cells were studied using automated storage, electrochemical impedance spectroscopy, gas production and long-term cycling experiments. Storage experiments showed that the voltage drop during storage at 4.3 or 4.4 V for both coated and uncoated cells was very similar for the same electrolyte choice. At 4.5 V or above, the LaPO4-coated cells had a significantly smaller voltage drop than the uncoated cells except when fluorinated electrolytes were used. Automated charge discharge cycling/impedance spectroscopy testing of cells held at 4.5 V for 24 h every cycle showed that all cells containing ethylene carbonate:ethyl methyl carbonate electrolyte or sulfolane:ethyl methyl carbonate electrolyte exhibited severe capacity fade. By contrast, cells containing fluorinated electrolytes had the best capacity retention and smallest impedance growth during these aggressive cycling/hold tests. Long-term cycling experiments to 4.5 V confirmed that cells containing fluorinated electrolyte had the best cycling performance in the uncoated LiNi0.4Mn0.4Co0.2O2/graphite cells while cells containing sulfolane:ethyl methyl carbonate electrolyte had the best cycling performance in coated LiNi0.4Mn0.4Co0.2O2/graphite cells.

  3. Low-EC-Content Electrolytes for Low-Temperature Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, Marshall; Bugga, Ratnakumar; Surampudi, Subbarao

    2003-01-01

    Electrolytes comprising LiPF6 dissolved at a concentration of 1.0 M in three different mixtures of alkyl carbonates have been found well suited for use in rechargeable lithium-ion electrochemical cells at low temperatures. These and other electrolytes have been investigated in continuing research directed toward extending the lower limit of practical operating temperatures of Li-ion cells down to -60 C. This research at earlier stages was reported in numerous previous NASA Tech Briefs articles, the three most recent being "Ethyl Methyl Carbonate as a Cosolvent for Lithium-Ion Cells" (NPO-20605), Vol. 25, Low-EC-Content Electrolytes for Low-Temperature Li-Ion Cells No. 6 (June 2001), page 53; "Alkyl Pyrocarbonate Electrolyte Additives for Li-Ion Cells" (NPO-20775), Vol. 26, No. 5 (May 2002), page 37; and "Fluorinated Alkyl Carbonates as Cosolvents in Li-Ion Cells (NPO-21076), Vol. 26, No. 5 (May 2002), page 38. The present solvent mixtures, in terms of volume proportions of their ingredients, are 1 ethylene carbonate (EC) + 1 diethyl carbonate (DEC) + 1 dimethyl carbonate (DMC) + 3 ethyl methyl carbonate (EMC); 3EC + 3DMC + 14EMC; and 1EC + 1DEC + 1DMC + 4EMC. Relative to similar mixtures reported previously, the present mixtures, which contain smaller proportions of EC, have been found to afford better performance in experimental Li-ion cells at temperatures < -20 C.

  4. Improved Li-TiS2 cell cycling in ether-based electrolytes with synergistic additives

    NASA Technical Reports Server (NTRS)

    Shen, D. H.; Subbarao, S.; Deligiannis, F.; Huang, C.-K.; Halpert, G.; Dominey, L.; Koch, V. R.; Goldman, J.

    1991-01-01

    Results of the application of 2-MeF and KOH additives to improve the lithium stability in THF, dioxolane, and THF/2-MeTHF solvent-based electrolytes are presented. The stability of these electrolytes with and without additives is evaluated by microcalorimetry and AC impedance spectroscopy. A novel method, cathode turnover number, is proposed to represent the electrolyte performance in a given system. The lithium cycling efficiency and cathode turnover number of the electrolytes are calculated from the cycle life data in experimental Li-TiS2 cells. Overall, THF/2-MeTHF electrolyte containing 2-MeF and/or KOH exhibited higher stability, lithium cycling efficiency, and cathode turnover number compared to THF and dioxolane electrolytes with and without additives.

  5. Improved Li-TiS2 cell cycling in ether-based electrolytes with synergistic additives

    NASA Astrophysics Data System (ADS)

    Shen, D. H.; Subbarao, S.; Deligiannis, F.; Huang, C.-K.; Halpert, G.; Dominey, L.; Koch, V. R.; Goldman, J.

    Results of the application of 2-MeF and KOH additives to improve the lithium stability in THF, dioxolane, and THF/2-MeTHF solvent-based electrolytes are presented. The stability of these electrolytes with and without additives is evaluated by microcalorimetry and AC impedance spectroscopy. A novel method, cathode turnover number, is proposed to represent the electrolyte performance in a given system. The lithium cycling efficiency and cathode turnover number of the electrolytes are calculated from the cycle life data in experimental Li-TiS2 cells. Overall, THF/2-MeTHF electrolyte containing 2-MeF and/or KOH exhibited higher stability, lithium cycling efficiency, and cathode turnover number compared to THF and dioxolane electrolytes with and without additives.

  6. On the chemical stability of post-lithiated garnet Al-stabilized Li7La3Zr2O12 solid state electrolyte thin films

    NASA Astrophysics Data System (ADS)

    Rawlence, Michael; Garbayo, Inigo; Buecheler, Stephan; Rupp, J. L. M.

    2016-08-01

    Garnet-based Al-doped Li7La3Zr2O12 has the potential to be used as a solid state electrolyte for future lithium microbattery architectures, due to its relatively high Li+ conductivity and stability against Li. Through this work, a model experiment is presented in which the effect of post-lithiation on phase formation and chemical stability is studied for pulsed laser deposited Al-doped Li7La3Zr2O12 thin films on MgO substrates. We report the implications of the newly suggested post-lithiation route for films with thicknesses between 90 and 380 nm. The phase changes from cubic, to a mix of cubic and tetragonal Li7La3Zr2O12, to a cubic Li7La3Zr2O12 and La2Zr2O7 containing film is accompanied by a reduction in the degree of de-wetting as the thickness increases. This study reveals that the thicker, dense, and continuous films remain predominantly in a mixed phase containing cubic Li7La3Zr2O12 and the lithium free La2Zr2O7 phase whereas the thinner, de-wetted films exhibit improved lithium incorporation resulting in the absence of the lithium free phase. For tuning the electrical conductivity and effective use of these structures in future batteries, understanding this material system is of great importance as the chemical stability of the cubic Li7La3Zr2O12 phase in the thin film system will control its effective use. We report a conductivity of 1.2 × 10-3 S cm-1 at 325 °C for a 380 nm thick solid state electrolyte film on MgO for potential operation in future all solid state battery assemblies.Garnet-based Al-doped Li7La3Zr2O12 has the potential to be used as a solid state electrolyte for future lithium microbattery architectures, due to its relatively high Li+ conductivity and stability against Li. Through this work, a model experiment is presented in which the effect of post-lithiation on phase formation and chemical stability is studied for pulsed laser deposited Al-doped Li7La3Zr2O12 thin films on MgO substrates. We report the implications of the newly

  7. Electrochemical performance of nanostructured spinel LiMn 2O 4 in different aqueous electrolytes

    NASA Astrophysics Data System (ADS)

    Tian, Lei; Yuan, Anbao

    A nanostructured spinel LiMn 2O 4 electrode material was prepared via a room-temperature solid-state grinding reaction route starting with hydrated lithium acetate (LiAc·2H 2O), manganese acetate (MnAc 2·4H 2O) and citric acid (C 6H 8O 7·H 2O) raw materials, followed by calcination of the precursor at 500 °C. The material was characterized by X-ray diffraction (XRD) and transmission electron microscope techniques. The electrochemical performance of the LiMn 2O 4 electrodes in 2 M Li 2SO 4, 1 M LiNO 3, 5 M LiNO 3 and 9 M LiNO 3 aqueous electrolytes was studied using cyclic voltammetry, ac impedance and galvanostatic charge/discharge methods. The LiMn 2O 4 electrode in 5 M LiNO 3 electrolyte exhibited good electrochemical performance in terms of specific capacity, rate dischargeability and charge/discharge cyclability, as evidenced by the charge/discharge results.

  8. Patternable gel electrolyte infiltrated into all-solid porous Li-ion electrodes

    NASA Astrophysics Data System (ADS)

    Sun, Ke; Dillon, Shen J.

    2014-06-01

    Gel electrolyte based on 1M LiPF6 in ethylene carbonate:dimethyl carbonate, polyethyleneglycol diacrylate oligomer, and 2,2'-azobis(2-methylpropionitrile) is infiltrated into porous sintered LiCoO2 electrodes and cured in situ. The associated batteries function well, which is consistent with microscopy observations indicating that the gel electrolyte penetrates the electrode well and wets to the electrode particles. Trimethyl silyl acrylate is used to functionalize glass substrates and will cross link with polyethyleneglycol diacrylate during curing to promote bonding between the substrate and the gel electrolyte. The functionalization can localize adhesion allowing the electrolyte to easily release from unfunctionalized glass, which can be used as a mold.

  9. High-performance gel electrolytes with tetra-armed polymer network for Li ion batteries

    NASA Astrophysics Data System (ADS)

    Hazama, Taisuke; Fujii, Kenta; Sakai, Takamasa; Aoki, Masahiro; Mimura, Hideyuki; Eguchi, Hisao; Todorov, Yanko; Yoshimoto, Nobuko; Morita, Masayuki

    2015-07-01

    An organo gel with only 6 wt % tetra-armed poly(ethylene glycol), TetraPEG, was prepared and applied as a novel gel electrolyte for Li ion batteries (LIBs). The TetraPEG gel electrolyte containing 1.0 M LiPF6 in binary or ternary mixtures, i.e., EC + DEC and EC + DEC + TFEP (EC: ethylene carbonate, DEC: diethyl carbonate and TFEP: tris(2,2,2-trifluoroethyl)phosphate showed high ionic conductivity required for the use in LIB systems. The TetraPEG gel based on ternary EC + DEC + TFEP system acts as a nonflammable gel electrolyte at the TFEP content higher than 20 vol%. In cyclic voltammetry and charge/discharge cycling tests, the TetraPEG gel electrolytes showed good reversibility for a graphite negative electrode.

  10. Reinvestigation on the state-of-the-art nonaqueous carbonate electrolytes for 5 V Li-ion battery applications

    SciTech Connect

    Xu, Wu; Chen, Xilin; Ding, Fei; Xiao, Jie; Wang, Deyu; Pan, Anqiang; Zheng, Jianming; Li, Xiaohong S.; Padmaperuma, Asanga B.; Zhang, Jiguang

    2012-09-01

    The charging voltage limits of mixed carbonate solvents for Li-ion batteries have been systematically investigated from 4.9 to 5.3 V in half cells using Cr-doped spinel cathode material LiNi0.45Cr0.05Mn1.5O4. We found that the stability of conventional carbonate electrolytes is strongly related to the stability and properties of the cathode materials at both lithiated and de-lithiated states. It is the first time to report that the conventional electrolytes based on mixtures of ethylene carbonate (EC) and linear carbonate (dimethyl carbonate - DMC, ethyl methyl carbonate - EMC, and diethyl carbonate - DEC) have shown very similar long-term cycling performance when cycled up to 5.2 V on LiNi0.45Cr0.05Mn1.5O4. The discharge capacity increases with the charge cutoff voltage and reaches the highest discharge capacity at 5.2 V. The capacity retention is about 87% after 500 cycles at 1C rate for all three carbonate mixtures when cycled between 3.0 V and 5.2V. The first-cycle efficiency has a maximum value at 5.1 V, with an average from 83% to 85% at C/10 rate. When cycled to 5.3 V, EC-DMC still shows good cycling performance but EC-EMC and EC-DEC show faster capacity fading. EC-DMC and EC-EMC have much better rate capability than EC-DEC. In addition, the first-cycle irreversible capacity loss increases with the cutoff voltage and the 'inactive' conductive carbon has also been found to be partly associated with the low first-cycle Coulombic efficiency at high voltages due to electrolyte decomposition and probably the PF6- anion irreversible intercalation.

  11. On the chemical stability of post-lithiated garnet Al-stabilized Li7La3Zr2O12 solid state electrolyte thin films.

    PubMed

    Rawlence, Michael; Garbayo, Inigo; Buecheler, Stephan; Rupp, J L M

    2016-08-21

    Garnet-based Al-doped Li7La3Zr2O12 has the potential to be used as a solid state electrolyte for future lithium microbattery architectures, due to its relatively high Li(+) conductivity and stability against Li. Through this work, a model experiment is presented in which the effect of post-lithiation on phase formation and chemical stability is studied for pulsed laser deposited Al-doped Li7La3Zr2O12 thin films on MgO substrates. We report the implications of the newly suggested post-lithiation route for films with thicknesses between 90 and 380 nm. The phase changes from cubic, to a mix of cubic and tetragonal Li7La3Zr2O12, to a cubic Li7La3Zr2O12 and La2Zr2O7 containing film is accompanied by a reduction in the degree of de-wetting as the thickness increases. This study reveals that the thicker, dense, and continuous films remain predominantly in a mixed phase containing cubic Li7La3Zr2O12 and the lithium free La2Zr2O7 phase whereas the thinner, de-wetted films exhibit improved lithium incorporation resulting in the absence of the lithium free phase. For tuning the electrical conductivity and effective use of these structures in future batteries, understanding this material system is of great importance as the chemical stability of the cubic Li7La3Zr2O12 phase in the thin film system will control its effective use. We report a conductivity of 1.2 × 10(-3) S cm(-1) at 325 °C for a 380 nm thick solid state electrolyte film on MgO for potential operation in future all solid state battery assemblies. PMID:27455404

  12. Li-Ion Electrolytes with Improved Safety and Tolerance to High-Voltage Systems

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Bugga, Ratnakumar V.; Prakash, Surya; Krause, Frederick C.

    2013-01-01

    Given that lithium-ion (Li-ion) technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. Therefore, extensive effort has been devoted to developing nonflammable electrolytes to reduce the flammability of the cells/battery. A number of promising electrolytes have been developed incorporating flame-retardant additives, and have been shown to have good performance in a number of systems. However, these electrolyte formulations did not perform well when utilizing carbonaceous anodes with the high-voltage materials. Thus, further development was required to improve the compatibility. A number of Li-ion battery electrolyte formulations containing a flame-retardant additive [i.e., triphenyl phosphate (TPP)] were developed and demonstrated in high-voltage systems. These electrolytes include: (1) formulations that incorporate varying concentrations of the flame-retardant additive (from 5 to 15%), (2) the use of mono-fluoroethylene carbonate (FEC) as a co-solvent, and (3) the use of LiBOB as an electrolyte additive intended to improve the compatibility with high-voltage systems. Thus, improved safety has been provided without loss of performance in the high-voltage, high-energy system.

  13. Interaction of High Flash Point Electrolytes and PE-Based Separators for Li-Ion Batteries

    PubMed Central

    Hofmann, Andreas; Kaufmann, Christoph; Müller, Marcus; Hanemann, Thomas

    2015-01-01

    In this study, promising electrolytes for use in Li-ion batteries are studied in terms of interacting and wetting polyethylene (PE) and particle-coated PE separators. The electrolytes are characterized according to their physicochemical properties, where the flow characteristics and the surface tension are of particular interest for electrolyte–separator interactions. The viscosity of the electrolytes is determined to be in a range of η = 4–400 mPa∙s and surface tension is finely graduated in a range of γL = 23.3–38.1 mN∙m−1. It is verified that the technique of drop shape analysis can only be used in a limited matter to prove the interaction, uptake and penetration of electrolytes by separators. Cell testing of Li|NMC half cells reveals that those cell results cannot be inevitably deduced from physicochemical electrolyte properties as well as contact angle analysis. On the other hand, techniques are more suitable which detect liquid penetration into the interior of the separator. It is expected that the results can help fundamental researchers as well as users of novel electrolytes in current-day Li-ion battery technologies for developing and using novel material combinations. PMID:26343636

  14. Mesoscopic Framework Enables Facile Ionic Transport in Solid Electrolytes for Li Batteries

    DOE PAGESBeta

    Ma, Cheng; Cheng, Yongqiang; Chen, Kai; Li, Juchuan; Sumpter, Bobby G.; Nan, Ce-Wen; More, Karren L.; Dudney, Nancy J.; Chi, Miaofang

    2016-03-29

    In Li-ion-conducting solid electrolytes can simultaneously overcome two grand challenges for Li-ion batteries: the severe safety concerns that limit the large-scale application and the poor electrolyte stability that forbids the use of high-voltage cathodes. Nevertheless, the ionic conductivity of solid electrolytes is typically low, compromising the battery performances. Precisely determining the ionic transport mechanism(s) is a prerequisite for the rational design of highly conductive solid electrolytes. For decades, the research on this subject has primarily focused on the atomic and microscopic scales, where the main features of interest are unit cells and microstructures, respectively. We show that the largely overlookedmore » mesoscopic scale lying between these extremes could be the key to fast ionic conduction. In a prototype system, (Li0.33La0.56)TiO3, a mesoscopic framework is revealed for the first time by state-of-the-art scanning transmission electron microscopy. Corroborated by theoretical calculations and impedance measurements, it is demonstrated that such a unique configuration maximizes the number of percolation directions and thus most effectively improves the ionic conductivity. Finally, this discovery reconciles the long-standing structure–property inconsistency in (Li0.33La0.56)TiO3 and also identifies mesoscopic ordering as a promising general strategy for optimizing Li+ conduction.« less

  15. Preperation and electrochemical characterization of Sm and Gd co-doped ceria/carbonate composite electrolytes for IT-SOFC applications

    NASA Astrophysics Data System (ADS)

    Dikmen, Sibel; Ozsakarya, Rabia; Dikmen, Erdal

    2014-03-01

    Sm and Gd co-doped ceria based composite electrolytes were prepared by mixing nanosized powders of Ce0.8Sm0.1Gd0.1O2-δ (SGDC) and alkaline carbonates (Na-Li)2CO3, (Li-K)2CO3,and(Na-K)2CO3 at a weight ratio of 4:1. Structure of the samples was characterized by powder X-ray diffraction. The microstructure and morphology were examined by SEM. Impedance spectroscopy was used to perform electrochemical characterization. The conductivities of the samples increase as the temperature increases and for the composite electrolytes SGDC(Na-Li)2CO3,andSGDC(Li-K)2CO3, there is a sharp increase in conductivity at around 475 and 450oC, respectively. This sudden change in the conductivity refers to superionic phase transition in the interfaces between SGDC phase and salt phase. The single cell power density reached a maximum of 1056, 826, and 565 mWcm-2 for SGDC/ (Na-Li)2CO3, SGDC/(Li-K)2CO3,andSGDC/(Na-K)2CO3 as the electrolytes, respectively. This work was funded by TUB?TAK 106T536, SDU-BAP 3231-YL1-12.

  16. Promoting solution phase discharge in Li-O2 batteries containing weakly solvating electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Gao, Xiangwen; Chen, Yuhui; Johnson, Lee; Bruce, Peter G.

    2016-08-01

    On discharge, the Li-O2 battery can form a Li2O2 film on the cathode surface, leading to low capacities, low rates and early cell death, or it can form Li2O2 particles in solution, leading to high capacities at relatively high rates and avoiding early cell death. Achieving discharge in solution is important and may be encouraged by the use of high donor or acceptor number solvents or salts that dissolve the LiO2 intermediate involved in the formation of Li2O2. However, the characteristics that make high donor or acceptor number solvents good (for example, high polarity) result in them being unstable towards LiO2 or Li2O2. Here we demonstrate that introduction of the additive 2,5-di-tert-butyl-1,4-benzoquinone (DBBQ) promotes solution phase formation of Li2O2 in low-polarity and weakly solvating electrolyte solutions. Importantly, it does so while simultaneously suppressing direct reduction to Li2O2 on the cathode surface, which would otherwise lead to Li2O2 film growth and premature cell death. It also halves the overpotential during discharge, increases the capacity 80- to 100-fold and enables rates >1 mA cmareal-2 for cathodes with capacities of >4 mAh cmareal-2. The DBBQ additive operates by a new mechanism that avoids the reactive LiO2 intermediate in solution.

  17. Electrolyte Solvation and Ionic Association. V. Acetonitrile-Lithium Bis(fluorosulfonyl)imide (LiFSI) Mixtures

    SciTech Connect

    Han, Sang D.; Borodin, Oleg; Seo, D. M.; Zhou, Zhi B.; Henderson, Wesley A.

    2014-09-30

    Electrolytes with the salt lithium bis(fluorosulfonyl)imide (LiFSI) have been evaluated relative to comparable electrolytes with other lithium salts. Acetonitrile (AN) has been used as a model electrolyte solvent. The information obtained from the thermal phase behavior, solvation/ionic association interactions, quantum chemical (QC) calculations and molecular dynamics (MD) simulations (with an APPLE&P many-body polarizable force field for the LiFSI salt) of the (AN)n-LiFSI mixtures provides detailed insight into the coordination interactions of the FSI- anions and the wide variability noted in the electrolyte transport property (i.e., viscosity and ionic conductivity).

  18. Conductivity and optical band gaps of polyethylene oxide doped with Li{sub 2}SO{sub 4} salt

    SciTech Connect

    Chapi, Sharanappa Raghu, S. Subramanya, K. Archana, K. Mini, V. Devendrappa, H.

    2014-04-24

    The conductivity and optical properties of Li{sub 2}SO{sub 4} doped polyethylene oxide (PEO) films were studied. The polymer electrolyte films are prepared using solution casting technique. The material phase change was confirmed by X-ray diffraction (XRD) technique. Optical absorption study was conducted using UV- Vis. Spectroscopy in the wavelength range 190–1100nm on pure and doped PEO films. The direct and indirect optical band gaps were found decreased from 5.81–4.51eV and 4.84–3.43eV respectively with increasing the Li{sub 2}SO{sub 4}. The conductivity found to increases with increasing the dopant concentration due to strong hopping mechanism at room temperature.

  19. Oxygen substitution effects in Li10GeP2S12 solid electrolyte

    NASA Astrophysics Data System (ADS)

    Sun, Yulong; Suzuki, Kota; Hara, Kosuke; Hori, Satoshi; Yano, Taka-aki; Hara, Masahiko; Hirayama, Masaaki; Kanno, Ryoji

    2016-08-01

    For the lithium super-ionic conductor Li10GeP2S12, the partial substitution of sulfur by oxygen is achieved via a solid-state reaction. The solid-solution range of oxygen is found to be 0 ≤ x < 0.9 in Li10GeP2S12-xOx. Structure refinements using synchrotron X-ray diffraction data confirm the preference for oxygen substitution in the PS4 tetrahedra. The local structural change in the P(S/O)4 tetrahedra upon substitution is also indicated by Raman spectroscopy. Ionic conduction properties are maintained even after the oxygen substitution in Li10GeP2S12; the ionic conductivity of Li10GeP2S12-xOx (0.3 ≤ x ≤ 0.6) ranges from 1.03 × 10-2 to 8.43 × 10-3 S cm-1 at 298 K. No redox current is observed by cyclic voltammetry from nearly 0 to 10 V versus Li/Li+ except for that due to the lithium deposition/dissolution reactions. All-solid-state batteries using Li10GeP2S12-xOx (x = 0.3 and 0.6) as solid electrolytes with Li metal anodes show discharge capacities exceeding 100 mAh g-1 and better cycling performance compared to batteries using the original Li10GeP2S12. The partial substitution of oxygen for sulfur in Li10GeP2S12 affords a novel solid electrolyte, Li10GeP2S12-xOx, with high conductive properties and electrochemical stability.

  20. Oxygen substitution effects in Li10GeP2S12 solid electrolyte

    NASA Astrophysics Data System (ADS)

    Sun, Yulong; Suzuki, Kota; Hara, Kosuke; Hori, Satoshi; Yano, Taka-aki; Hara, Masahiko; Hirayama, Masaaki; Kanno, Ryoji

    2016-08-01

    For the lithium super-ionic conductor Li10GeP2S12, the partial substitution of sulfur by oxygen is achieved via a solid-state reaction. The solid-solution range of oxygen is found to be 0 ≤ x < 0.9 in Li10GeP2S12-xOx. Structure refinements using synchrotron X-ray diffraction data confirm the preference for oxygen substitution in the PS4 tetrahedra. The local structural change in the P(S/O)4 tetrahedra upon substitution is also indicated by Raman spectroscopy. Ionic conduction properties are maintained even after the oxygen substitution in Li10GeP2S12; the ionic conductivity of Li10GeP2S12-xOx (0.3 ≤ x ≤ 0.6) ranges from 1.03 × 10-2 to 8.43 × 10-3 S cm-1 at 298 K. No redox current is observed by cyclic voltammetry from nearly 0 to 10 V versus Li/Li+ except for that due to the lithium deposition/dissolution reactions. All-solid-state batteries using Li10GeP2S12-xOx (x = 0.3 and 0.6) as solid electrolytes with Li metal anodes show discharge capacities exceeding 100 mAh g-1 and better cycling performance compared to batteries using the original Li10GeP2S12. The partial substitution of oxygen for sulfur in Li10GeP2S12 affords a novel solid electrolyte, Li10GeP2S12-xOx, with high conductive properties and electrochemical stability.

  1. Solvate Structures and Computational/Spectroscopic Characterization of LiBF4 Electrolytes

    SciTech Connect

    Seo, D. M.; Boyle, Paul D.; Allen, Joshua L.; Han, Sang D.; Jonsson, Erlendur; Johansson, Patrik; Henderson, Wesley A.

    2014-07-21

    Crystal structures have been determined for both LiBF4 and HBF4 solvates—(acetonitrile)2:LiBF4, (ethylene glycol diethyl ether)1:LiBF4, (diethylene glycol diethyl ether)1:LiBF4, (tetrahydrofuran)1:LiBF4, (methyl methoxyacetate)1:LiBF4, (suc-cinonitrile)1:LiBF4, (N,N,N',N",N"-pentamethyldiethylenetriamine)1:HBF4, (N,N,N',N'-tetramethylethylenediamine)3/2:HBF4 and (phenanthroline)2:HBF4. These, as well as other known LiBF4 solvate structures, have been characterized by Raman vibrational spectroscopy to unambiguously assign the anion Raman band positions to specific forms of BF4-...Li+ cation coordination. In addition, complementary DFT calculations of BF4-...Li+ cation complexes have provided additional insight into the challenges associated with accurately interpreting the anion interactions from experimental Raman spectra. This information provides a crucial tool for the characterization of the ionic association interactions within electrolytes.

  2. AFM study of oxygen reduction products on HOPG in the LiPF6-DMSO electrolyte.

    PubMed

    Herrera, Santiago E; Tesio, Alvaro Y; Clarenc, Romain; Calvo, Ernesto J

    2014-06-01

    Ex situ atomic force microscopy (AFM) has been used to study the morphology of oxygen reduction products in the LiPF6-dimethyl sulfoxide (DMSO) electrolyte, i.e. Li2O2 on a highly oriented pyrolytic graphite (HOPG) surface. Both cyclic voltammetry and chronoamperometry have shown that at low cathodic polarization the initial deposits decorate the edge steps of HOPG. At higher overpotentials a massive deposit covers the terraces. Upon charging the battery cathode Li2O2 oxidation and dissolution do not take place until high overpotentials are reached at which solvent decomposition has been demonstrated by in situ FTIR studies.

  3. Performance of Low Temperature Electrolytes in Experimental and Prototype Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Whitcanack, L. D.

    2007-01-01

    Due to their attractive properties and proven success, Li-ion batteries have become identified as the battery chemistry of choice for a number of future NASA missions. A number of these applications would be greatly benefited by improved performance of Li-ion technology over a wider operating temperature range, especially at low temperatures, such as future ESMD missions. In many cases, these technology improvements may be mission enabling, and at the very least mission enhancing. In addition to aerospace applications, the DoE has interest in developing advanced Li-ion batteries that can operate over a wide temperature range to enable terrestrial HEV applications. Thus, our focus at JPL in recent years has been to extend the operating temperature range of Li-ion batteries, especially at low temperatures. To accomplish this, the main focus of the research has been devoted to developing improved lithium-ion conducting electrolytes. In the present paper, we would like to present some of the results we have obtained with ethylene carbonate-based electrolytes optimized for low temperature in experimental MCMB-LiNixCo1_x0 2 cells. In addition to obtaining discharge and charge rate performance data at various temperatures, electrochemical measurements were performed on individual electrodes (made possible by the incorporation of Li reference electrodes), including EIS, linear polarization and Tafel polarization measurements. The combination of techniques enables the elucidation of various trends associated with electrolyte composition. In addition to investigating the behavior in experimental cells, the performance of many promising low temperature electrolytes was demonstrated in large capacity, aerospace quality Li-ion prototype cells. These cells were subjected to a number of performance tests, including discharge rate characterization, charge rate characterization, cycle life performance at various temperatures, and power characterization tests.

  4. Estimation of energy density of Li-S batteries with liquid and solid electrolytes

    NASA Astrophysics Data System (ADS)

    Li, Chunmei; Zhang, Heng; Otaegui, Laida; Singh, Gurpreet; Armand, Michel; Rodriguez-Martinez, Lide M.

    2016-09-01

    With the exponential growth of technology in mobile devices and the rapid expansion of electric vehicles into the market, it appears that the energy density of the state-of-the-art Li-ion batteries (LIBs) cannot satisfy the practical requirements. Sulfur has been one of the best cathode material choices due to its high charge storage (1675 mAh g-1), natural abundance and easy accessibility. In this paper, calculations are performed for different cell design parameters such as the active material loading, the amount/thickness of electrolyte, the sulfur utilization, etc. to predict the energy density of Li-S cells based on liquid, polymeric and ceramic electrolytes. It demonstrates that Li-S battery is most likely to be competitive in gravimetric energy density, but not volumetric energy density, with current technology, when comparing with LIBs. Furthermore, the cells with polymer and thin ceramic electrolytes show promising potential in terms of high gravimetric energy density, especially the cells with the polymer electrolyte. This estimation study of Li-S energy density can be used as a good guidance for controlling the key design parameters in order to get desirable energy density at cell-level.

  5. Ester-Based Electrolytes for Low-Temperature Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, Marshall; Bugga, Ratnakumar

    2005-01-01

    Electrolytes comprising LiPF6 dissolved at a concentration of 1.0 M in five different solvent mixtures of alkyl carbonates have been found to afford improved performance in rechargeable lithium-ion electrochemical cells at temperatures as low as -70 C. These and other electrolytes have been investigated in continuing research directed toward extending the lower limit of practical operating temperatures of Li-ion cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles, the most recent being Low-EC-Content Electrolytes for Low-Temperature Li-Ion Cells (NPO-30226), NASA Tech Briefs, Vol. 27, No. 1 (January 2003), page 46. The ingredients of the present solvent mixtures are ethylene carbonate (EC), ethyl methyl carbonate (EMC), methyl butyrate (MB), methyl propionate (MP), ethyl propionate (EP), ethyl butyrate (EB), and ethyl valerate (EV). In terms of volume proportions of these ingredients, the present solvent mixtures are 1EC + 1EMC + 8MB, 1EC + 1EMC + 8EB, 1EC + 1EMC + 8MP, 1EC + 1EMC + 8EV, and 1EC + 9EMC. These electrolytes were placed in Liion cells containing carbon anodes and LiNi0.8Co0.2O2 cathodes, and the low-temperature electrical performances of the cells were measured. The cells containing the MB and MP mixtures performed best.

  6. Reversible lithium intercalation in a lithium-rich layered rocksalt Li2RuO3 cathode through a Li3PO4 solid electrolyte

    NASA Astrophysics Data System (ADS)

    Zheng, Yueming; Hirayama, Masaaki; Taminato, Sou; Lee, Soyeon; Oshima, Yoshifumi; Takayanagi, Kunio; Suzuki, Kota; Kanno, Ryoji

    2015-12-01

    Li2RuO3 (001) films with a lithium-rich layered rocksalt structure are epitaxially grown on a Al2O3(0001) substrate through pulsed laser deposition, followed by stacking of an amorphous Li3PO4 solid electrolyte. A half solid-state battery with a Li3PO4/Li2RuO3 cathode, liquid electrolyte, and lithium anode exhibits two redox peak pairs at 3.4 and 3.6 V, demonstrating lithium intercalation in the Li2RuO3 through the Li3PO4 solid electrolyte. All-solid-state batteries are fabricated by Li or In metal anode deposition on the Li3PO4/Li2RuO3. The Li/Li3PO4/Li2RuO3 cell delivers an initial discharge capacity of 101 mAh g-1, which does not fade significantly over 30 cycles. Furthermore, the Li2RuO3 rate capability is comparable to that of a liquid-type battery. Lithium-rich layered materials are available for use as cathodes in all-solid-state batteries.

  7. Effect of electrolytes on the structure and evolution of the solid electrolyte interphase (SEI) in Li-ion batteries: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Kim, Sang-Pil; Duin, Adri C. T. van; Shenoy, Vivek B.

    2011-10-01

    We have studied the formation and growth of solid-electrolyte interphase (SEI) for the case of ethylene carbonate (EC), dimethyl carbonate (DMC) and mixtures of these electrolytes using molecular dynamics simulations. We have considered SEI growth on both Li metal surfaces and using a simulation framework that allows us to vary the Li surface density on the anode surface. Using our simulations we have obtained the detailed structure and distribution of different constituents in the SEI as a function of the distance from the anode surfaces. We find that SEI films formed in the presence of EC are rich in Li2CO3 and Li2O, while LiOCH3 is the primary constituent of DMC films. We find that dilithium ethylene dicarbonate, LiEDC, is formed in the presence of EC at low Li surface densities, but it quickly decomposes to inorganic salts during subsequent growth in Li rich environments. The surface films formed in our simulations have a multilayer structure with regions rich in inorganic and organic salts located near the anode surface and the electrolyte interface, respectively, in agreement with depth profiling experiments. Our computed formation potentials 1.0 V vs. Li/Li+ is also in excellent accord with experimental measurements. We have also calculated the elastic stiffness of the SEI films; we find that they are significantly stiffer than Li metal, but are somewhat more compliant compared to the graphite anode.

  8. New-concept Batteries Based on Aqueous Li+/Na+ Mixed-ion Electrolytes

    PubMed Central

    Chen, Liang; Gu, Qingwen; Zhou, Xufeng; Lee, Saixi; Xia, Yonggao; Liu, Zhaoping

    2013-01-01

    Rechargeable batteries made from low-cost and abundant materials operating in safe aqueous electrolytes are attractive for large-scale energy storage. Sodium-ion battery is considered as a potential alternative of current lithium-ion battery. As sodium-intercalation compounds suitable for aqueous batteries are limited, we adopt a novel concept of Li+/Na+ mixed-ion electrolytes to create two batteries (LiMn2O4/Na0.22MnO2 and Na0.44MnO2/TiP2O7), which relies on two electrochemical processes. One involves Li+ insertion/extraction reaction, and the other mainly relates to Na+ extraction/insertion reaction. Two batteries exhibit specific energy of 17 Wh kg−1 and 25 Wh kg−1 based on the total weight of active electrode materials, respectively. As well, aqueous LiMn2O4/Na0.22MnO2 battery is capable of separating Li+ and Na+ due to its specific mechanism unlike the traditional “rocking-chair” lithium-ion batteries. Hence, the Li+/Na+ mixed-ion batteries offer promising applications in energy storage and Li+/Na+ separation. PMID:23736113

  9. Li-Ion Cells Employing Electrolytes With Methyl Propionate and Ethyl Butyrate Co-Solvents

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Bugga, Ratnakumar V.

    2011-01-01

    Future NASA missions aimed at exploring Mars and the outer planets require rechargeable batteries that can operate at low temperatures to satisfy the requirements of such applications as landers, rovers, and penetrators. A number of terrestrial applications, such as hybrid electric vehicles (HEVs) and electric vehicles (EVs) also require energy storage devices that can operate over a wide temperature range (i.e., -40 to +70 C), while still providing high power capability and long life. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-30 to +40 C); however, the rate capability at the lower temperatures is very poor. These limitations at very low temperatures are due to poor electrolyte conductivity, poor lithium intercalation kinetics over the electrode surface layers, and poor ionic diffusion in the electrode bulk. Two wide-operating-temperature-range electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed include further optimization of electrolytes containing methyl propionate (MP) and ethyl butyrate (EB), which are effective co-solvents, to widen the operating temperature range beyond the baseline systems. Attention was focused on further optimizing ester-based electrolyte formulations that have exhibited the best performance at temperatures ranging from -60 to +60 C, with an emphasis upon improving the rate capability at -20 to -40 C. This was accomplished by increasing electrolyte salt concentration to 1.20M and increasing the ester content to 60 percent by volume to increase the ionic conductivity at low temperatures. Two JPL-developed electrolytes 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %) operate effectively over a wide

  10. Li-air batteries having ether-based electrolytes

    DOEpatents

    Amine, Khalil; Curtiss, Larry A; Lu, Jun; Lau, Kah Chun; Zhang, Zhengcheng; Sun, Yang-Kook

    2015-03-03

    A lithium-air battery includes a cathode including a porous active carbon material, a separator, an anode including lithium, and an electrolyte including a lithium salt and polyalkylene glycol ether, where the porous active carbon material is free of a metal-based catalyst.

  11. Assessment of Various Low Temperature Electrolytes in Prototype Li-Ion Cells Developed for ESMD Applications

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Whitcanack, L. D.

    2008-01-01

    Due to their attractive properties and proven success, Li-ion batteries have become identified as the battery chemistry of choice for a number of future NASA missions. A number of these applications would be greatly benefited by improved performance of Li-ion technology over a wider operating temperature range, especially at low temperatures, such as future ESMD missions. In many cases, these technology improvements may be mission enabling, and at the very least mission enhancing. In addition to aerospace applications, the DoE has interest in developing advanced Li-ion batteries that can operate over a wide temperature range to enable terrestrial HEV applications. Thus, our focus at JPL in recent years has been to extend the operating temperature range of Li-ion batteries, especially at low temperatures. To accomplish this, the main focus of the research has been devoted to developing improved lithium-ion conducting electrolytes. In the present paper, we would like to present some of the results we have obtained with six different ethylene carbonate-based electrolytes optimized for low temperature. In addition to investigating the behavior in experimental cells initially, the performance of these promising low temperature electrolytes was demonstrated in large capacity, aerospace quality Li-ion prototype cells, manufactured by Yardney Technical Products and Saft America, Inc. These cells were subjected to a number of performance tests, including discharge rate characterization, charge rate characterization, cycle life performance at various temperatures, and power characterization tests.

  12. Effect of electrolyte water content on the anodic passivation of lithium in IM LiC104-propylene carbonate

    NASA Astrophysics Data System (ADS)

    James, S. D.; Nagao, A. R.

    1982-06-01

    This work deals with the effect of aqueous contamination on the anode passivation of Li in 1M LiC10 4-propylene carbonate. Passivation occurs more readily with increasing electrolyte water content. Preliminary evidence suggests that anodic passivation may be due to anodic enrichment and eventual precipitation of LiC10 4 in the superficial anolyte layer.

  13. Performance of Li-ion cells with new electrolytes conceived for low-temperature applications

    NASA Astrophysics Data System (ADS)

    Sazhin, Sergey V.; Khimchenko, Mikhail Yu; Tritenichenko, Yevgeniy N.; Lim, Hong S.

    In an effort to develop a useful electrolyte for a Li-ion cell applicable in a wide operation temperature, we have studied a number of ternary electrolytes containing a cyclic carbonate (ethylene carbonate (EC)), a linear carbonate (dimethyl carbonate (DMC), diethyl carbonate (DEC), or ethylmethyl carbonate (EMC)), and a low-temperature freezing solvent (methyl acetate, ethyl acetate, isopropyl acetate, isoamyl acetate, or ethyl propionate (EP)). We have studied performance including cycle life of Li-ion cells containing these electrolytes at various temperatures. The performance was various with various electrolyte compositions showing a significant effect of the low-temperature freezing solvents while the effect of the linear carbonates was relatively minor. Cells containing an electrolyte of EC-DMC-MA showed an excellent initial performance at -20°C but it did not give a good cycle life compared with others. Two electrolyte compositions containing EP, EC-DEC-EP and EC-EMC-EP, showed the most attractive overall performance including initial performance at -20°C, cycle life and rate capability at room temperature as well as 50°C.

  14. Power capability of LiTDI-based electrolytes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Paillet, Sabrina; Schmidt, Gregory; Ladouceur, Sébastien; Fréchette, Joël; Barray, Francis; Clément, Daniel; Hovington, Pierre; Guerfi, Abdelbast; Vijh, Ashok; Cayrefourcq, Ian; Zaghib, Karim

    2015-10-01

    We report results obtained with lithium 4,5-dicyano-2-(trifluoromethyl) imidazolide (LiTDI), which we believe is a promising lithium salt for electrolytes in lithium-ion batteries. This "Hückel"- type salt has high charge delocalizations which contribute to good lithium-ion dissociation. In addition, it has high thermal stability and safer degradation products compared to LiPF6, which were identified by TGA-MS. It also does not corrode but passivate the aluminum current collector. Cyclic voltammetry measurements showed a stability up to 4.5 V, which is sufficient for use with standard cathode materials. The power capability of half cells containing LiTDI in EC/DEC was evaluated with standard cathodes used in lithium-ion batteries: LFP, NMC, LCO and LMO. Two LiTDI concentrations were investigated: 1 M and 0.6 M and compared with a reference electrolyte: 1 M LiPF6. In spite of a slightly lower conductivity than the LiPF6, LiTDI (1 M and 0.6 M) shows similar power capability up to 2C with LFP (84% of specific capacity recovered), 10C with NMC (61% of specific capacity recovered), and up to 20C for LMO (88% of specific capacity recovered). Furthermore, better power capability was obtained with 0.6 M LiTDI with LCO, which yielded 82% of specific capacity recovered at 1C (67% for 1 M LiTDI and 1 M LiPF6).

  15. Compatibility of lithium difluoro(sulfato)borate-based electrolyte for LiMn2O4 cathode

    NASA Astrophysics Data System (ADS)

    Li, Shiyou; Liu, Jinliang; Li, Lingxia; Li, Xiaopeng; Jing, Jie; Cui, Xiaoling

    2015-03-01

    Lithium difluoro(sulfato)borate (LiBF2SO4) is investigated as a lithium salt for non-aqueous electrolytes for LiMn2O4 cathode in lithium-ion batteries. Inductively coupled plasma-atomic emission spectrometry analysis is used to analyze the Mn dissolution. Scanning electron microscopy and AC impedance measurements analysis are used to analyze the formation of the surface film on the surface of LiMn2O4 cathode. These results demonstrate that LiBF2SO4-based electrolyte favourably facilitates the formation of an effective and conductive interface film on the cathode surface to improve the stabilization of cathode/electrolyte interface. Besides, LiMn2O4 cells using LiBF2SO4-based electrolyte exerts several advantages, such as stable cycling performance, low cell impedance, low polarization resistance, and good rate performance. It suggests that LiBF2SO4-based electrolyte has good compatibility with LiMn2O4 cathode, and LiBF2SO4 would be a very promising lithium salt for LiMn2O4 cathode in lithium-ion batteries.

  16. Facile Synthesis of Boron-Doped rGO as Cathode Material for High Energy Li-O2 Batteries.

    PubMed

    Wu, Feng; Xing, Yi; Li, Li; Qian, Ji; Qu, Wenjie; Wen, Jianguo; Miller, Dean; Ye, Yusheng; Chen, Renjie; Amine, Khalil; Lu, Jun

    2016-09-14

    To improve the electrochemical performance of the high energy Li-O2 batteries, it is important to design and construct a suitable and effective oxygen-breathing cathode. Herein, a three-dimensional (3D) porous boron-doped reduction graphite oxide (B-rGO) material with a hierarchical structure has been prepared by a facile freeze-drying method. In this design, boric acid as the boron source helps to form the 3D porous structure, owing to its cross-linking and pore-forming function. This architecture facilitates the rapid oxygen diffusion and electrolyte penetration in the electrode. Meanwhile, the boron-oxygen functional groups linking to the carbon surface or edge serve as additional reaction sites to activate the ORR process. It is vital that boron atoms have been doped into the carbon lattices to greatly activate the electrons in the carbon π system, which is beneficial for fast charge under large current densities. Density functional theory calculation demonstrates that B-rGO exhibits much stronger interactions with Li5O6 clusters, so that B-rGO more effectively activates Li-O bonds to decompose Li2O2 during charge than rGO does. With B-rGO as a catalytic substrate, the Li-O2 battery achieves a high discharge capacity and excellent rate capability. Moreover, catalysts could be added into the B-rGO substrate to further lower the overpotential and enhance the cycling performance in future. PMID:27549204

  17. Air-Stable, High-Conduction Solid Electrolytes of Arsenic-Substituted Li4SnS4

    SciTech Connect

    Sahu, Gayatri; Lin, Zhan; Li, Juchuan; Liu, Zengcai; Dudney, Nancy J; Liang, Chengdu

    2014-01-01

    Lithium-ion-conducting solid electrolytes show promise for enabling high-energy secondary battery chemistries and solving safety issues associated with conventional lithium batteries. Achieving the combination of high ionic conductivity and outstanding chemical stability in solid electrolytes is a grand challenge for the synthesis of solid electrolytes. Herein we report the design of aliovalent substitution of Li4SnS4 to achieve high conduction and excellent air stability based on the hard and soft acids and bases theory. The composition of Li3.833Sn0.833As 0.166S4 has a high ionic conductivity of 1.39 mS/cm 1 at 25 C. Considering the high Li+ transference number, this phase conducts Li+ as well as carbonate-based liquid electrolytes. This research also addresses the compatibility of the sulfide-based solid electrolytes through chemical passivation.

  18. Electrochemical quartz crystal microbalance measurement of a Li4Ti5O12 composite electrode in a carbonate electrolyte

    NASA Astrophysics Data System (ADS)

    Serizawa, Nobuyuki; Shono, Kumi; Kobayashi, Yo; Miyashiro, Hajime; Katayama, Yasushi; Miura, Takashi

    2015-11-01

    Electrochemical quartz crystal microbalance (EQCM) measurement is conducted with a Li4Ti5O12 (lithium titanium oxide, LTO)-coated quartz crystal electrode in a carbonate electrolyte (ethylene carbonate + dimethyl carbonate; 50: 50 vol%) containing 1 M LiPF6. In-situ monitoring of the mass change during the charge and discharge of the LTO electrode can be achieved quantitatively because of the "zero-strain" property of LTO with Li+ insertion and the probably low reactivity between LTO and the electrolyte. The local changes of viscosity and density of the electrolyte contacting the LTO electrode are detected via the resonance resistance of the quartz crystal electrode, suggesting the local concentrations of Li+ and counter anion changed significantly during insertion and extraction of Li+ in the organic electrolyte.

  19. Preparation and electrochemical properties of Zr-site substituted Li7La3(Zr2-xMx)O12 (M = Ta, Nb) solid electrolytes

    NASA Astrophysics Data System (ADS)

    Huang, Mian; Shoji, Mao; Shen, Yang; Nan, Ce-Wen; Munakata, Hirokazu; Kanamura, Kiyoshi

    2014-09-01

    Li7La3Zr2O12 (LLZ) solid electrolytes with Zr site partially substituted by Ta and Nb elements were prepared via the conventional solid-state reaction. All the compositions could lead to the cubic garnet-type structure after sintering at 1150 °C. The use of γ-Al2O3 as a sintering aid in the preparation of doped LLZ was studied. It was shown that Al could help to improve the micro-structure for Nb doping, but not necessary for Ta doping. The Ta and Nb doping enhanced the ionic conductivity at 25 °C to 4.09 × 10-4 S cm-1 and 4.50 × 10-4 S cm-1, respectively. A conductivity as high as 1.23 × 10-3 S cm-1 was obtained when measured at 50 °C in air for the Nb-doped LLZ. All-solid-state batteries with LLZTa and LLZNb solid electrolytes were assembled and tested. The cyclic voltammetry (CV) measurement indicated the successful working of the batteries.

  20. Solvate Structures and Computational/Spectroscopic Characterization of LiPF6 Electrolytes

    SciTech Connect

    Han, Sang D.; Yun, Sung-Hyun; Borodin, Oleg; Seo, D. M.; Sommer, Roger D.; Young, Victor G.; Henderson, Wesley A.

    2015-04-23

    Raman spectroscopy is a powerful method for identifying ion-ion interactions, but only if the vibrational band signature for the anion coordination modes can be accurately deciphered. The present study characterizes the PF6- anion P-F Raman symmetric stretching vibrational band for evaluating the PF6-...Li+ cation interactions within LiPF6 crystalline solvates to create a characterization tool for liquid electrolytes. To facilitate this, the crystal structures for two new solvates—(G3)1:LiPF6 and (DEC)2:LiPF6 with triglyme and diethyl carbonate, respectively—are reported. The information obtained from this analysis provides key guidance about the ionic association information which may be obtained from a Raman spectroscopic evaluation of electrolytes containing the LiPF6 salt and aprotic solvents. Of particular note is the overlap of the Raman bands for both solvent-separated ion pair (SSIP) and contact ion pair (CIP) coordination in which the PF6- anions are uncoordinated or coordinated to a single Li+ cation, respectively.

  1. Li doped ZnO thin films for optoelectronic applications

    NASA Astrophysics Data System (ADS)

    Sandeep, K. M.; Bhat, Shreesha; Serrao, F. J.; Dharmaprakash, S. M.

    2016-05-01

    We have prepared undoped (ZnO) and Li doped ZnO (LZO) thin films using cost effective sol gel spin coating method.The structural properties were analyzed by X-ray diffraction, and it showed that Li ions occupied interstitial positions in the LZO film. The optical properties like band bending effect, absorption length, band edge sharpness, which have direct impact on solar cell performance has been calculated. The room temperature photoluminescence spectra of the films showed dominant blue emission with CIE coordinate numbers (0.1384, 0.0836) for ZnO and (0.1356, 0.0910) for LZO. The dominating wavelength of the blue emission is present at 470.9 nm and 472.3 nm for ZnO and LZO films respectively. The structural and optical parameters determined in the present study could be used in LED applications.

  2. Mechanism of Li-doping into Li 4Ti 5O 12 negative active material for Li-ion cells by new chemical method

    NASA Astrophysics Data System (ADS)

    Tabuchi, Toru; Yasuda, Hideo; Yamachi, Masanori

    Li 4+ XTi 5O 12 (X > 0) negative active material has been successfully synthesized by a new chemical method for Li-doping with the catalytic function of naphthalene in Li-organic complex solution of butylmethylether (BME) or dimethoxyethane (DME) solvent. The Li-doping reaction rate constant in BME was found to be greater than that of the case of DME and its value was 5.10 and 2.78 × 10 -4 S -1/2, respectively, by the calculation from the slope of distinct straight line in the relationship between ln(1/1 - Y) and √{ t } , where Y is molar fraction of Li-doping materials of Li 7Ti 5O 12.

  3. PC based electrolytes with LiDFOB as an alternative salt for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Knight, Brandon M.

    Lithium-ion batteries (LIBs) have been greatly sought after as a source of renewable energy storage. LIBs have a wide range of applications including but not limited portable electronic devices, electric vehicles, and power tools. As a direct result of their commercial viability an insatiable hunger for knowledge, advancement within the field of LIBs has been omnipresent for the last two decades. However, there are set backs evident within the LIB field; most notably the limitations of standard electrolyte formulations and LiPF6 lithium salt. The standard primary carbonate of ethylene carbonate (EC) has a very limited operating range due to its innate physical properties, and the LiPF6 salt is known to readily decompose to form HF which can further degrade LIB longevity. The goal of our research is to explore the use of a new primary salt LiDFOB in conjunction with a propylene carbonate based electrolyte to establish a more flexible electrolyte formulation by constructing coin cells and cycling them under various conditions to give a clear understanding of each formulation inherent performance capabilities. Our studies show that 1.2M LiDFOB in 3:7 PC/EMC + 1.5% VC is capable of performing comparably to the standard 1.2M LiPF6 in 3:7 EC/EMC at 25°C and the PC electrolyte also illustrates performance superior to the standard at 55°C. The degradation of lithium manganese spinel electrodes, including LiNi 0.5Mn1.5O4, is an area of great concern within the field of lithium ion batteries (LIBs). Manganese containing cathode materials frequently have problems associated with Mn dissolution which significantly reduces the cycle life of LIB. Thus the stability of the cathode material is paramount to the performance of Mn spinel cathode materials in LIBs. In an effort to gain a better understanding of the stability of LiNi0.5 Mn1.5O4 in common LiPF6/carbonate electrolytes, samples were stored at elevated temperature in the presence of electrolyte. Then after storage both

  4. Electrode-electrolyte interface in Li-ion batteries: current understanding and new insights.

    PubMed

    Gauthier, Magali; Carney, Thomas J; Grimaud, Alexis; Giordano, Livia; Pour, Nir; Chang, Hao-Hsun; Fenning, David P; Lux, Simon F; Paschos, Odysseas; Bauer, Christoph; Maglia, Filippo; Lupart, Saskia; Lamp, Peter; Shao-Horn, Yang

    2015-11-19

    Understanding reactions at the electrode/electrolyte interface (EEI) is essential to developing strategies to enhance cycle life and safety of lithium batteries. Despite research in the past four decades, there is still limited understanding by what means different components are formed at the EEI and how they influence EEI layer properties. We review findings used to establish the well-known mosaic structure model for the EEI (often referred to as solid electrolyte interphase or SEI) on negative electrodes including lithium, graphite, tin, and silicon. Much less understanding exists for EEI layers for positive electrodes. High-capacity Li-rich layered oxides yLi2-xMnO3·(1-y)Li1-xMO2, which can generate highly reactive species toward the electrolyte via oxygen anion redox, highlight the critical need to understand reactions with the electrolyte and EEI layers for advanced positive electrodes. Recent advances in in situ characterization of well-defined electrode surfaces can provide mechanistic insights and strategies to tailor EEI layer composition and properties. PMID:26510477

  5. Nitrogen-doped graphene-decorated LiVPO4F nanocomposite as high-voltage cathode material for rechargeable lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Cui, Kai; Hu, Shuchun; Li, Yongkui

    2016-09-01

    In this study, nitrogen-doped graphene decorated LiVPO4F cathode material is firstly synthesized via a facile method. Well-dispersed LiVPO4F nanoparticles are embedded in nitrogen-doped graphene nanosheets, forming an effective conducting network. The added nitrogen-doped graphene nanosheets greatly enhance the electronic conductivity and Li-ion diffusion of LiVPO4F sample. When tested as cathode material for rechargeable lithium-ion batteries, the hybrid electrode exhibits superior high-rate performance and long-term cycling stability between 3.0 and 4.5 V. It delivers a large discharge capacity of 152.7 mAhg-1 at 0.1 C and shows a capacity retention of 97.8% after 60 cycles. Moreover, a reversible capacity of 90.1 mAhg-1 is maintained even after 500 cycles at a high rate of 20 C. The charge-transfer resistance of LiVPO4F electrode is also reduced in the nitrogen-doped graphene, revealing that its electrode-electrolyte complex reactions take place easily and thus improve the electrochemical performance. The above results provide a facile and effective strategy for the synthesis of LiVPO4F cathode material for high-performance lithium-ion batteries.

  6. Importance of Reaction Kinetics and Oxygen Crossover in aprotic Li-O2 Batteries Based on a Dimethyl Sulfoxide Electrolyte.

    PubMed

    Marinaro, M; Balasubramanian, P; Gucciardi, E; Theil, S; Jörissen, L; Wohlfahrt-Mehrens, M

    2015-09-21

    Although still in their embryonic state, aprotic rechargeable Li-O2 batteries have, theoretically, the capabilities of reaching higher specific energy densities than Li-ion batteries. There are, however, significant drawbacks that must be addressed to allow stable electrochemical performance; these will ultimately be solved by a deeper understanding of the chemical and electrochemical processes occurring during battery operations. We report a study on the electrochemical and chemical stability of Li-O2 batteries comprising Au-coated carbon cathodes, a dimethyl sulfoxide (DMSO)-based electrolyte and Li metal negative electrodes. The use of the aforementioned Au-coated cathodes in combination with a 1 M lithium bis(trifluoromethane)sulfonimide (LiTFSI)-DMSO electrolyte guarantees very good cycling stability (>300 cycles) by minimizing eventual side reactions. The main drawbacks arise from the high reactivity of the Li metal electrode when in contact with the O2 -saturated DMSO-based electrolyte.

  7. Use of phosphoranimines to reduce organic carbonate content in Li-ion battery electrolytes

    DOE PAGESBeta

    Dufek, Eric J.; Klaehn, John R.; McNally, Joshua S.; Rollins, Harry W.; Jamison, David K.

    2016-05-09

    In this study, the use of phosphoranimines (PAs), a class of linear, monomeric phosphazenes, as electrolytes for Li-ion battery applications has been investigated as a route to improve safety and stability for Li-ion batteries. Of the potential PAs for use in battery applications, this work focuses on the initial synthetic preparation and analysis of N-trimethylsilyl-P,P-bis((2-methoxyethoxy)ethoxy)-P-ethylphosphoranimine (PA-5). PA-5 has high LiPF6 solubility in excess of 2 M, high thermal stability with a melting point below -80°C and high thermal stability as a neat compound to at least 250°C. As part of electrolyte blends, the inclusion of PA-5 shifts the onset ofmore » thermal degradation by close to 40°C at 35% loading and by 20°C at a 10% loading, improves the low temperature performance of the electrolyte, and when used as a primary solvent leads to increases in the flash point (by 20°C) when compared to more traditional EC:EMC blends. Cycling capabilities of full-coin cells with graphite negative electrodes and Li1+w[Ni0.5Mn0.3Co0.2]1-wO2 positive electrodes using PA-5:EC:EMC electrolyte blends are comparable with the performance seen for traditional EC:EMC blends. Analysis of the impact of the use of additives such as vinylene carbonate in PA-5:EC:EMC blended electrolyte results in enhanced capacity retention and improved coulombic efficiency.« less

  8. Electrolytes for Low-Temperature Operation of Li-CFx Cells

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Whitacre, Jay F.; Bugga, Ratnakumar V.; Prakash, G. K. Surya; Bhalla, Pooja; Smith, Kiah

    2009-01-01

    A report describes a study of electrolyte compositions selected as candidates for improving the low-temperature performances of primary electrochemical cells that contain lithium anodes and fluorinated carbonaceous (CFx) cathodes. This study complements the developments reported in Additive for Low-Temperature Operation of Li-(CF)n Cells (NPO- 43579) and Li/CFx Cells Optimized for Low-Temperature Operation (NPO- 43585), which appear elsewhere in this issue of NASA Tech Briefs. Similar to lithium-based electrolytes described in several previous NASA Tech Briefs articles, each of these electrolytes consisted of a lithium salt dissolved in a nonaqueous solvent mixture. Each such mixture consisted of two or more of the following ingredients: propylene carbonate (PC); 1,2-dimethoxyethane (DME); trifluoropropylene carbonate; bis(2,2,2-trifluoroethyl) ether; diethyl carbonate; dimethyl carbonate; and ethyl methyl carbonate. The report describes the physical and chemical principles underlying the selection of the compositions (which were not optimized) and presents results of preliminary tests made to determine effects of the compositions upon the low-temperature capabilities of Li-CFx cells, relative to a baseline composition of LiBF4 at a concentration of 1.0 M in a solvent comprising equal volume parts of PC and DME.

  9. Improved Low-Temperature Performance of Li-Ion Cells Using New Electrolytes

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Buga, Ratnakumar V.; Gozdz, Antoni S.; Mani, Suresh

    2010-01-01

    As part of the continuing efforts to develop advanced electrolytes to improve the performance of lithium-ion cells, especially at low temperatures, a number of electrolyte formulations have been developed that result in improved low-temperature performance (down to 60 C) of 26650 A123Systems commercial lithium-ion cells. The cell type/design, in which the new technology has been demonstrated, has found wide application in the commercial sector (i.e., these cells are currently being used in commercial portable power tools). In addition, the technology is actively being considered for hybrid electric vehicle (HEV) and electric vehicle (EV) applications. In current work, a number of low-temperature electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed, which include the use of ternary mixtures of carbonates, the use of ester co-solvents [e.g., methyl butyrate (MB)], and optimized lithium salt concentrations (e.g., LiPF6), were compared with the commercial baseline electrolyte, as well as an electrolyte being actively considered for DoE HEV applications and previously developed by a commercial enterprise, namely LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC)(30:70%).

  10. Li conductivity in siloxane-based polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Stacy, Eric; Fan, Fei; Feng, Hongbo; Gainaru, Catalin; Mays, Jimmy; Sokolov, Alexei

    Polymer electrolytes containing lithium ions are ideal candidates for electrochemical devices and energy storage applications. Understanding their ionic transport mechanism is the key for rational designing of highly conductive polymer matrices. Complementing dielectric spectroscopy investigations by results from rheology and differential scanning calorimetry we focused on the interplay between dynamics of lithium ions and the polymer matrix based on polysiloxane backbone. Our results demonstrate that the conductivity and the degree of decoupling between ion dynamics and structural relaxation depend strongly not only on the ions concentration, but also on the polarity and size of the polymeric side-groups. Chemical Science Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States.

  11. Electrolytes with Improved Safety Characteristics for High Voltage, High Specific Energy Li-ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Krause, F. C.; Hwang, C.; West, W. C.; Soler, J.; Whitcanack, L. W.; Prakash, G. K. S.; Ratnakumar, B. V.

    2012-01-01

    (1) NASA is actively pursuing the development of advanced electrochemical energy storage and conversion devices for future lunar and Mars missions; (2) The Exploration Technology Development Program, Energy Storage Project is sponsoring the development of advanced Li-ion batteries and PEM fuel cell and regenerative fuel cell systems for the Altair Lunar Lander, Extravehicular Activities (EVA), and rovers and as the primary energy storage system for Lunar Surface Systems; (3) At JPL, in collaboration with NASA-GRC, NASA-JSC and industry, we are actively developing advanced Li-ion batteries with improved specific energy, energy density and safety. One effort is focused upon developing Li-ion battery electrolyte with enhanced safety characteristics (i.e., low flammability); and (4) A number of commercial applications also require Li-ion batteries with enhanced safety, especially for automotive applications.

  12. Current-induced composition gradients in molten LiCl-KCl battery electrolytes

    SciTech Connect

    Braunstein, J.; Cantor, S.; Vallet, C.E.

    1985-01-01

    Current induced composition gradients were demonstrated in molten LiCl-KCl eutectic mixture, the electrolyte of a LiAl/LiCl-KCl/FeS/sub x/ battery. The gradients were produced by electrolysis of the salt between LiAl electrodes at currents of 50-100 mA cm/sup -2/, and quenching. Analysis of composition profiles in quenched samples was by atomic absorption spectroscopy (AA), which gave good precision, and by x-ray fluorescence spectroscopy in a scanning electron microscope (SEM/EDX), which gave good distance resolution. Work is in progress to improve the precision of the SEM/EDX measurements to that demonstrated in model systems. 5 references, 5 figures, 1 table.

  13. The effectiveness of electrolyte additives in fluorinated electrolytes for high voltage Li[Ni0.4Mn0.4Co0.2]O2/graphite pouch Li-ion cells

    NASA Astrophysics Data System (ADS)

    Xia, Jian; Petibon, R.; Xiao, A.; Lamanna, W. M.; Dahn, J. R.

    2016-10-01

    The effectiveness of electrolyte additives in fluorinated electrolytes containing 1 M LiPF6/fluoroethylene carbonate:bis (2,2,2-trifluoroethyl) carbonate (1:1 w:w) were studied in high voltage Li(Ni0.4Mn0.4Co0.2)O2/graphite pouch cells tested to 4.5 V. The results showed that fluorinated electrolytes containing prop-1-ene-1,3-sultone alone or in combination with other additives exhibited significant improvements in terms of coulombic efficiency and charge endpoint capacity slippage during UHPC cycling, voltage drop during storage, as well as capacity retention during long-term cycling compared with state-of-the-art ethylene carbonate-based (ethylene carbonate: ethylmethyl carbonate 3:7) or sulfolane-based electrolytes (sulfolane: ethylmethyl carbonate 3:7) with some promising additive blends. These results indicate that fluorinated electrolytes offer an interesting alternative for high voltage Li-ion batteries.

  14. Partially fluorinated solvent as a co-solvent for the non-aqueous electrolyte of Li/air battery

    NASA Astrophysics Data System (ADS)

    Zhang, Sheng S.; Read, Jeffrey

    2011-03-01

    In this work we study methyl nonafluorobutyl ether (MFE) and tris(2,2,2-trifluoroethyl) phosphite (TTFP), respectively, as a co-solvent for the non-aqueous electrolyte of Li-air battery. Results show that in certain solvent ratios, both solvents are able to increase the specific capacity of carbon in Li/O2 and Li/air cells. More interestingly, the improvement in discharge performance of the Li/air cells increases with discharge current density. These results cannot be explained by the ionic conductivity and viscosity data of the electrolytes since the participation of fluorinated co-solvents hardly changes viscosity of the solvent blends while reversely reduces ionic conductivity of the electrolyte. In particular, we find that a 30 wt.% (vs. solvent) addition of TTFP into a 0.2 m (molality) LiSO3CF3 PC electrolyte can significantly improve the discharge performance of Li/air cells, and that the resultant electrolyte is able to support long-term operation of Li/air cells in dry ambient environments due to its low volatility. We believe that the observed performance improvement is associated with the increased dissolution kinetics and solubility of oxygen in fluorinated solvent containing electrolyte.

  15. A Unique Hybrid Quasi-Solid-State Electrolyte for Li-O2 Batteries with Improved Cycle Life and Safety.

    PubMed

    Yi, Jin; Zhou, Haoshen

    2016-09-01

    In the context of the development of electric vehicle to solve the contemporary energy and environmental issues, the possibility of pushing future application of Li-O2 batteries as a power source for electric vehicles is particularly attractive. However, safety concerns, mainly derived from the use of flammable organic liquid electrolytes, become a major bottleneck for the strategically crucial applications of Li-O2 batteries. To overcome this issue, rechargeable solid-state Li-O2 batteries with enhanced safety is regarded as an appealing candidate. In this study, a hybrid quasi-solid-state electrolyte combing a polymer electrolyte with a ceramic electrolyte is first designed and explored for Li-O2 batteries. The proposed rechargeable solid-state Li-O2 battery delivers improved cycle life (>100 cycles) and safety. The feasibility study demonstrates that the hybrid quasi-solid-state electrolytes could be employed as a promising alternative strategy for the development of rechargeable Li-O2 batteries, hence encouraging more efforts devoted to explore other hybrid solid-state electrolytes for Li-O2 batteries upon future application. PMID:27487523

  16. A Unique Hybrid Quasi-Solid-State Electrolyte for Li-O2 Batteries with Improved Cycle Life and Safety.

    PubMed

    Yi, Jin; Zhou, Haoshen

    2016-09-01

    In the context of the development of electric vehicle to solve the contemporary energy and environmental issues, the possibility of pushing future application of Li-O2 batteries as a power source for electric vehicles is particularly attractive. However, safety concerns, mainly derived from the use of flammable organic liquid electrolytes, become a major bottleneck for the strategically crucial applications of Li-O2 batteries. To overcome this issue, rechargeable solid-state Li-O2 batteries with enhanced safety is regarded as an appealing candidate. In this study, a hybrid quasi-solid-state electrolyte combing a polymer electrolyte with a ceramic electrolyte is first designed and explored for Li-O2 batteries. The proposed rechargeable solid-state Li-O2 battery delivers improved cycle life (>100 cycles) and safety. The feasibility study demonstrates that the hybrid quasi-solid-state electrolytes could be employed as a promising alternative strategy for the development of rechargeable Li-O2 batteries, hence encouraging more efforts devoted to explore other hybrid solid-state electrolytes for Li-O2 batteries upon future application.

  17. Characterization of proton conducting blend polymer electrolyte using PVA-PAN doped with NH4SCN

    NASA Astrophysics Data System (ADS)

    Premalatha, M.; Mathavan, T.; Selvasekarapandian, S.; Genova, F. Kingslin Mary; Umamaheswari, R.

    2016-05-01

    Polymer electrolytes with proton conductivity based on blend polymer using polyvinyl alcohol (PVA) and poly acrylo nitrile (PAN) doped with ammonium thiocyanate have been prepared by solution casting method using DMF as solvent. The complex formation between the blend polymer and the salt has been confirmed by FTIR Spectroscopy. The amorphous nature of the blend polymer electrolytes have been confirmed by XRD analysis. The highest conductivity at 303 K has been found to be 3.25 × 10-3 S cm-1 for 20 mol % NH4SCN doped 92.5PVA:7.5PAN system. The increase in conductivity of the doped blend polymer electrolytes with increasing temperature suggests the Arrhenius type thermally activated process. The activation energy is found to be low (0.066 eV) for the highest conductivity sample.

  18. Non-aqueous solution preparation of doped and undoped Li{sub x}Mn{sub y}O{sub z}

    DOEpatents

    Boyle, T.J.; Voigt, J.A.

    1997-05-20

    A method is described for generation of phase-pure doped and undoped Li{sub x}Mn{sub y}O{sub z} precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder. 1 fig.

  19. Characterization of high-voltage cathodes in CsBr-LiBr-KBr eutectic electrolyte

    SciTech Connect

    GUIDOTTI,RONALD A.; REINHARDT,FREDERICK W.

    2000-04-20

    The transition-metal oxides LiMn{sub 2}O{sub 4}, MnO{sub 2}, CrO{sub 2}, and LiCoO{sub 2} were evaluated for possible use as high-voltage cathodes for potential geothermal power applications. These were coupled with Li(Si) anodes and a low-melting CsBr-LiBr-KBr eutectic electrolyte that melts at 228.5 C. Single-cell tests at 250 C and 300 C at 15.8 and 31.6 mA/cm{sup 2} showed that MnO{sub 2} performed the best overall and had the lowest polarization. A 5-cell battery test using LiMn{sub 2}O{sub 4} cathodes was only modestly successful due to possible parasitic chemical reactions between the cathode and electrolyte at the much higher temperature (500 C) during discharge. The overall energy densities for these cathode were still less than for FeS{sub 2}.

  20. Design of composite polymer electrolytes for Li ion batteries based on mechanical stability criteria

    SciTech Connect

    Kalnaus, Sergiy; Sabau, Adrian S; Tenhaeff, Wyatt E; Daniel, Claus; Dudney, Nancy J

    2012-01-01

    Mechanical properties and conductivity were computed for several composite polymer electrolyte structures. A multi-phase effective medium approach was used to estimate effective conductivity. The Mori-Tanaka approach was applied for calculating the effective stiffness tensor of the composites. An analysis of effective mechanical properties was performed in order to identify the composite structures, which would be capable of blocking the dendrites forming in Li-ion battery when Li metal is used as anode. The data on conductivity, elastic modulus, and Poisson s ratio can be used to formulate design criteria for solid electrolytes that would exhibit appropriate stiffness and compressibility to suppress lithium dendrite growth while maintaining high effective conductivities.

  1. Pseudo-binary electrolyte, LiBH4-LiCl, for bulk-type all-solid-state lithium-sulfur battery.

    PubMed

    Unemoto, Atsushi; Chen, ChunLin; Wang, Zhongchang; Matsuo, Motoaki; Ikeshoji, Tamio; Orimo, Shin-Ichi

    2015-01-26

    The ionic conduction and electrochemical and thermal stabilities of the LiBH4-LiCl solid-state electrolyte were investigated for use in bulk-type all-solid-state lithium-sulfur batteries. The LiBH4-LiCl solid-state electrolyte exhibiting a lithium ionic conductivity of [Formula: see text] at 373 K, forms a reversible interface with a lithium metal electrode and has a wide electrochemical potential window up to 5 V. By means of the high-energy mechanical ball-milling technique, we prepared a composite powder consisting of elemental sulfur and mixed conductive additive, i.e., Ketjen black and Maxsorb. In that composite powder, homogeneous dispersion of the materials is achieved on a nanometer scale, and thereby a high concentration of the interface among them is induced. Such nanometer-scale dispersals of both elemental sulfur and carbon materials play an important role in enhancing the electrochemical reaction of elemental sulfur. The highly deformable LiBH4-LiCl electrolyte assists in the formation of a high concentration of tight interfaces with the sulfur-carbon composite powder. The LiBH4-LiCl electrolyte also allows the formation of the interface between the positive electrode and the electrolyte layers, and thus the Li-ion transport paths are established at that interface. As a result, our battery exhibits high discharge capacities of 1377, 856, and 636 mAh g(-1) for the 1st, 2nd, and 5th discharges, respectively, at 373 K. These results imply that complex hydride-based solid-state electrolytes that contain Cl-ions in the crystal would be integrated into rechargeable batteries.

  2. Pseudo-binary electrolyte, LiBH4-LiCl, for bulk-type all-solid-state lithium-sulfur battery

    NASA Astrophysics Data System (ADS)

    Unemoto, Atsushi; Chen, ChunLin; Wang, Zhongchang; Matsuo, Motoaki; Ikeshoji, Tamio; Orimo, Shin-ichi

    2015-06-01

    The ionic conduction and electrochemical and thermal stabilities of the LiBH4-LiCl solid-state electrolyte were investigated for use in bulk-type all-solid-state lithium-sulfur batteries. The LiBH4-LiCl solid-state electrolyte exhibiting a lithium ionic conductivity of log ≤ft( σ /S c{{m}-1} \\right)=-3.3 at 373 K, forms a reversible interface with a lithium metal electrode and has a wide electrochemical potential window up to 5 V. By means of the high-energy mechanical ball-milling technique, we prepared a composite powder consisting of elemental sulfur and mixed conductive additive, i.e., Ketjen black and Maxsorb. In that composite powder, homogeneous dispersion of the materials is achieved on a nanometer scale, and thereby a high concentration of the interface among them is induced. Such nanometer-scale dispersals of both elemental sulfur and carbon materials play an important role in enhancing the electrochemical reaction of elemental sulfur. The highly deformable LiBH4-LiCl electrolyte assists in the formation of a high concentration of tight interfaces with the sulfur-carbon composite powder. The LiBH4-LiCl electrolyte also allows the formation of the interface between the positive electrode and the electrolyte layers, and thus the Li-ion transport paths are established at that interface. As a result, our battery exhibits high discharge capacities of 1377, 856, and 636 mAh g-1 for the 1st, 2nd, and 5th discharges, respectively, at 373 K. These results imply that complex hydride-based solid-state electrolytes that contain Cl-ions in the crystal would be integrated into rechargeable batteries.

  3. Modern battery electrolytes: ion-ion interactions in Li+/Na+ conductors from DFT calculations.

    PubMed

    Jónsson, Erlendur; Johansson, Patrik

    2012-08-14

    Sodium-ion batteries, the sodium counterpart of the ubiquitous lithium-ion batteries, are currently being developed as a complementary technology to assure resource availability. As battery electrolytes tend to be one of the more limiting parts of any battery for both performance and life-length, chemical and physical data on sodium-ion battery electrolytes are important for rational development. Here the cation-anion interaction, a key property of any salt used in an electrolyte, of a number of salts is probed using numerous DFT methods via the ion-pair dissociation reaction: AlkAn ⇌ Alk(+) + An(-), where An(-) is any anion and Alk(+) is Na(+) or Li(+), the latter used here for a straight-forward literature and methodology comparison. Furthermore, the applicability of different DFT functionals for these types of calculations is benchmarked vs. a robust higher accuracy method (G4MP2). PMID:22751486

  4. LiCl/PVA gel electrolyte stabilizes vanadium oxide nanowire electrodes for pseudocapacitors.

    PubMed

    Wang, Gongming; Lu, Xihong; Ling, Yichuan; Zhai, Teng; Wang, Hanyu; Tong, Yexiang; Li, Yat

    2012-11-27

    Here we report a new strategy to improve the electrochemical stability of vanadium oxide electrodes for pseudocapacitors. Vanadium oxides are known to suffer from severe capacitance loss during charging/discharging cycling, due to chemical dissolution and ion intercalation/deintercalation-induced material pulverization. We demonstrate that these two issues can be addressed by using a neutral pH LiCl/PVA gel electrolyte. The function of the gel electrolyte is twofold: (i) it reduces the chemical dissolution of amphoteric vanadium oxides by minimizing water content and providing a neutral pH medium and (ii) it serves as a matrix to maintain the vanadium oxide nanowire network structure. Vanadium oxide nanowire pseudocapacitors with gel electrolyte exhibit excellent capacitance retention rates of more than 85% after cycling for 5000 cycles, without sacrificing the electrochemical performance of vanadium oxides.

  5. Optimized Li-Ion Electrolytes Containing Triphenyl Phosphate as a Flame-Retardant Additive

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Bugga, Ratnakumar V.; Prakash, G. K. Surya; Krause, Frederick C.

    2011-01-01

    A number of future NASA missions involving the exploration of the Moon and Mars will be human-rated and thus require high-specific-energy rechargeable batteries that possess enhanced safety characteristics. Given that Li-ion technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. There is also a strong desire to develop Li-ion batteries with improved safety characteristics for terrestrial applications, most notably for hybrid electric vehicle (HEV) and plug-in hybrid electric vehicle (PHEV) automotive applications. Therefore, extensive effort has been devoted recently to developing non-flammable electrolytes to reduce the flammability of the cells/battery. A number of electrolyte formulations have been developed, including systems that (1) incorporate greater concentrations of the flame-retardant additive (FRA); (2) use di-2,2,2-trifluoroethyl carbonate (DTFEC) as a co-solvent; (3) use 2,2,2- trifluoroethyl methyl carbonate (TFEMC); (4) use mono-fluoroethylene carbonate (FEC) as a co-solvent and/or a replacement for ethylene carbonate in the electrolyte mixture; and (5) utilize vinylene carbonate as a "SEI promoting" electrolyte additive, to build on the favorable results previously obtained. To extend the family of electrolytes developed under previous work, a number of additional electrolyte formulations containing FRAs, most notably triphenyl phosphate (TPP), were investigated and demonstrated in experimental MCMB (mesocarbon micro beads) carbon- LiNi(0.8)Co(0.2)O2 cells. The use of higher concentrations of the FRA is known to reduce the flammability of the electrolyte solution, thus, a concentration range was investigated (i.e., 5 to 20 percent by volume). The desired concentration of the FRA is the highest amount tolerable without adversely affecting the performance in terms of reversibility, ability to operate over a wide temperature range, and

  6. Studies on the thermal breakdown of common Li-ion battery electrolyte components

    DOE PAGESBeta

    Lamb, Joshua; Orendorff, Christopher J.; Roth, Emanuel Peter; Langendorf, Jill Louise

    2015-08-06

    While much attention is paid to the impact of the active materials on the catastrophic failure of lithium ion batteries, much of the severity of a battery failure is also governed by the electrolytes used, which are typically flammable themselves and can decompose during battery failure. The use of LiPF6 salt can be problematic as well, not only catalyzing electrolyte decomposition, but also providing a mechanism for HF production. This work evaluates the safety performance of the common components ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) in the context of the gasses producedmore » during thermal decomposition, looking at both the quantity and composition of the vapor produced. EC and DEC were found to be the largest contributors to gas production, both producing upwards of 1.5 moles of gas/mole of electrolyte. DMC was found to be relatively stable, producing very little gas regardless of the presence of LiPF6. EMC was stable on its own, but the addition of LiPF6 catalyzed decomposition of the solvent. As a result, while gas analysis did not show evidence of significant quantities of any acutely toxic materials, the gasses themselves all contained enough flammable components to potentially ignite in air.« less

  7. Studies on the thermal breakdown of common Li-ion battery electrolyte components

    SciTech Connect

    Lamb, Joshua; Orendorff, Christopher J.; Roth, Emanuel Peter; Langendorf, Jill Louise

    2015-08-06

    While much attention is paid to the impact of the active materials on the catastrophic failure of lithium ion batteries, much of the severity of a battery failure is also governed by the electrolytes used, which are typically flammable themselves and can decompose during battery failure. The use of LiPF6 salt can be problematic as well, not only catalyzing electrolyte decomposition, but also providing a mechanism for HF production. This work evaluates the safety performance of the common components ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) in the context of the gasses produced during thermal decomposition, looking at both the quantity and composition of the vapor produced. EC and DEC were found to be the largest contributors to gas production, both producing upwards of 1.5 moles of gas/mole of electrolyte. DMC was found to be relatively stable, producing very little gas regardless of the presence of LiPF6. EMC was stable on its own, but the addition of LiPF6 catalyzed decomposition of the solvent. As a result, while gas analysis did not show evidence of significant quantities of any acutely toxic materials, the gasses themselves all contained enough flammable components to potentially ignite in air.

  8. Study of novel nonflammable electrolytes in Sandia-built Li-ion cells.

    SciTech Connect

    Nagasubramanian, Ganesan; Orendorff, Christopher J.

    2010-04-01

    Even after decades of research, Li-ion cells still lack thermal stability. A number of approaches, including adding fire retardants or fluoro compounds to the electrolyte to mitigate fire, have been investigated. These additives improved the thermal stability of the cells (only marginally) but not enough for use in transportation applications. Recent investigations indicate that hydrofluoro-ethers are promising as nonflammable additives1. We describe here the results of our studies on electrolytes containing the hydrofluoro-ethers in cells fabricated at Sandia. In particular, we are investigating two solvents as nonflammable additives. These are: (1) 2-trifluoromethyl-3-methoxyperfluoropentane {l_brace}TMMP{r_brace} and (2) 2-trifluoro-2-fluoro-3-difluoropropoxy-3-difluoro-4-fluoro-5-trifluoropentane {l_brace}TPTP{r_brace}. These electrolytes not only have good thermal stability compared to the conventional electrolytes but respectable ionic conductivity. Sandia made 18650 cells successfully completed the formational cycle. The impedance behavior is typical of Li-ion cells.

  9. SEI Formation and Interfacial Stability of a Si Electrode in a LiTDI-Salt Based Electrolyte with FEC and VC Additives for Li-Ion Batteries.

    PubMed

    Lindgren, Fredrik; Xu, Chao; Niedzicki, Leszek; Marcinek, Marek; Gustafsson, Torbjörn; Björefors, Fredrik; Edström, Kristina; Younesi, Reza

    2016-06-22

    An electrolyte based on the new salt, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI), is evaluated in combination with nano-Si composite electrodes for potential use in Li-ion batteries. The additives fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are also added to the electrolyte to enable an efficient SEI formation. By employing hard X-ray photoelectron spectroscopy (HAXPES), the SEI formation and the development of the active material is probed during the first 100 cycles. With this electrolyte formulation, the Si electrode can cycle at 1200 mAh g(-1) for more than 100 cycles at a coulombic efficiency of 99%. With extended cycling, a decrease in Si particle size is observed as well as an increase in silicon oxide amount. As opposed to LiPF6 based electrolytes, this electrolyte or its decomposition products has no side reactions with the active Si material. The present results further acknowledge the positive effects of SEI forming additives. It is suggested that polycarbonates and a high LiF content are favorable components in the SEI over other kinds of carbonates formed by ethylene carbonate (EC) and dimethyl carbonate (DMC) decomposition. This work thus confirms that LiTDI in combination with the investigated additives is a promising salt for Si electrodes in future Li-ion batteries. PMID:27220376

  10. Structural and Mechanistic Insights into Fast Lithium-Ion Conduction in Li4SiO4-Li3PO4 Solid Electrolytes.

    PubMed

    Deng, Yue; Eames, Christopher; Chotard, Jean-Noël; Lalère, Fabien; Seznec, Vincent; Emge, Steffen; Pecher, Oliver; Grey, Clare P; Masquelier, Christian; Islam, M Saiful

    2015-07-22

    Solid electrolytes that are chemically stable and have a high ionic conductivity would dramatically enhance the safety and operating lifespan of rechargeable lithium batteries. Here, we apply a multi-technique approach to the Li-ion conducting system (1-z)Li4SiO4-(z)Li3PO4 with the aim of developing a solid electrolyte with enhanced ionic conductivity. Previously unidentified superstructure and immiscibility features in high-purity samples are characterized by X-ray and neutron diffraction across a range of compositions (z = 0.0-1.0). Ionic conductivities from AC impedance measurements and large-scale molecular dynamics (MD) simulations are in good agreement, showing very low values in the parent phases (Li4SiO4 and Li3PO4) but orders of magnitude higher conductivities (10(-3) S/cm at 573 K) in the mixed compositions. The MD simulations reveal new mechanistic insights into the mixed Si/P compositions in which Li-ion conduction occurs through 3D pathways and a cooperative interstitial mechanism; such correlated motion is a key factor in promoting high ionic conductivity. Solid-state (6)Li, (7)Li, and (31)P NMR experiments reveal enhanced local Li-ion dynamics and atomic disorder in the solid solutions, which are correlated to the ionic diffusivity. These unique insights will be valuable in developing strategies to optimize the ionic conductivity in this system and to identify next-generation solid electrolytes.

  11. Investigation of interfacial resistance between LiCoO 2 cathode and LiPON electrolyte in the thin film battery

    NASA Astrophysics Data System (ADS)

    Jeong, Eunkyung; Hong, Chan; Tak, Yongsug; Nam, Sang Cheol; Cho, Sungbaek

    All solid-state thin film battery was prepared with conventional sputtering technologies. Low conductivity of lithium phosphorus oxynitride (LiPON) electrolyte and higher resistance at the interface of LiCoO 2/LiPON was crucial for the development of thin film battery. Presence of thermally treated Al 2O 3 thin film at the interface of LiCoO 2/LiPON decreased the interfacial resistance and increased the discharge capacity with the better cycling behaviors. Surface analysis and electrochemical impedance measurement indicate the formation of solid solution LiCo 1- yAl yO 2 at the interface of LiCoO 2/LiPON.

  12. Thermal stability of LiPF 6 salt and Li-ion battery electrolytes containing LiPF 6

    NASA Astrophysics Data System (ADS)

    Yang, Hui; Zhuang, Guorong V.; Ross, Philip N.

    The thermal stability of the neat lithium hexafluorophosphate (LiPF 6) salt and of 1 molal (m) solutions of LiPF 6 in prototypical Li-ion battery solvents was studied with thermogravimetric analysis (TGA) and on-line Fourier transform infrared (FTIR). Pure LiPF 6 salt is thermally stable up to 107 °C in a dry inert atmosphere, and its decomposition path is a simple dissociation producing lithium fluoride (LiF) as solid and PF 5 as gaseous products. In the presence of water (300 ppm) in the carrier gas, its decomposition onset temperature is lowered as a result of direct thermal reaction between LiPF 6 and water vapor to form phosphorous oxyfluoride (POF 3) and hydrofluoric acid (HF). No new products were observed in 1 m solutions of LiPF 6 in ethylene carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) by on-line TGA-FTIR analysis. The storage of the same solutions in sealed containers at 85 °C for 300-420 h did not produce any significant quantity of new products as well. In particular, no alkylflurophosphates were found in the solutions after storage at elevated temperature. In the absence of either an impurity like alcohol or cathode active material that may (or may not) act as a catalyst, there is no evidence of thermally induced reaction between LiPF 6 and the prototypical Li-ion battery solvents EC, PC, DMC or EMC.

  13. Optimized Li-Ion Electrolytes Containing Fluorinated Ester Co-Solvents

    NASA Technical Reports Server (NTRS)

    Prakash, G. K. Surya; Smart, Marshall; Smith, Kiah; Bugga, Ratnakumar

    2010-01-01

    A number of experimental lithium-ion cells, consisting of MCMB (meso-carbon microbeads) carbon anodes and LiNi(0.8)Co(0.2)O2 cathodes, have been fabricated with increased safety and expanded capability. These cells serve to verify and demonstrate the reversibility, low-temperature performance, and electrochemical aspects of each electrode as determined from a number of electrochemical characterization techniques. A number of Li-ion electrolytes possessing fluorinated ester co-solvents, namely trifluoroethyl butyrate (TFEB) and trifluoroethyl propionate (TFEP), were demonstrated to deliver good performance over a wide temperature range in experimental lithium-ion cells. The general approach taken in the development of these electrolyte formulations is to optimize the type and composition of the co-solvents in ternary and quaternary solutions, focusing upon adequate stability [i.e., EC (ethylene carbonate) content needed for anode passivation, and EMC (ethyl methyl carbonate) content needed for lowering the viscosity and widening the temperature range, while still providing good stability], enhancing the inherent safety characteristics (incorporation of fluorinated esters), and widening the temperature range of operation (the use of both fluorinated and non-fluorinated esters). Further - more, the use of electrolyte additives, such as VC (vinylene carbonate) [solid electrolyte interface (SEI) promoter] and DMAc (thermal stabilizing additive), provide enhanced high-temperature life characteristics. Multi-component electrolyte formulations enhance performance over a temperature range of -60 to +60 C. With the need for more safety with the use of these batteries, flammability was a consideration. One of the solvents investigated, TFEB, had the best performance with improved low-temperature capability and high-temperature resilience. This work optimized the use of TFEB as a co-solvent by developing the multi-component electrolytes, which also contain non

  14. Sol-gel synthesis of aliovalent vanadium-doped LiNi(0.5)Mn(1.5)O(4) cathodes with excellent performance at high temperatures.

    PubMed

    Kim, Min Chul; Nam, Kyung-Wan; Hu, Enyuan; Yang, Xiao-Qing; Kim, Hyungsub; Kang, Kisuk; Aravindan, Vanchiappan; Kim, Woo-Seong; Lee, Yun-Sung

    2014-03-01

    Extraordinary performance at elevated temperature is achieved for high-voltage spinel-phase LiNi0.5 Mn1.5 O4 cathodes prepared using an adipic-acid-assisted sol-gel technique and doped with vanadium. V-substitution in the Li sites (Wykoff position 8a) is confirmed by V K-edge X-ray absorption spectroscopy and Rietveld refinement (Li0.995 V0.005 Ni0.5 Mn1.5 O4 ). V-doped LiNi0.5 Mn1.5 O4 delivered a reversible capacity of approximately 130 and 142 mAh g(-1) at ambient and elevated temperature conditions, respectively. Furthermore, the Li0.995 V0.005 Ni0.5 Mn1.5 O4 phase rendered approximately 94 % and 84 % of initial capacity compared to approximately 85 % and 3 % for the LiNi0.5 Mn1.5 O4 phase after 100 cycles in ambient and elevated temperature conditions, respectively. The enhancements are mainly because of the suppression of Mn dissolution and unwanted side reaction with electrolyte counterpart, and to the increase in conductivity, improving the electrochemical profiles for the V-doped phase. PMID:24399460

  15. Composite Gel Polymer Electrolyte Based on Poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) with Modified Aluminum-Doped Lithium Lanthanum Titanate (A-LLTO) for High-Performance Lithium Rechargeable Batteries.

    PubMed

    Le, Hang T T; Ngo, Duc Tung; Kalubarme, Ramchandra S; Cao, Guozhong; Park, Choong-Nyeon; Park, Chan-Jin

    2016-08-17

    A composite gel polymer electrolyte (CGPE) based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) polymer that includes Al-doped Li0.33La0.56TiO3 (A-LLTO) particles covered with a modified SiO2 (m-SiO2) layer was fabricated through a simple solution-casting method followed by activation in a liquid electrolyte. The obtained CGPE possessed high ionic conductivity, a large electrochemical stability window, and interfacial stability-all superior to that of the pure gel polymer electrolyte (GPE). In addition, under a highly polarized condition, the CGPE effectively suppressed the growth of Li dendrites due to the improved hardness of the GPE by the addition of inorganic A-LLTO/m-SiO2 particles. Accordingly, the Li-ion polymer and Li-O2 cells employing the CGPE exhibited remarkably improved cyclability compared to cells without CGPE. In particular, the CGPE as a protection layer for the Li metal electrode in a Li-O2 cell was effective in blocking the contamination of the Li electrode by oxygen gas or impurities diffused from the cathode side while suppressing the Li dendrites. PMID:27463563

  16. Temperature-Dependent Morphology, Magnetic and Optical Properties of Li-Doped MgO

    SciTech Connect

    Myrach, Philipp; Niklas, Nilius; Levchenko, Sergey; Gonchar, Anastasia; Risse, Thomas; Klaus-Peter, Dinse; Boatner, Lynn A; Frandsen, Wiebke; Horn, Raimund; Hans-Joachim, Freund; Schlçgl, Robert; Scheffler, Matthias

    2010-01-01

    Li-doped MgO is a potential catalyst for the oxidative coupling of methane, whereby surface Li+ O centers are suggested to be the chemically active species. To elucidate the role of Li in the MgO matrix, two model systems are prepared and their morphological, optical and magnetic properties as a function of Li doping are investigated. The first is an MgO film deposited on Mo(001) and doped with various amounts of Li, whereas the second is a powder sample fabricated by calcination of Li and Mg precursors in an oxygen atmosphere. Scanning tunneling and transmission electron microscopy are performed to characterize the morphology of both samples. At temperatures above 700 K, Li starts segregating towards the surface and forms irregular Li-rich oxide patches. Above 1050 K, Li desorbs from the MgO surface, leaving behind a characteristic defect pattern. Traces of Li also dissolve into the MgO, as concluded from a distinct optical signature that is absent in the pristine oxide. No electron paramagnetic resonance signal that would be compatible with Li+O centers is detected in the two Li/ MgO samples. Density-functional theory calculations are used to determine the thermodynamic stability of various Li-induced defects in the MgO. The calculations clarify the driving forces for Li segregation towards the MgO surface, but also rationalize the absence of Li+O centers. From the combination of experimental and theoretical results, a detailed picture arises on the role of Li for the MgO properties, which can be used as a starting point to analyze the chemical behavior of the doped oxide in future.

  17. Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li-O2 battery capacity.

    PubMed

    Burke, Colin M; Pande, Vikram; Khetan, Abhishek; Viswanathan, Venkatasubramanian; McCloskey, Bryan D

    2015-07-28

    Among the "beyond Li-ion" battery chemistries, nonaqueous Li-O2 batteries have the highest theoretical specific energy and, as a result, have attracted significant research attention over the past decade. A critical scientific challenge facing nonaqueous Li-O2 batteries is the electronically insulating nature of the primary discharge product, lithium peroxide, which passivates the battery cathode as it is formed, leading to low ultimate cell capacities. Recently, strategies to enhance solubility to circumvent this issue have been reported, but rely upon electrolyte formulations that further decrease the overall electrochemical stability of the system, thereby deleteriously affecting battery rechargeability. In this study, we report that a significant enhancement (greater than fourfold) in Li-O2 cell capacity is possible by appropriately selecting the salt anion in the electrolyte solution. Using (7)Li NMR and modeling, we confirm that this improvement is a result of enhanced Li(+) stability in solution, which, in turn, induces solubility of the intermediate to Li2O2 formation. Using this strategy, the challenging task of identifying an electrolyte solvent that possesses the anticorrelated properties of high intermediate solubility and solvent stability is alleviated, potentially providing a pathway to develop an electrolyte that affords both high capacity and rechargeability. We believe the model and strategy presented here will be generally useful to enhance Coulombic efficiency in many electrochemical systems (e.g., Li-S batteries) where improving intermediate stability in solution could induce desired mechanisms of product formation. PMID:26170330

  18. Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li-O2 battery capacity.

    PubMed

    Burke, Colin M; Pande, Vikram; Khetan, Abhishek; Viswanathan, Venkatasubramanian; McCloskey, Bryan D

    2015-07-28

    Among the "beyond Li-ion" battery chemistries, nonaqueous Li-O2 batteries have the highest theoretical specific energy and, as a result, have attracted significant research attention over the past decade. A critical scientific challenge facing nonaqueous Li-O2 batteries is the electronically insulating nature of the primary discharge product, lithium peroxide, which passivates the battery cathode as it is formed, leading to low ultimate cell capacities. Recently, strategies to enhance solubility to circumvent this issue have been reported, but rely upon electrolyte formulations that further decrease the overall electrochemical stability of the system, thereby deleteriously affecting battery rechargeability. In this study, we report that a significant enhancement (greater than fourfold) in Li-O2 cell capacity is possible by appropriately selecting the salt anion in the electrolyte solution. Using (7)Li NMR and modeling, we confirm that this improvement is a result of enhanced Li(+) stability in solution, which, in turn, induces solubility of the intermediate to Li2O2 formation. Using this strategy, the challenging task of identifying an electrolyte solvent that possesses the anticorrelated properties of high intermediate solubility and solvent stability is alleviated, potentially providing a pathway to develop an electrolyte that affords both high capacity and rechargeability. We believe the model and strategy presented here will be generally useful to enhance Coulombic efficiency in many electrochemical systems (e.g., Li-S batteries) where improving intermediate stability in solution could induce desired mechanisms of product formation.

  19. Li-doping process for Li xSiO-negative active material synthesized by chemical method for lithium-ion cells

    NASA Astrophysics Data System (ADS)

    Tabuchi, Toru; Yasuda, Hideo; Yamachi, Masanori

    Li-doped SiO-negative active material (Li xSiO) has been successfully synthesized by chemical method with immersion in Li-organic complex solution obtained by dissolving naphthalene and metallic Li into butyl methyl ether (BME) solvent. The rest potential of resultant Li xSiO electrode drastically shifts to less noble value at the beginning of immersion and tends to be stable at around 0.21 V versus Li/Li +, which means the progress of Li-doping into SiO-negative active material. Furthermore, this chemical Li-doping process proceeds by the catalysis function of naphthalene and leads to reduce the irreversible capacity of SiO-negative electrode caused by consumption of Li sources provided from positive electrode.

  20. Development of bulk-type all-solid-state lithium-sulfur battery using LiBH4 electrolyte

    NASA Astrophysics Data System (ADS)

    Unemoto, Atsushi; Yasaku, Syun; Nogami, Genki; Tazawa, Masaru; Taniguchi, Mitsugu; Matsuo, Motoaki; Ikeshoji, Tamio; Orimo, Shin-ichi

    2014-08-01

    Stable battery operation of a bulk-type all-solid-state lithium-sulfur battery was demonstrated by using a LiBH4 electrolyte. The electrochemical activity of insulating elemental sulfur as the positive electrode was enhanced by the mutual dispersion of elemental sulfur and carbon in the composite powders. Subsequently, a tight interface between the sulfur-carbon composite and the LiBH4 powders was manifested only by cold-pressing owing to the highly deformable nature of the LiBH4 electrolyte. The high reducing ability of LiBH4 allows using the use of a Li negative electrode that enhances the energy density. The results demonstrate the interface modification of insulating sulfur and the architecture of an all-solid-state Li-S battery configuration with high energy density.

  1. Irreversible morphological changes of a graphite negative-electrode at high potentials in LiPF6-based electrolyte solution.

    PubMed

    Domi, Yasuhiro; Doi, Takayuki; Tsubouchi, Shigetaka; Yamanaka, Toshiro; Abe, Takeshi; Ogumi, Zempachi

    2016-08-10

    The degradation mechanism of a graphite negative-electrode in LiPF6-based electrolyte solution was investigated using the basal plane of highly oriented pyrolytic graphite (HOPG) as a model electrode. Changes in the surface morphology were observed by in situ atomic force microscopy. In the initial cathodic scan, a number of pits appeared at around 1.75 V vs. Li(+)/Li, and fine particles formed on the terrace of the HOPG basal plane at about 1.5 V vs. Li(+)/Li. The fine particles were characterized by spectroscopic analysis, such as X-ray photoelectron spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy. We added one of the components to LiClO4-based electrolyte solution, and successfully reproduced the formation of pits and fine particles on the basal plane of HOPG. Based on these results, the formation mechanisms of pits and fine particle layers were proposed.

  2. Development of bulk-type all-solid-state lithium-sulfur battery using LiBH{sub 4} electrolyte

    SciTech Connect

    Unemoto, Atsushi Ikeshoji, Tamio; Yasaku, Syun; Matsuo, Motoaki; Nogami, Genki; Tazawa, Masaru; Taniguchi, Mitsugu; Orimo, Shin-ichi

    2014-08-25

    Stable battery operation of a bulk-type all-solid-state lithium-sulfur battery was demonstrated by using a LiBH{sub 4} electrolyte. The electrochemical activity of insulating elemental sulfur as the positive electrode was enhanced by the mutual dispersion of elemental sulfur and carbon in the composite powders. Subsequently, a tight interface between the sulfur-carbon composite and the LiBH{sub 4} powders was manifested only by cold-pressing owing to the highly deformable nature of the LiBH{sub 4} electrolyte. The high reducing ability of LiBH{sub 4} allows using the use of a Li negative electrode that enhances the energy density. The results demonstrate the interface modification of insulating sulfur and the architecture of an all-solid-state Li-S battery configuration with high energy density.

  3. Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

    SciTech Connect

    Costa, Luciano T.

    2015-07-14

    This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li{sup +} coordination and transportation were studied in the ternary electrolyte system, i.e., PEO{sub 16}LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

  4. Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

    NASA Astrophysics Data System (ADS)

    Costa, Luciano T.; Sun, Bing; Jeschull, Fabian; Brandell, Daniel

    2015-07-01

    This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li+ coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSIṡ1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

  5. Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend.

    PubMed

    Costa, Luciano T; Sun, Bing; Jeschull, Fabian; Brandell, Daniel

    2015-07-14

    This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li(+) coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

  6. Separators for Li-ion and Li-metal battery including ionic liquid based electrolytes based on the TFSI- and FSI- anions.

    PubMed

    Kirchhöfer, Marija; von Zamory, Jan; Paillard, Elie; Passerini, Stefano

    2014-08-22

    The characterization of separators for Li-ion or Li-metal batteries incorporating hydrophobic ionic liquid electrolytes is reported herein. Ionic liquids made of N-butyl-N-methylpyrrolidinium (PYR14+) or N-methoxyethyl-N-methylpyrrolidinium (PYR12O1+), paired with bis(trifluoromethanesulfonyl)imide (TFSI-) or bis(fluorosulfonyl)imide (FSI-) anions, were tested in combination with separators having different chemistries and morphologies in terms of wetting behavior, Gurley and McMullin number, as well as Li/(Separator+Electrolyte) interfacial properties. It is shown that non-functionalized microporous polyolefin separators are poorly wetted by FSI--based electrolytes (contrary to TFSI--based electrolytes), while the ceramic coated separator Separion® allows good wetting with all electrolytes. Furthermore, by comparing the lithium solid electrolyte interphase (SEI) resistance evolution at open circuit and during cycling, depending on separator morphologies and chemistries, it is possible to propose a scale for SEI forming properties in the order: PYR12O1FSI>PYR14FSI>PYR14TFSI>PYR12O1TFSI. Finally, the impact the separator morphology is evidenced by the SEI resistance evolution and by comparing Li electrodes cycled using separators with two different morphologies.

  7. Separators for Li-Ion and Li-Metal Battery Including Ionic Liquid Based Electrolytes Based on the TFSI− and FSI− Anions

    PubMed Central

    Kirchhöfer, Marija; von Zamory, Jan; Paillard, Elie; Passerini, Stefano

    2014-01-01

    The characterization of separators for Li-ion or Li-metal batteries incorporating hydrophobic ionic liquid electrolytes is reported herein. Ionic liquids made of N-butyl-N-methylpyrrolidinium (PYR14+) or N-methoxyethyl-N-methylpyrrolidinium (PYR12O1+), paired with bis(trifluoromethanesulfonyl)imide (TFSI−) or bis(fluorosulfonyl)imide (FSI−) anions, were tested in combination with separators having different chemistries and morphologies in terms of wetting behavior, Gurley and McMullin number, as well as Li/(Separator + Electrolyte) interfacial properties. It is shown that non-functionalized microporous polyolefin separators are poorly wetted by FSI−-based electrolytes (contrary to TFSI−-based electrolytes), while the ceramic coated separator Separion® allows good wetting with all electrolytes. Furthermore, by comparing the lithium solid electrolyte interphase (SEI) resistance evolution at open circuit and during cycling, depending on separator morphologies and chemistries, it is possible to propose a scale for SEI forming properties in the order: PYR12O1FSI > PYR14FSI > PYR14TFSI > PYR12O1TFSI. Finally, the impact the separator morphology is evidenced by the SEI resistance evolution and by comparing Li electrodes cycled using separators with two different morphologies. PMID:25153637

  8. Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters

    SciTech Connect

    Sacci, Robert L; Black, Jennifer M.; Wisinger, Nina; Dudney, Nancy J.; More, Karren Leslie; Unocic, Raymond R.

    2015-02-23

    The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase formation and Li electrodeposition from a standard battery electrolyte, we use in situ electrochemical scanning transmission electron microscopy for controlled potential sweep-hold electrochemical measurements with simultaneous BF and ADF STEM image acquisition. Through a combined quantitative electrochemical measurement and quantitative STEM imaging approach, based upon electron scattering theory, we show that chemically sensitive ADF STEM imaging can be used to estimate the density of evolving SEI constituents and distinguish contrast mechanisms of Li-bearing components in the liquid cell.

  9. Improved Wide Operating Temperature Range of LiNiCoAiO2-based Li-ion Cells with Methyl Propionate-based Electrolytes

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Tomcsi, Michael R.; Hwang, C.; Whitcanack, L. D.; Bugga, Ratnakumar V.; Nagata, Mikito; Visco, Vince; Tsukamoto, Hisashi

    2012-01-01

    Demonstration of wide operating temperature range Li-ion electrolytes Methyl propionate-based wide operating temperature range electrolytes were demonstrated to provide dramatic improvement of the low temperature capability of Quallion prototype Li-ion cells (MCMB-LiNiCoAlO2). Some formulations were observed to deliver over 60% of the room temperature capacity using a 5C rate at - 40oC !! Represents over a 4-fold improvement over the baseline electrolyte system. Demonstrated operational capability of a number of systems over a wide temperature range (-40 to +70 C) Demonstrated reasonably good long term cycle life performance at high temperature (i.e., at +40deg and +50 C) A number of formulations containing electrolytes additives (i.e., FEC, VC, LiBOB, and lithium oxalate) have been shown to have enhanced lithium kinetics at low temperature and promising high temperature resilience. Demonstrated good performance in larger capacity (12 Ah) Quallion Li-ion cells with methyl propionate-based electrolytes. Current efforts focused upon performing life studies and the impact upon low temperature capability.

  10. Electrolyte Mixtures Based on Ethylene Carbonate and Dimethyl Sulfone for Li-Ion Batteries with Improved Safety Characteristics.

    PubMed

    Hofmann, Andreas; Migeot, Matthias; Thißen, Eva; Schulz, Michael; Heinzmann, Ralf; Indris, Sylvio; Bergfeldt, Thomas; Lei, Boxia; Ziebert, Carlos; Hanemann, Thomas

    2015-06-01

    In this study, novel electrolyte mixtures for Li-ion cells are presented with highly improved safety features. The electrolyte formulations are composed of ethylene carbonate/dimethyl sulfone (80:20 wt/wt) as the solvent mixture and LiBF4 , lithium bis(trifluoromethanesulfonyl)azanide, and lithium bis(oxalato)borate as the conducting salts. Initially, the electrolytes are characterized with regard to their physical properties, their lithium transport properties, and their electrochemical stability. The key advantages of the electrolytes are high flash points of >140 °C, which enhance significantly the intrinsic safety of Li-ion cells containing these electrolytes. This has been quantified by measurements in an accelerating rate calorimeter. By using the newly developed electrolytes, which are liquid down to T=-10 °C, it is possible to achieve C-rates of up to 1.5 C with >80 % of the initial specific capacity. During 100 cycles in cell tests (graphite||LiNi1/3 Co1/3 Mn1/3 O2 ), it is proven that the retention of the specific capacity is >98 % of the third discharge cycle with dependence on the conducting salt. The best electrolyte mixture yields a capacity retention of >96 % after 200 cycles in coin cells. PMID:25950145

  11. Electrolyte Mixtures Based on Ethylene Carbonate and Dimethyl Sulfone for Li-Ion Batteries with Improved Safety Characteristics.

    PubMed

    Hofmann, Andreas; Migeot, Matthias; Thißen, Eva; Schulz, Michael; Heinzmann, Ralf; Indris, Sylvio; Bergfeldt, Thomas; Lei, Boxia; Ziebert, Carlos; Hanemann, Thomas

    2015-06-01

    In this study, novel electrolyte mixtures for Li-ion cells are presented with highly improved safety features. The electrolyte formulations are composed of ethylene carbonate/dimethyl sulfone (80:20 wt/wt) as the solvent mixture and LiBF4 , lithium bis(trifluoromethanesulfonyl)azanide, and lithium bis(oxalato)borate as the conducting salts. Initially, the electrolytes are characterized with regard to their physical properties, their lithium transport properties, and their electrochemical stability. The key advantages of the electrolytes are high flash points of >140 °C, which enhance significantly the intrinsic safety of Li-ion cells containing these electrolytes. This has been quantified by measurements in an accelerating rate calorimeter. By using the newly developed electrolytes, which are liquid down to T=-10 °C, it is possible to achieve C-rates of up to 1.5 C with >80 % of the initial specific capacity. During 100 cycles in cell tests (graphite||LiNi1/3 Co1/3 Mn1/3 O2 ), it is proven that the retention of the specific capacity is >98 % of the third discharge cycle with dependence on the conducting salt. The best electrolyte mixture yields a capacity retention of >96 % after 200 cycles in coin cells.

  12. Structure of the polymer electrolyte poly(ethylene oxide)6:LiAsF6

    NASA Astrophysics Data System (ADS)

    Macglashan, Graham S.; Andreev, Yuri G.; Bruce, Peter G.

    1999-04-01

    Polymer electrolytes-salts (such as LiCF3SO3) dissolved in solid, high-molar-mass polymers (for example, poly(ethylene oxide), PEO),,-hold the key to the development of all-solid-state rechargeable lithium batteries. They also represent an unusual class of coordination compounds in the solid state. Conductivities of up to 10-4Scm-1 may be obtained, but higher levels are needed for applications in batteries,,. To achieve such levels requires a better understanding of the conduction mechanism, and crucial to this is a knowledge of polymer-electrolyte structure. Crystalline forms of polymer electrolytes are obtained at only a few discrete compositions. The structures of 3:1 and 4:1 complexes (denoting the ratio of ether oxygens to cations) have been determined,,. But the 6:1 complex is of greater interest as the conductivity of polymer electrolytes increases significantly on raising the polymer content from 3:1 to 6:1 (refs 10, 11). Furthermore, many highly conducting polymer-electrolyte systems form crystalline 6:1 complexes whereas those with lower conductivities do not. Here we report the structure of the PEO:LiAsF6 complex with a 6:1 composition. Determination of the structure was carried out abinitio by employing a method for flexible molecular structures, involving full profile fitting to the X-ray powder diffraction data by simulated annealing. Whereas in the 3:1 complexes the polymer chains form helices, those in the 6:1 complex form double non-helical chains which interlock to form a cylinder. The lithium ions reside inside these cylinders and, in contrast to other complexes, are not coordinated by the anions.

  13. Neutron and X-ray scattering on Li-doped BPO 4

    NASA Astrophysics Data System (ADS)

    Jak, M. J. G.; Verhoeven, V. W. J.; de Schepper, I. M.; Mulder, F. M.; Kelder, E. M.; Schoonman, J.

    1999-05-01

    The structure of pure BPO 4 and Li-doped BPO 4 has been studied by neutron and X-ray scattering. Rietveld refinement of the neutron and X-ray spectra of the doped material did not show additional phases or a lithium superstructure. It appears that the interstitial Li +-ions as well as the charge compensating boron vacancies and substitutionally incorporated Li +-ions on boron sites are randomly distributed over the lattice resulting only in a slight change in peak intensities. The relevance of QENS for ceramic Li-ion batteries is discussed.

  14. Optically pumped cerium-doped LiSrAlF.sub.6 and LiCaAlF.sub.6

    DOEpatents

    Marshall, Christopher D.; Payne, Stephen A.; Krupke, William F.

    1996-01-01

    Ce.sup.3+ -doped LiSrAlF.sub.6 crystals are pumped by ultraviolet light which is polarized along the c axis of the crystals to effectively energize the laser system. In one embodiment, the polarized fourth harmonic light output from a conventional Nd:YAG laser operating at 266 nm is arranged to pump Ce:LiSrAlF.sub.6 with the pump light polarized along the c axis of the crystal. The Ce:LiSrAlF.sub.6 crystal may be placed in a laser cavity for generating tunable coherent ultraviolet radiation in the range of 280-320 nm. Additionally, Ce-doped crystals possessing the LiSrAlF.sub.6 type of chemical formula, e.g. Ce-doped LiCaAlF.sub.6 and LiSrGaF.sub.6, can be used. Alternative pump sources include an ultraviolet-capable krypton or argon laser, or ultraviolet emitting flashlamps. The polarization of the pump light will impact operation. The laser system will operate efficiently when light in the 280-320 nm gain region is injected or recirculated in the system such that the beam is also polarized along the c axis of the crystal. The Ce:LiSrAlF.sub.6 laser system can be configured to generate ultrashort pulses, and it may be used to pump other devices, such as an optical parametric oscillator.

  15. Optically pumped cerium-doped LiSrAlF{sub 6} and LiCaAlF{sub 6}

    DOEpatents

    Marshall, C.D.; Payne, S.A.; Krupke, W.F.

    1996-05-14

    Ce{sup 3+}-doped LiSrAlF{sub 6} crystals are pumped by ultraviolet light which is polarized along the c axis of the crystals to effectively energize the laser system. In one embodiment, the polarized fourth harmonic light output from a conventional Nd:YAG laser operating at 266 nm is arranged to pump Ce:LiSrAlF{sub 6} with the pump light polarized along the c axis of the crystal. The Ce:LiSrAlF{sub 6} crystal may be placed in a laser cavity for generating tunable coherent ultraviolet radiation in the range of 280-320 nm. Additionally, Ce-doped crystals possessing the LiSrAlF{sub 6} type of chemical formula, e.g. Ce-doped LiCaAlF{sub 6} and LiSrGaF{sub 6}, can be used. Alternative pump sources include an ultraviolet-capable krypton or argon laser, or ultraviolet emitting flashlamps. The polarization of the pump light will impact operation. The laser system will operate efficiently when light in the 280-320 nm gain region is injected or recirculated in the system such that the beam is also polarized along the c axis of the crystal. The Ce:LiSrAlF{sub 6} laser system can be configured to generate ultrashort pulses, and it may be used to pump other devices, such as an optical parametric oscillator. 10 figs.

  16. A LiAl/Cl2 battery with a four-component alkali-metal chloride electrolyte

    NASA Astrophysics Data System (ADS)

    Thomas, Daniel L.; Bennion, Douglas N.

    1989-12-01

    A LiAl/Cl2 cell operating at 280 C was investigated. This electrolyte is a mixture of LiC, KCl, RbCl, and CsCl with a eutectic melting point of 258 C. The positive electrode is a gas-diffusion electrode formed by coating one side of a porous carbon electrode with PTCE. The limiting discharge current of the cell was controlled by solid-state diffusion of Li in the LiAl alloy. Polarization of Cl2 electrode was caused by the low cross-sectional area of the electrolyte film compared with the pore cross-sectional area. Deactivation of the positive electrode was caused by impurities, such as Cu(+), in the electrolyte. Mathematical models of the negative and positive electrodes in a LiAl/Cl2 cell with a gas diffusion Cl2 electrode have been formulated. A thin film gas diffusion electrode model was used for the positive electrode, while solid-state diffusion of Li-in alpha-LiAl was assumed to limit the negative electrode and the cell current. Comparison of the experimental results with the model indicate that the diffusivity of Li in alpha-LiAl is of the order of 10 to the -12 sq cm/sec.

  17. Ferromagnetism in (Mn,Li) co-doped CdSe

    NASA Astrophysics Data System (ADS)

    Nabi, Z.; Ahuja, R.

    2008-12-01

    Ab initio calculations based on the density functional theory are reported for the Mn-doped CdSe for 5.5% and 12.5% Mn on a Cd sublattice. It is found that Mn-doped CdSe is antiferromagnetic. An essential ingredient to stabilize the ferromagnetism in bulk Cd1-xMnxSe can be realized by the co-doping of Li. We demonstrate that CdSe co-doped with Mn and Li has a stable ferromagnetic ground state and we show that the electronic structure of Cd1-2xMnxLixSe has a nearly metallic character.

  18. Fluorinated electrolyte for 4.5 V Li(Ni0.4Mn0.4Co0.2)O2/graphite Li-ion cells

    NASA Astrophysics Data System (ADS)

    Xia, Jian; Nie, M.; Burns, J. C.; Xiao, A.; Lamanna, W. M.; Dahn, J. R.

    2016-03-01

    A fluorinated electrolyte mixture, containing 1 M LiPF6/fluoroethylene carbonate:bis (2,2,2-trifluoroethyl) carbonate (1:1 w:w) with prop-1-ene-1,3-sultone as an electrolyte additive exhibited promising cycling and storage performance in Li(Ni0.4Mn0.4Co0.2)O2/graphite pouch type Li-ion cells tested to 4.5 V. The prop-1-ene-1,3-sultone additive was added to help control gas evolution in the fluorinated electrolyte cells, which was improved but still problematic even with the additive. Cells with the fluorinated electrolyte demonstrated higher impedance in early cycles compared to cells with carbonate solvents and state of the art additives. Symmetric cells were used to show this high impedance originated at the negative electrode/electrolyte interface. Nevertheless, in charge-discharge cycling tests to 4.5 V, cells with the fluorinated electrolyte and 1, 2 or 3% prop-1-ene-1,3-sultone additive, outperformed all non-fluorinated electrolytes with all additives tested. With further work, these, or other fluorinated carbonates, coupled with appropriate additives, may represent a viable path to NMC/graphite cells that can operate to 4.5 V and above.

  19. X-Ray absorption spectroscopy of LiBF4 in propylene carbonate: a model lithium ion battery electrolyte.

    PubMed

    Smith, Jacob W; Lam, Royce K; Sheardy, Alex T; Shih, Orion; Rizzuto, Anthony M; Borodin, Oleg; Harris, Stephen J; Prendergast, David; Saykally, Richard J

    2014-11-21

    Since their introduction into the commercial marketplace in 1991, lithium ion batteries have become increasingly ubiquitous in portable technology. Nevertheless, improvements to existing battery technology are necessary to expand their utility for larger-scale applications, such as electric vehicles. Advances may be realized from improvements to the liquid electrolyte; however, current understanding of the liquid structure and properties remains incomplete. X-ray absorption spectroscopy of solutions of LiBF4 in propylene carbonate (PC), interpreted using first-principles electronic structure calculations within the eXcited electron and Core Hole (XCH) approximation, yields new insight into the solvation structure of the Li(+) ion in this model electrolyte. By generating linear combinations of the computed spectra of Li(+)-associating and free PC molecules and comparing to the experimental spectrum, we find a Li(+)-solvent interaction number of 4.5. This result suggests that computational models of lithium ion battery electrolytes should move beyond tetrahedral coordination structures.

  20. Neutron scattering study on cathode LiMn2O4 and solid electrolyte 5(Li2O)(P2O5)

    NASA Astrophysics Data System (ADS)

    Kartini, E.; Putra, Teguh P.; Jahya, A. K.; Insani, A.; Adams, S.

    2014-09-01

    Neutron scattering is very important technique in order to investigate the energy storage materials such as lithium-ion battery. The unique advantages, neutron can see the light atoms such as Hydrogen, Lithium, and Oxygen, where those elements are negligible by other corresponding X-ray method. On the other hand, the energy storage materials, such as lithium ion battery is very important for the application in the electric vehicles, electronic devices or home appliances. The battery contains electrodes (anode and cathode), and the electrolyte materials. There are many challenging to improve the existing lithium ion battery materials, in order to increase their life time, cyclic ability and also its stability. One of the most scientific challenging is to investigate the crystal structure of both electrode and electrolyte, such as cathodes LiCoO2, LiMn2O4 and LiFePO4, and solid electrolyte Li3PO4. Since all those battery materials contain Lithium ions and Oxygen, the used of neutron scattering techniques to study their structure and related properties are very important and indispensable. This article will review some works of investigating electrodes and electrolytes, LiMn2O4 and 5(Li2O)(P2O5), by using a high resolution powder diffraction (HRPD) at the multipurpose research reactor, RSG-Sywabessy of the National Nuclear Energy Agency (BATAN), Indonesia.

  1. Fast Li ion dynamics in the solid electrolyte Li7 P3 S11 as probed by (6,7) Li NMR spin-lattice relaxation.

    PubMed

    Wohlmuth, Dominik; Epp, Viktor; Wilkening, Martin

    2015-08-24

    The development of safe and long-lasting all-solid-state batteries with high energy density requires a thorough characterization of ion dynamics in solid electrolytes. Commonly, conductivity spectroscopy is used to study ion transport; much less frequently, however, atomic-scale methods such as nuclear magnetic resonance (NMR) are employed. Here, we studied long-range as well as short-range Li ion dynamics in the glass-ceramic Li7 P3 S11 . Li(+) diffusivity was probed by using a combination of different NMR techniques; the results are compared with those obtained from electrical conductivity measurements. Our NMR relaxometry data clearly reveal a very high Li(+) diffusivity, which is reflected in a so-called diffusion-induced (6) Li NMR spin-lattice relaxation peak showing up at temperatures as low as 313 K. At this temperature, the mean residence time between two successful Li jumps is in the order of 3×10(8) s(-1) , which corresponds to a Li(+) ion conductivity in the order of 10(-4) to 10(-3) S cm(-1) . Such a value is in perfect agreement with expectations for the crystalline but metastable glass ceramic Li7 P3 S11 . In contrast to conductivity measurements, NMR analysis reveals a range of activation energies with values ranging from 0.17 to 0.26 eV, characterizing Li diffusivity in the bulk. In our case, through-going Li ion transport, when probed by using macroscopic conductivity spectroscopy, however, seems to be influenced by blocking grain boundaries including, for example, amorphous regions surrounding the Li7 P3 S11 crystallites. As a result of this, long-range ion transport as seen by impedance spectroscopy is governed by an activation energy of approximately 0.38 eV. The findings emphasize how surface and grain boundary effects can drastically affect long-range ionic conduction. If we are to succeed in solid-state battery technology, such effects have to be brought under control by, for example, sophisticated densification or through the preparation

  2. Doped carbon-sulfur species nanocomposite cathode for Li--S batteries

    SciTech Connect

    Wang, Donghai; Xu, Tianren; Song, Jiangxuan

    2015-12-29

    We report a heteroatom-doped carbon framework that acts both as conductive network and polysulfide immobilizer for lithium-sulfur cathodes. The doped carbon forms chemical bonding with elemental sulfur and/or sulfur compound. This can significantly inhibit the diffusion of lithium polysulfides in the electrolyte, leading to high capacity retention and high coulombic efficiency.

  3. Reversible ion exchange and structural stability of garnet-type Nb-doped Li7La3Zr2O12 in water for applications in lithium batteries

    NASA Astrophysics Data System (ADS)

    Liu, Cai; Rui, Kun; Shen, Chen; Badding, Michael E.; Zhang, Gaoxiao; Wen, Zhaoyin

    2015-05-01

    H+/Li+ ion exchange and structural stability of the high ionic conductivity Nb-doped Zr-garnet Li6.75La3Nb0.25Zr1.75O12 (LLNZO) are investigated in this study. Relationships between ion exchange and Li-population per unit cell, which are necessary to establish the practical framework of garnet electrolytes, are deduced for garnet oxides within ion-exchange process. H+/Li+ ion exchange of cubic LLNZO powder is performed continuously in distilled water and products with various exchange levels are obtained via this simple method. FTIR spectra show the evolution of H-O bonding through the ion-exchange process. A maximum of 74.8% exchange of Li+ by H+ was found, consistent with a preferential replacement of octahedrally coordinated Li. The cubic garnet phase is maintained throughout all levels of proton exchange observed. The formation of garnet-type solid solution of Li6.75-xHxLa3Nb0.25Zr1.75O12 is indicated by well-resolved lattice fringes as well as the linear evolution of crystal lattice parameters with the ion exchange level. The reverse ion exchange of H+ by Li+ is successfully achieved in Li+ containing aqueous solutions, demonstrating its high structural stability and good compatibility for promising applications in lithium batteries.

  4. Effect of Eutectic Concentration on Conductivity in PEO:LiX Based Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Zhan, Pengfei; Ganapatibhotla, Lalitha; Maranas, Janna

    Polyethylene oxide (PEO) and lithium salt based solid polymer electrolytes (SPEs) have been widely proposed as a substitution for the liquid electrolyte in Li-ion batteries. As salt concentration varies, these systems demonstrate rich phase behavior. Conductivity as a function of salt concentration has been measured for decades and various concentration dependences have been observed. A PEO:LiX mixture can have one or two conductivity maximums, while some mixtures with salt of high ionic strength will have higher conductivity as the salt concentration decrease. The factors that affect the conductivity are specific for each sample. The universal factor that affects conductivity is still not clear. In this work, we measured the conductivity of a series of PEO:LiX mixtures and statistical analysis shows conductivity is affected by the concentration difference from the eutectic concentration (Δc). The correlation with Δc is stronger than the correlation with glass transition temperature. We believe that at the eutectic concentration, during the solidification process, unique structures can form which aid conduction. Currently at Dow Chemical.

  5. Li doping to the 2212 phase in the BiSrCaCuO system

    NASA Astrophysics Data System (ADS)

    Fujiwara, Masashi; Nagae, Masahiro; Kusano, Yoshihiro; Fujii, Tatsuo; Takada, Jun

    1997-02-01

    The effects of Li doping on the formation process of the 2212 phase in the BiSrCaCuO system, and its structural and superconducting features were studied. Samples with nominal compositions of Bi:Sr:Ca:Cu:Li = 2:1.5:1.5:2: x where 0 ≤ x ≤ 0.6 were heated in air at temperatures ranging between 560°C and 850°C. Li doping greatly promoted the formation of the 2212 phase; the monophasic samples were rapidly obtained for x ≤ 0.4 by firing even at 730°C, which is about 100°C lower than that of the non-doped 2212 phase. A newly found oxide phase containing Li, which was formed below 710°C, is considered to play an important role as a precursor to accelerate the formation of the 2212 phase. The Li content in the monophasic samples determined by ICP analysis decreased to about a half of the nominal composition due to partial Li escape during heating. Monophasic composition range of the Li-doped 2212 phase was 0 ≤ y ≤ 0.19 as Bi 2Sr 1.5Ca 1.5Cu 2Li yO z. Increase in both lattice parameter c and oxygen content z with increasing Li content y in the 2212 phase was accompanied with a rise of Tc up to 90 K.

  6. Enhanced cycling performance of a Li metal anode in a dimethylsulfoxide-based electrolyte using highly concentrated lithium salt for a lithium-oxygen battery

    NASA Astrophysics Data System (ADS)

    Togasaki, Norihiro; Momma, Toshiyuki; Osaka, Tetsuya

    2016-03-01

    Stable charge-discharge cycling behavior for a lithium metal anode in a dimethylsulfoxide (DMSO)-based electrolyte is strongly desired of lithium-oxygen batteries, because the Li anode is rapidly exhausted as a result of side reactions during cycling in the DMSO solution. Herein, we report a novel electrolyte design for enhancing the cycling performance of Li anodes by using a highly concentrated DMSO-based electrolyte with a specific Li salt. Lithium nitrate (LiNO3), which forms an inorganic compound (Li2O) instead of a soluble product (Li2S) on a lithium surface, exhibits a >20% higher coulombic efficiency than lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium perchlorate, regardless of the loading current density. Moreover, the stable cycling of Li anodes in DMSO-based electrolytes depends critically on the salt concentration. The highly concentrated electrolyte 4.0 M LiNO3/DMSO displays enhanced and stable cycling performance comparable to that of carbonate-based electrolytes, which had not previously been achieved. We suppose this enhancement is due to the absence of free DMSO solvent in the electrolyte and the promotion of the desolvation of Li ions on the solid electrolyte interphase surface, both being consequences of the unique structure of the electrolyte.

  7. A study of tetrabromobisphenol A (TBBA) as a flame retardant additive for Li-ion battery electrolytes

    NASA Astrophysics Data System (ADS)

    Belov, Dmitry G.; Shieh, D. T.

    2014-02-01

    Electrochemical behavior and flammability of tetrabromobisphenol A (TBBA)-mixed electrolyte solutions are investigated using 1 mol L-1 LiPF6-EC:EMC (1:2 vol.%) with 0 wt.% (reference electrolyte) and 1-3 wt.% of TBBA. The cycling performance (at room and elevated temperature) and rate capability of the 18650 cell (LiMn2O4:Li(Ni1/3Co1/3Mn1/3)O2 (8:2)/Li4Ti5O12) cell containing TBBA-mixed electrolyte is similar to that of cell containing the reference electrolyte. A detailed analysis of the surface on both the anode and the cathode electrodes via X-ray photoelectron spectroscopy (XPS) indicated that the cathode electrode contains more Br components than the anode electrode. Within the first few cycles, on the positive electrode, we observe competing redox processes between the cathode material containing Mn and TBBA, which generate hydroxy radicals and other by-products. This process and the electrochemical reductive decomposition of TBBA to HBr, Br2 and bisphenole A are responsible for the increased flame retardant properties of the electrolyte containing TBBA. Safety tests were performed using an 18650 cell showed that even 1 wt.% of TBBA in the electrolyte significantly reduces cell flammability.

  8. Novel electrolyte mixtures based on dimethyl sulfone, ethylene carbonate and LiPF6 for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Hofmann, Andreas; Hanemann, Thomas

    2015-12-01

    In this study, novel electrolyte mixtures for Li-ion cells are presented which are composed of ethylene carbonate/dimethyl sulfone (80:20 wt./wt.) as a solvent mixture and LiPF6, lithium bis(oxalato)borate and lithium difluoro(oxalato)borate as conducting salts. The main advantages of the solvent mixture are high flash points of >140 °C which enhance the intrinsic safety of Li-ion cells while maintaining good cell performance above 0-5 °C. The movability of the lithium ions in the electrolyte is investigated via programmed current derivative chronopotentiometry. It is found that pure electrolyte properties cannot necessarily predict the electrolyte behavior in real Li-ion cells but the complex interplay between electrolytes, electrode materials and separators has to be taken into account. Using the newly developed electrolytes, it is possible to achieve C-rates up to 1.5C with >80% of the initial specific discharge capacity (25 °C). Within 200 cycles during one month in cell tests (C||NMC) it is proven that the retention of the specific capacity is >98% of the third discharge cycle in dependence of the conducting salt.

  9. PVA:LiClO4: a robust, high Tg polymer electrolyte for adjustable ion gating of 2D materials

    NASA Astrophysics Data System (ADS)

    Kinder, Erich; Fullerton, Susan; CenterLow Energy Systems Technology Team

    2015-03-01

    Polymer electrolytes are an effective way to gate organic semiconductors and nanomaterials, such as nanotubes and 2D materials, by establishing an electrostatic double layer with large capacitance. Widely used solid electrolytes, such as those based on polyethylene oxide, have a glass transition temperature below room temperature. This permits relatively fast ion mobility at T = 23 °C, but requires a constant applied field to maintain a doping profile. Moreover, PEO-based electrolytes cannot withstand a variety of solvents, limiting its use. Here, we demonstrate a polymer electrolyte using polyvinyl alcohol (PVA) with Tg >23 °C, through which a doping profile can be defined by a potential applied when the polymer is heated above Tg, then ``locked-in'' by cooling the electrolyte to room temperature (electrolyte gate bias. Hall bar measurements are used to quantify the charge carrier density. Owing to PVA's chemical stability, photolithography can be performed directly on the polymer electrolyte, which allows for the deposition of a patterned, metal gate directly on the electrolyte, as well as the ability to pattern the electrolyte itself. This work was supported in part by the Center for Low Energy Systems Technology (LEAST), one of the six SRC STARnet Centers, sponsored by MARCO and DARPA.

  10. DMAC and NMP as Electrolyte Additives for Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, Marshall; Bugga, Ratnakumar; Lucht, Brett

    2008-01-01

    Dimethyl acetamide (DMAC) and N-methyl pyrrolidinone (NMP) have been found to be useful as high-temperature-resilience-enhancing additives to a baseline electrolyte used in rechargeable lithium-ion electrochemical cells. The baseline electrolyte, which was previously formulated to improve low-temperature performance, comprises LiPF6 dissolved at a concentration of 1.0 M in a mixture comprising equal volume proportions of ethylene carbonate, diethyl carbonate, and dimethyl carbonate. This and other electrolytes comprising lithium salts dissolved in mixtures of esters (including alkyl carbonates) have been studied in continuing research directed toward extending the lower limits of operating temperatures and, more recently, enhancing the high-temperature resilience of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. Although these electrolytes provide excellent performance at low temperatures (typically as low as -40 C), when the affected Li-ion cells are subjected to high temperatures during storage and cycling, there occur irreversible losses of capacity accompanied by power fade and deterioration of low-temperature performance. The term "high-temperature resilience" signifies, loosely, the ability of a cell to resist such deterioration, retaining as much as possible of its initial charge/discharge capacity during operation or during storage in the fully charged condition at high temperature. For the purposes of the present development, a temperature is considered to be high if it equals or exceeds the upper limit (typically, 30 C) of the operating-temperature range for which the cells in question are generally designed.

  11. Magnetic properties of high Li doped ZnO sol–gel thin films

    SciTech Connect

    Vettumperumal, R.; Kalyanaraman, S.; Santoshkumar, B.; Thangavel, R.

    2014-02-01

    Highlights: • Ferromagnetism in high Li doped ZnO films. • Magnetic properties observed by Guoy's and VSM method. • The rod and wrinkle like structures are observed from the surface of the films. • Band gap of ZnO does not get altered by high Li doping. - Abstract: Undoped and Li doped ZnO thin films were deposited on a glass substrate using the sol–gel dip coating method. The films were prepared at 5 mol.% and 10 mol.% of Li doped ZnO at 550 °C annealing temperature and the deposited films were characterized by X-ray diffraction (XRD), microscopic studies, Gouy's method, vibrating sample magnetometer (VSM) and UV–visible spectroscopy. All the deposited thin films had a hexagonal wurtzite structure with polycrystalline grains at random. Primarily magnetic properties of pure and Li doped ZnO films were observed by Guoy's method which depicted Dia and Para magnetic behavior at room temperature. VSM measurement reveals a coercivity of 97.7 Oe in the films. An inverse relative ferromagnetism was perceived in Li doped ZnO films which had an average transmission of <90%.

  12. Y-doped Li8ZrO6: A Li-Ion Battery Cathode Material with High Capacity.

    PubMed

    Huang, Shuping; Wilson, Benjamin E; Wang, Bo; Fang, Yuan; Buffington, Keegan; Stein, Andreas; Truhlar, Donald G

    2015-09-01

    We study--experimentally and theoretically--the energetics, structural changes, and charge flows during the charging and discharging processes for a new high-capacity cathode material, Li8ZrO6 (LZO), which we study both pure and yttrium-doped. We quantum mechanically calculated the stable delithiated configurations, the delithiation energy, the charge flow during delithiation, and the stability of the delithiated materials. We find that Li atoms are easier to extract from tetrahedral sites than octahedral ones. We calculate a large average voltage of 4.04 eV vs Li/Li(+) for delithiation of the first Li atom in a primitive cell, which is confirmed by galvanostatic charge/discharge cycling data. Energy calculations indicate that topotactic delithiation is kinetically favored over decomposition into Li, ZrO2, and O2 during the charging process, although the thermodynamic energy of the topotactic reaction is less favorable. When one or two lithium atoms are extracted from a primitive cell of LZO, its volume and structure change little, whereas extraction of the third lithium greatly distorts the layered structure. The Li6ZrO6 and Li5ZrO6 delithiation products can be thermodynamically metastable to release of O2. Experimentally, materials with sufficiently small particle size for efficient delithiation and relithiation were achieved within an yttrium-doped LZO/carbon composite cathode that exhibited an initial discharge capacity of at least 200 mAh/g over the first 10 cycles, with 142 mAh/g maintained after 60 cycles. Computations predict that during the charging process, the oxygen ion near the Li vacancy is oxidized for both pure LZO and yttrium-doped LZO, which leads to a small-polaron hole. PMID:26264394

  13. Anodic polymerization of vinyl ethylene carbonate in Li-Ion battery electrolyte

    SciTech Connect

    Chen, Guoying; Zhuang, Guorong V.; Richardson, Thomas J.; Gao, Liu; Ross Jr., Philip N.

    2005-02-28

    A study of the anodic oxidation of vinyl ethylene carbonate (VEC) was conducted with post-mortem analysis of reaction products by ATR-FTIR and gel permeation chromatography (GPC). The half-wave potential (E1/2) for oxidation of VEC is ca. 3.6 V producing a resistive film on the electrode surface. GPC analysis of the film on a gold electrode produced by anodization of a commercial Li-ion battery electrolyte containing 2 percent VEC at 4.1 V showed the presence of a high molecular weight polymer. IR analysis indicated polycarbonate with alkyl carbonate rings linked by aliphatic methylene and methyl branches.

  14. B₂O₃-added lithium aluminium germanium phosphate solid electrolyte for Li-O₂ rechargeable batteries.

    PubMed

    Jadhav, Harsharaj S; Kalubarme, Ramchandra S; Jang, Seong-Yong; Jung, Kyu-Nam; Shin, Kyoung-Hee; Park, Chan-Jin

    2014-08-14

    B2O3-added Li(1.5)Al(0.5)Ge(1.5)(PO4)3 (LAGP) glass ceramics showing a room temperature ionic conductivity of 0.67 mS cm(-1) have been synthesized by using a melt-quenching method. The prepared glass ceramics are observed to be stable in tetraethylene glycol dimethyl ether containing lithium bis(trifluoromethane) sulfonamide. The augmented conductivity of the B2O3-added LAGP glass ceramic has improved the plateau potential during discharge. Furthermore, the B2O3-added LAGP glass ceramics are successfully employed as a solid electrolyte in a Li-O2 battery to obtain a stable cycling lifetime of up to 15 cycles with the limited capacity protocol.

  15. Lithium difluoro(oxalate)borate and LiBF4 blend salts electrolyte for LiNi0.5Mn1.5O4 cathode material

    NASA Astrophysics Data System (ADS)

    Zhou, Hongming; Xiao, Kaiwen; Li, Jian

    2016-01-01

    The electrochemical behaviors of lithium difluoro(oxalate)borate (LiODFB) and LiBF4 blend salts in ethylene carbonate + dimethyl carbonate + ethyl(methyl) carbonate (EC + DMC + EMC, 1:1:1, by wt.) have been investigated for LiNi0.5Mn1.5O4 cathode in lithium-ion batteries. The electric conductivity tests are utilized to examine the relationship among solution conductivity, the electrolyte composition and temperature. Through cyclic voltammetry, charge-discharge test and AC impedance measurements, we compare the capacity and cycling efficiency of LNMO cathode in different electrolyte systems at different temperatures and discharge current rates. Scanning electron microscopy (SEM) analysis and X-ray photoelectron spectroscopy (XPS) are served to analyze the surface nature of LNMO cathode after cycles at elevated temperature. These results demonstrate that LNMO cathode can exert excellent electrochemical performance with the increase of LiODFB concentration at room temperature and elevated temperature and it is found that just slight LiBF4, mixed with LiODFB as blend salts, can strikingly improve the cyclability at -20 °C, especially in high-rate cycling. Grouped together, the optimum LiODFB/LiBF4 molar ratio is around 4:1, which can present an excellent affinity to LNMO cathode in a wide electrochemical window.

  16. Tri(ethylene glycol)-substituted trimethylsilane/lithium bis(oxalate)borate electrolyte for LiMn2O4/graphite system

    NASA Astrophysics Data System (ADS)

    Kusachi, Yuki; Dong, Jian; Zhang, Zhengcheng; Amine, Khalil

    2011-10-01

    Silane-based electrolyte is a promising candidate for safer electrochemical energy storage devices because it is thermally and electrochemical stable, less flammable and environmental benign. In this paper, electrochemical properties of one of the silane-based electrolytes, tri(ethylene glycol)-substituted trimethylsilane (1NM3)-lithium bis(oxalate)borate (LiBOB) was studied using LiMn2O4 as cathode and MAG graphite as anode. When combined with LiBOB as lithium salt, the 1NM3-LiBOB electrolyte can provide solid electrolyte interface (SEI) formation due to the reductive decomposition of LiBOB at first charging cycle. Compared to the electrolyte used in the conventional lithium-ion batteries, 1NM3-LiBOB electrolyte showed compatible battery performance in LiMn2O4/MAG chemistry. The AC impedance measurement indicates that the activation energy (Ea) obtained from the charge transfer impedance for 1NM3-LiBOB was higher than that of the state-of-the-art electrolyte. Due to its low conductivity, the rate capability of 1NM3-LiBOB electrolyte needs to be improved.

  17. Alkylphosphate-based nonflammable gel electrolyte for LiMn 2O 4 positive electrode in lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Yoshimoto, Nobuko; Gotoh, Daisuke; Egashira, Minato; Morita, Masayuki

    Polymeric gel containing alkylphosphate has been examined as nonflammable gel electrolyte for LiMn 2O 4 positive electrode of lithium-ion battery (LIB). The gel was composed of a polymer matrix of poly(vinylidenefluoride- co-hexafluoropropylene) (PVdF-HFP) and a liquid component consisting of ternary solvent of trimethyl phosphate (TMP) mixed with ethylene carbonate (EC) and diethyl carbonate (DEC) that dissolves lithium salt (LiPF 6 or LiBF 4). The gel composition of 0.8 M (mol dm -3) LiX (X = PF 6 and BF 4) dissolved in EC + DEC + TMP (55:25:20) with PVdF-HFP showed excellent nonflammable characteristics and high ionic conductivity of ca. 3.1 mS cm -1 at room temperature (20 °C). The charge-discharge cycling test of LiMn 2O 4 positive electrode gave good reversibility with high capacitance in the gel electrolyte. With respect to the electrolyte salt, LiBF 4 was better than LiPF 6 due to its thermal stability during the gel preparation.

  18. A LiAl/Cl sub 2 battery with a four-component alkali-metal chloride electrolyte

    SciTech Connect

    Thomas, D.L. ); Bennion, D.N. )

    1989-01-01

    A LiAl/Cl{sub 2} cell operating at 280{degrees}C was investigated. The electrolyte is a mixture of LiCl, KCl, RbCl, and CsCl with a eutectic melting point of 258 {degrees}C. The positive electrode is a gas-diffusion electrode formed by coating one side of a porous carbon electrode with PTFE. The limiting discharge current of the cell was controlled by solid-state diffusion of Li in the LiA1 alloy. Polarization of the Cl{sub 2} electrode was caused by the low cross-sectional area of the electrolyte film compared with the pore cross-sectional area. Deactivation of the positive electrode was caused by impurities, such as Cu{sup +}, in the electrolyte. Mathematical models of the negative and positive electrodes in a LiAl/Cl{sub 2} cell with a gas diffusion Cl{sub 2} electrode have been formulated. A thin film gas diffusion electrode model was used for the positive electrode, while solid-state diffusion of Li in {alpha}-LiAl was assumed to limit the negative electrode and the cell current. The thin film is liquid salt on the porous electrode walls through which chlorine diffuses.

  19. Li2S encapsulated by nitrogen-doped carbon for lithium sulfur batteries

    DOE PAGESBeta

    Chen, Lin; Liu, Yuzi; Ashuri, Maziar; Liu, Caihong; Shaw, Leon L.

    2014-09-26

    Using high-energy ball milling of the Li2S plus carbon black mixture followed by carbonization of pyrrole, we have established a facile approach to synthesize Li2S-plus-C composite particles of average size 400 nm, encapsulated by a nitrogen-doped carbon shell. Such an engineered core–shell structure exhibits an ultrahigh initial discharge specific capacity (1029 mAh/g), reaching 88% of the theoretical capacity (1,166 mAh/g of Li2S) and thus offering the highest utilization of Li2S in the cathode among all of the reported works for the encapsulated Li2S cathodes. This Li2S/C composite core with a nitrogen-doped carbon shell can still retain 652 mAh/g after prolongedmore » 100 cycles. These superior properties are attributed to the nitrogen-doped carbon shell that can improve the conductivity to enhance the utilization of Li2S in the cathode. As a result, fine particle sizes and the presence of carbon black within the Li2S core may also play a role in high utilization of Li2S in the cathode.« less

  20. Treatment of electrochemical cell components with lithium tetrachloroaluminate (LiAlCl.sub.4) to promote electrolyte wetting

    DOEpatents

    Eberhart, James G.; Battles, James E.

    1980-01-01

    Electrochemical cell components such as interelectrode separators, retaining screens and current collectors are contacted with lithium tetrachloroaluminate prior to contact with molten electrolytic salt to improve electrolyte wetting. The LiAlCl.sub.4 can be applied in powdered, molten or solution form but, since this material has a lower melting point than the electrolytic salt used in high-temperature cells, the powdered LiAlCl.sub.4 forms a molten flux prior to contact by the molten electrolyte when both materials are initially provided in solid form. Components of materials such as boron nitride and other materials which are difficult to wet with molten salts are advantageously treated by this process.

  1. Ion conduction and relaxation in PEO-LiTFSI-Al2O3 polymer nanocomposite electrolytes

    NASA Astrophysics Data System (ADS)

    Das, S.; Ghosh, A.

    2015-05-01

    Ion conduction and relaxation in PEO-LiTFSI-Al2O3 polymer nanocomposite electrolytes have been studied for different concentrations of Al2O3 nanoparticles. X-ray diffraction and differential scanning calorimetric studies show that the maximum amorphous phase of PEO is observed for PEO-LiTFSI embedded with 5 wt. % Al2O3. The maximum ionic conductivity ˜3.3 × 10-4 S cm-1 has been obtained for this composition. The transmission electron microscopic image shows a distribution of Al2O3 nanoparticles in all compositions with size of <50 nm. The temperature dependence of the ionic conductivity follows Vogel-Tamman-Fulcher nature, indicating a strong coupling between ionic and polymer chain segmental motions. The scaling of the ac conductivity implies that relaxation dynamics follows a common mechanism for different temperatures and Al2O3 concentrations. The imaginary modulus spectra are asymmetric and skewed toward the high frequency sides of the maxima and analyzed using Havriliak-Negami formalism. The temperature dependence of the relaxation time obtained from modulus spectra also exhibits Vogel-Tamman-Fulcher nature. The values of the stretched exponent obtained from Kohlrausch-Williams-Watts fit to the modulus data are fairly low, suggesting highly non-exponential relaxation for all concentrations of Al2O3 in these electrolytes.

  2. Transport properties of the solid polymer electrolyte system P(EO){sub n}LiTFSI

    SciTech Connect

    Edman, L.; Doeff, M.M.; Ferry, A.; Kerr, J.; De Jonghe, L.C.

    2000-04-20

    Values for the lithium ion transference number ({tau}{sub +}{sup 0}) are reported for the solid polymer electrolyte system poly(ethylene oxide) (PEO) complexed with Li(CF{sub 3}SO{sub 2}){sub 2}N (LiTFSI). {tau}{sub +}{sup 0} ranges from 0.17 {+-} 0.17 to 0.60 {+-} 0.03 in the salt concentration (c) region of 742 to 2,982 mol/m{sup 3} at 85 C. The concentration dependence of {tau}{sub +}{sup 0} and the molar ionic conductivity ({Lambda}) are shown to be in good agreement with a free volume approach over the salt-rich composition range investigated. The present {tau}{sub +}{sup 0} results were obtained using an electrochemical technique based on concentrated solution theory. This experimentally straightforward method is herein demonstrated to give accurate results for a highly concentrated SPE system, without relying on any dubious simplifications regarding the state of the electrolyte.

  3. Effect of Ca-doping on the ionic conductivity of LiSi2N3

    NASA Astrophysics Data System (ADS)

    Narimatsu, E.; Yamamoto, Y.; Takeda, T.; Nishimura, T.; Hirosaki, N.

    2011-05-01

    Effect of Ca-doping on the ionic conductivity of LiSi2N3 was studied. The compositions of Li1-2xCaxSi2N3 (x=0-0.2) were synthesized by the reaction of Li3N, Si3N4, and Ca3N2 at temperature of 1873K-2073K. Ca was incorporated into the LiSi2N3 host lattice and formed the solid solution, Li1-2xCaxSi2N3. Activation energy for ionic conduction was decreased and ionic conductivity at room temperature was enhanced by Ca doping. At 298K, the ionic conductivity of densified Li1-2xCaxSi2N3 (x=0.075) ceramics achieved 1.6×10-5Sm-1, almost 4 orders of magnitude higher than that of densified Li1-2xCaxSi2N3(x=0) ceramics (3.1×10-9Sm-1). The LiSi2N3 framework change by Ca doping decreased the interaction between the ions and increased the defects of the structure. Thus, mobile Li+ ion could migrate easier. Moreover, incorporation of aliovalent substitutional Ca2+ ions in the LiSi2N3 lattice might be expected to create a Li+ vacancy (VLi) for charge compensation (Li1-2xCaxVLiSi2N3), thereby increasing the number of mobile Li+ ions.

  4. Electrolytes with Improved Safety Developed for High Specific Energy Li-Ion Cells with Si-Based Anodes

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Krause, F. C.; Hwang, C.; Soler, J.; West, W. C.; Ratnakumar, B. V.; Prakash, G. K. S.

    2012-01-01

    A number of electrolyte formulations that have improved safety characteristics have been developed for use with high capacity silicon-based anodes. To improve the compatibility with Si-based anodes, a number of technical approaches have been employed, including: (1) the use of mono-fluoroethylene carbonate (FEC) in conjunction with, or in lieu of, ethylene carbonate (EC), (2) the use of high proportions of fluorinated co-solvents, (3) the use of vinylene carbonate (VC) to stabilize the Si/C electrode, and (4) the use of lithium bis(oxalato)borate (LiBOB) to improve the compatibility of the electrolyte when Si/C electrodes are used in conjunction with high voltage cathodes. Candidate electrolytes were studied in Li/Si-C and Si-C/ Li(MnNiCo)O2 (NMC) coin cells, as well as in larger Si-C/NMC three-electrode cells equipped with lithium reference electrodes. In summary, many electrolytes that contain triphenyl phosphate (TPP), which is used as a flame retardant additive up to concentrations of 15 volume percent, and possess FEC as a co-solvent have been demonstrated to outperform the all-carbonate baseline electrolytes when evaluated in Si-C/ Li(MnNiCo)O2 cells.

  5. Improved electrical properties of Fe nanofiller impregnated PEO + PVP:Li+ blended polymer electrolytes for lithium battery applications

    NASA Astrophysics Data System (ADS)

    Naveen Kumar, K.; Saijyothi, K.; Kang, Misook; Ratnakaram, Y. C.; Hari Krishna, K.; Jin, Dahee; Lee, Yong Min

    2016-07-01

    Solid polymer-blended electrolyte films of polyethylene oxide (PEO) + polyvinyl pyrrolidone (PVP)/lithium perchlorate embedded with iron (Fe) nanofiller in different concentrations have been synthesized by a solution casting method. The semicrystalline nature of these polymer electrolyte films has been confirmed from their XRD profiles. Polymer complex formation and ion-polymer interactions are systematically studied by FTIR and laser Raman spectral analysis. Surface morphological studies are carried out from SEM analysis. Dispersed Fe nanofiller size evaluation study has been carried out using transmission electron microscopy (TEM). In order to evaluate the thermal stability, decomposition temperature, and thermogravimetric dynamics, we carried out the TG/DTA measurement. Upon addition of Fe nanofiller to the PEO + PVP/Li+ electrolyte system, it was found to result in the enhancement of ionic conductivity. The maximum ionic conductivity has been set up to be 1.14 × 10-4 Scm-1 at the optimized concentration of 4 wt% Fe nanofiller-embedded PEO + PVP/Li+ polymer electrolyte nanocomposite at an ambient temperature. PEO + PVP/Li+ + Fe nanofiller (4 wt%) cell exhibited better performance in terms of cell parameters. Based on the cell parameters, the 4 wt% Fe nanofiller-dispersed PEO + PVP/Li+ polymer electrolyte system could be suggested as a perspective candidate for solid-state battery applications.

  6. A High-Conduction Ge Substituted Li3AsS4 Solid Electrolyte with Exceptional Low Activation Energy

    SciTech Connect

    Sahu, Gayatri; Rangasamy, Ezhiylmurugan; Li, Juchuan; Chen, Yan; An, Ke; Dudney, Nancy J; Liang, Chengdu

    2014-01-01

    Lithium-ion conducting solid electrolytes show potential to enable high-energy-density secondary batteries and offer distinctive safety features as an advantage over traditional liquid electrolytes. Achieving the combination of high ionic conductivity, low activation energy, and outstanding electrochemical stability in crystalline solid electrolytes is a challenge for the synthesis of novel solid electrolytes. Herein we report an exceptionally low activation energy (Ea) and high room temperature superionic conductivity via facile aliovalent substitution of Li3AsS4 by Ge, which increased the conductivity by two orders of magnitude as compared to the parent compound. The composition Li3.334Ge0.334As0.666S4 has a high ionic conductivity of 1.12 mScm-1 at 27oC. Local Li+ hopping in this material is accompanied by distinctive low activation energy Ea of 0.17 eV being the lowest of Li+ solid conductors. Furthermore, this study demonstrates the efficacy of surface passivation of solid electrolyte to achieve compatibility with metallic lithium electrodes.

  7. Determining the 6Li doped side of a glass scintillator for ultra cold neutrons

    NASA Astrophysics Data System (ADS)

    Jamieson, Blair; Rebenitsch, Lori Ann

    2015-08-01

    Ultracold neutron (UCN) detectors using two visually very similar, to the microscopic level, pieces of optically contacted cerium doped lithium glasses have been proposed for high rate UCN experiments. The chief difference between the two glass scintillators is that one side is 6Li depleted and the other side 6Li doped. This note outlines a method to determine which side of the glass stack is doped with 6Li using AmBe and 252Cf neutron sources, and a Si surface barrier detector. The method sees an excess of events around the α and triton energies of neutron capture on 6Li when the enriched side is facing the Si surface barrier detector.

  8. In situ Raman and electrochemical characterization of the role of electrolyte additives in Li/SOCl2 batteries

    NASA Astrophysics Data System (ADS)

    Kovac, M.; Milicev, S.; Kovac, A.; Pejovnik, S.

    1995-05-01

    A simple glass cell has been constructed for in situ Raman characterization of discharge products in Li/SOCl2 batteries with polyvinyl chloride (PVC) and LiAl(SO3Cl4) additives. The assembly enables the characterization of catholyte-soluble discharge products in the electrolyte as well as products on the lithium and carbon electrode surfaces. The effect of the additives was also examined by scanning electron microscopy/energy dispersive spectroscopy and impedance spectroscopy and correlated to the voltage delay in batteries. The best results, as regards to the elimination of the delay effect, were obtained with a new electrolyte consisting of LiAlCl4/SOCl2 with an admixture of PVC and LiAl(SO3Cl4).

  9. Enhancement of Li+ ion conductivity in solid polymer electrolytes using surface tailored porous silica nanofillers

    NASA Astrophysics Data System (ADS)

    Mohanta, Jagdeep; Singh, Udai P.; Panda, Subhendu K.; Si, Satyabrata

    2016-09-01

    The current study represents the design and synthesis of polyethylene oxide (PEO)-based solid polymer electrolytes by solvent casting approach using surface tailored porous silica as nanofillers. The surface tailoring of porous silica nanostructure is achieved through silanization chemistry using 3-glycidyloxypropyl trimethoxysilane in which silane part get anchored to the silica surface whereas epoxy group get stellated from the silica surface. Surface tailoring of silica with epoxy group increases the room temperature electrochemical performances of the resulting polymer electrolytes. Ammonical hydrolysis of organosilicate precursor is used for both silica preparation and their surface tailoring. The composite solid polymer electrolyte films are prepared by solution mixing of PEO with lithium salt in presence of silica nanofillers and cast into film by solvent drying, which are then characterized by impedance measurement for conductivity study and wide angle x-ray diffraction for change in polymer crystallinity. Room temperature impedance measurement reveals Li+ ion conductivity in the order of 10‑4 S cm‑1, which is correlated to the decrease in PEO crystallinity. The enhancement of conductivity is further observed to be dependent on the amount of silica as well as on their surface characteristics.

  10. Enhancement of Li+ ion conductivity in solid polymer electrolytes using surface tailored porous silica nanofillers

    NASA Astrophysics Data System (ADS)

    Mohanta, Jagdeep; Singh, Udai P.; Panda, Subhendu K.; Si, Satyabrata

    2016-09-01

    The current study represents the design and synthesis of polyethylene oxide (PEO)-based solid polymer electrolytes by solvent casting approach using surface tailored porous silica as nanofillers. The surface tailoring of porous silica nanostructure is achieved through silanization chemistry using 3-glycidyloxypropyl trimethoxysilane in which silane part get anchored to the silica surface whereas epoxy group get stellated from the silica surface. Surface tailoring of silica with epoxy group increases the room temperature electrochemical performances of the resulting polymer electrolytes. Ammonical hydrolysis of organosilicate precursor is used for both silica preparation and their surface tailoring. The composite solid polymer electrolyte films are prepared by solution mixing of PEO with lithium salt in presence of silica nanofillers and cast into film by solvent drying, which are then characterized by impedance measurement for conductivity study and wide angle x-ray diffraction for change in polymer crystallinity. Room temperature impedance measurement reveals Li+ ion conductivity in the order of 10-4 S cm-1, which is correlated to the decrease in PEO crystallinity. The enhancement of conductivity is further observed to be dependent on the amount of silica as well as on their surface characteristics.

  11. Electrochemical properties of LiCoPO4-thin film electrodes in LiF-based electrolyte solution with anion receptors

    NASA Astrophysics Data System (ADS)

    Fukutsuka, Tomokazu; Nakagawa, Takuya; Miyazaki, Kohei; Abe, Takeshi

    2016-02-01

    Compatibility of LiF + anion receptors/propylene carbonate (PC) electrolyte solution with high potential positive electrode for lithium-ion batteries was examined by cyclic voltammetry. As anion receptors, tripropyl borate (TPB), tris(pentafluorophenyl) borane (TPFPB), and tris(hexafluoroisopropyl) borate (THFIPB) were used. LiCoPO4 thin-film electrodes were prepared by sol-gel method and used as both carbon- and binder-free model electrodes. From cyclic voltammograms, LiCoPO4 showed better cycleability in 0.1 mol dm-3 LiF + 0.1 mol dm-3 THFIPB/PC, however, other anion receptors did not give positive influence. It is indicated that the surface protecting layer from F--THFIPB complex and made LiCoPO4 stable. Electrochemical behavior depending on anion receptors was discussed according to reaction activity of F-.

  12. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li+/H+ exchange in aqueous solutions

    DOE PAGESBeta

    Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu; Sakamoto, Jeffrey; More, Karren Leslie; Chi, Miaofang

    2014-10-21

    Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long-term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7La3Zr2O12 garnet as a Li-stable solid electrolyte. The material underwent a Li+/H+ exchange in aqueous solutions. Nevertheless, its structure remained unchangedmore » even under a high exchange rate of 63.6%. When treated with a 2 M LiOH solution, the Li+/H+ exchange was reversed without any structural change. Furthermore, these observations suggest that cubic Li7La3Zr2O12 is a promising candidate for the separator in aqueous lithium batteries.« less

  13. Dynamic structural changes at LiMn2O4/electrolyte interface during lithium battery reaction.

    PubMed

    Hirayama, Masaaki; Ido, Hedekazu; Kim, KyungSu; Cho, Woosuk; Tamura, Kazuhisa; Mizuki, Jun'ichiro; Kanno, Ryoji

    2010-11-01

    Gaining a thorough understanding of the reactions on the electrode surfaces of lithium batteries is critical for designing new electrode materials suitable for high-power, long-life operation. A technique for directly observing surface structural changes has been developed that employs an epitaxial LiMn(2)O(4) thin-film model electrode and surface X-ray diffraction (SXRD). Epitaxial LiMn(2)O(4) thin films with restricted lattice planes (111) and (110) are grown on SrTiO(3) substrates by pulsed laser deposition. In situ SXRD studies have revealed dynamic structural changes that reduce the atomic symmetry at the electrode surface during the initial electrochemical reaction. The surface structural changes commence with the formation of an electric double layer, which is followed by surface reconstruction when a voltage is applied in the first charge process. Transmission electron microscopy images after 10 cycles confirm the formation of a solid electrolyte interface (SEI) layer on both the (111) and (110) surfaces and Mn dissolution from the (110) surface. The (111) surface is more stable than the (110) surface. The electrode stability of LiMn(2)O(4) depends on the reaction rate of SEI formation and the stability of the reconstructed surface structure. PMID:20939527

  14. Atomic-Scale Mechanisms for Electrolyte Decomposition in Li-ion Battery Cathodes

    NASA Astrophysics Data System (ADS)

    Fuhst, Mallory; Siegel, Donald

    Li-ion batteries using high energy density LiCoO2 (LCO) intercalation cathodes are known to generate gaseous species inside the cell, which can lead to venting flammable solvent vapor. It has been hypothesized that reactions at the cathode/electrolyte interface catalyze the production of these gaseous species. To elucidate the underlying reaction mechanism, first principles calculations were used to model interactions between LCO surfaces and Ethylene Carbonate (EC), a commonly used solvent in Li-ion batteries. A Metropolis Monte Carlo algorithm was used to identify likely low energy adsorption configurations for EC on the (10-14) surface of LCO. Several of these geometries were further analyzed with DFT. The thermodynamics and kinetics of EC decomposition were evaluated for plausible reaction pathways and associated various solvent decomposition mechanisms, such as hydrogen abstraction. Preliminary results indicate that hydrogen abstraction may lead to the spontaneous decomposition of EC into CO and other adsorbed species at the surface. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE 1256260.

  15. Predicting autoxidation stability of ether- and amide-based electrolyte solvents for Li-air batteries.

    PubMed

    Bryantsev, Vyacheslav S; Faglioni, Francesco

    2012-07-01

    Finding suitable solvents remains one of the most elusive challenges in rechargeable, nonaqueous Li-air battery technology. Although ether and amides are identified as stable classes of aprotic solvents against nucleophilic attack by superoxide, many of them are prone to autoxidation under oxygen atmosphere. In this work, we use density functional theory calculations coupled with an implicit solvent model to investigate the autoxidative stability of ether- and N,N-dialkylamide-based solvents. The change in the activation free energy for the C-H bond cleavage by O(2) is consistent with the extent of peroxide production for each class of solvent. Conversely, the thermodynamic stability alone is not sufficient to account for the observed variation in solvent reactivity toward O(2). A detailed understanding of the factors influencing the autoxidative stability provides several strategies for designing molecules with enhanced air/O(2) stability, comparable or superior to that of structurally related hydrocarbons. The mechanism of superoxide-mediated oxidation of hydroperoxides derived from ethers and amides is presented. The degradation mechanism accounts for the primary decomposition products (esters and carboxylates) observed in the Li-air battery with ether-based electrolytes. The identification of solvents having resistance to autoxidation is critical for the development of rechargeable Li-air batteries with long cycle life. PMID:22681046

  16. Predicting autoxidation stability of ether- and amide-based electrolyte solvents for Li-air batteries.

    PubMed

    Bryantsev, Vyacheslav S; Faglioni, Francesco

    2012-07-01

    Finding suitable solvents remains one of the most elusive challenges in rechargeable, nonaqueous Li-air battery technology. Although ether and amides are identified as stable classes of aprotic solvents against nucleophilic attack by superoxide, many of them are prone to autoxidation under oxygen atmosphere. In this work, we use density functional theory calculations coupled with an implicit solvent model to investigate the autoxidative stability of ether- and N,N-dialkylamide-based solvents. The change in the activation free energy for the C-H bond cleavage by O(2) is consistent with the extent of peroxide production for each class of solvent. Conversely, the thermodynamic stability alone is not sufficient to account for the observed variation in solvent reactivity toward O(2). A detailed understanding of the factors influencing the autoxidative stability provides several strategies for designing molecules with enhanced air/O(2) stability, comparable or superior to that of structurally related hydrocarbons. The mechanism of superoxide-mediated oxidation of hydroperoxides derived from ethers and amides is presented. The degradation mechanism accounts for the primary decomposition products (esters and carboxylates) observed in the Li-air battery with ether-based electrolytes. The identification of solvents having resistance to autoxidation is critical for the development of rechargeable Li-air batteries with long cycle life.

  17. Promising Cell Configuration for Next-Generation Energy Storage: Li2S/Graphite Battery Enabled by a Solvate Ionic Liquid Electrolyte.

    PubMed

    Li, Zhe; Zhang, Shiguo; Terada, Shoshi; Ma, Xiaofeng; Ikeda, Kohei; Kamei, Yutaro; Zhang, Ce; Dokko, Kaoru; Watanabe, Masayoshi

    2016-06-29

    Lithium-ion sulfur batteries with a [graphite|solvate ionic liquid electrolyte|lithium sulfide (Li2S)] structure are developed to realize high performance batteries without the issue of lithium anode. Li2S has recently emerged as a promising cathode material, due to its high theoretical specific capacity of 1166 mAh/g and its great potential in the development of lithium-ion sulfur batteries with a lithium-free anode such as graphite. Unfortunately, the electrochemical Li(+) intercalation/deintercalation in graphite is highly electrolyte-selective: whereas the process works well in the carbonate electrolytes inherited from Li-ion batteries, it cannot take place in the ether electrolytes commonly used for Li-S batteries, because the cointercalation of the solvent destroys the crystalline structure of graphite. Thus, only very few studies have focused on graphite-based Li-S full cells. In this work, simple graphite-based Li-S full cells were fabricated employing electrolytes beyond the conventional carbonates, in combination with highly loaded Li2S/graphene composite cathodes (Li2S loading: 2.2 mg/cm(2)). In particular, solvate ionic liquids can act as a single-phase electrolyte simultaneously compatible with both the Li2S cathode and the graphite anode and can further improve the battery performance by suppressing the shuttle effect. Consequently, these lithium-ion sulfur batteries show a stable and reversible charge-discharge behavior, along with a very high Coulombic efficiency.

  18. NMR Study of Ionic Distribution in Li-Doped BPO 4

    NASA Astrophysics Data System (ADS)

    Dodd, A. J.; van Eck, E. R. H.; Jak, M. J. G.; Kelder, E. M.; Schoonman, J.

    2000-09-01

    7Li nuclear magnetic resonance studies of a series of lithium-doped boron phosphates (LixB1-x/3PO4, 0Li ions in the lattice. It is shown that Li ions form in clusters, most likely around a boron vacancy. High-temperature measurements are used to obtain ionic mobility as a function of concentration, and activation energy for hopping of Li ions is shown to increase with concentration.

  19. 3D hierarchical assembly of ultrathin MnO2 nanoflakes on silicon nanowires for high performance micro-supercapacitors in Li- doped ionic liquid

    PubMed Central

    Dubal, Deepak P.; Aradilla, David; Bidan, Gérard; Gentile, Pascal; Schubert, Thomas J.S.; Wimberg, Jan; Sadki, Saïd; Gomez-Romero, Pedro

    2015-01-01

    Building of hierarchical core-shell hetero-structures is currently the subject of intensive research in the electrochemical field owing to its potential for making improved electrodes for high-performance micro-supercapacitors. Here we report a novel architecture design of hierarchical MnO2@silicon nanowires (MnO2@SiNWs) hetero-structures directly supported onto silicon wafer coupled with Li-ion doped 1-Methyl-1-propylpyrrolidinium bis(trifluromethylsulfonyl)imide (PMPyrrBTA) ionic liquids as electrolyte for micro-supercapacitors. A unique 3D mesoporous MnO2@SiNWs in Li-ion doped IL electrolyte can be cycled reversibly across a voltage of 2.2 V and exhibits a high areal capacitance of 13 mFcm−2. The high conductivity of the SiNWs arrays combined with the large surface area of ultrathin MnO2 nanoflakes are responsible for the remarkable performance of these MnO2@SiNWs hetero-structures which exhibit high energy density and excellent cycling stability. This combination of hybrid electrode and hybrid electrolyte opens up a novel avenue to design electrode materials for high-performance micro-supercapacitors. PMID:25985388

  20. 3D hierarchical assembly of ultrathin MnO2 nanoflakes on silicon nanowires for high performance micro-supercapacitors in Li- doped ionic liquid.

    PubMed

    Dubal, Deepak P; Aradilla, David; Bidan, Gérard; Gentile, Pascal; Schubert, Thomas J S; Wimberg, Jan; Sadki, Saïd; Gomez-Romero, Pedro

    2015-05-18

    Building of hierarchical core-shell hetero-structures is currently the subject of intensive research in the electrochemical field owing to its potential for making improved electrodes for high-performance micro-supercapacitors. Here we report a novel architecture design of hierarchical MnO2@silicon nanowires (MnO2@SiNWs) hetero-structures directly supported onto silicon wafer coupled with Li-ion doped 1-Methyl-1-propylpyrrolidinium bis(trifluromethylsulfonyl)imide (PMPyrrBTA) ionic liquids as electrolyte for micro-supercapacitors. A unique 3D mesoporous MnO2@SiNWs in Li-ion doped IL electrolyte can be cycled reversibly across a voltage of 2.2 V and exhibits a high areal capacitance of 13 mFcm(-2). The high conductivity of the SiNWs arrays combined with the large surface area of ultrathin MnO2 nanoflakes are responsible for the remarkable performance of these MnO2@SiNWs hetero-structures which exhibit high energy density and excellent cycling stability. This combination of hybrid electrode and hybrid electrolyte opens up a novel avenue to design electrode materials for high-performance micro-supercapacitors.

  1. Li-DOPING Effect on the Cathodoluminescent Properties of Y2O3:Eu3+ Phosphors

    NASA Astrophysics Data System (ADS)

    Bae, J. S.; Yoon, J. H.; Park, S. K.; Kim, J. P.; Jeong, E. D.; Won, M. S.; Jeong, J. H.; Shim, K. S.; Yang, H. K.; Yi, S. S.

    Influence of lithium doping on the crystallization, the surface morphology, the chemical states and the luminescent properties of Y2O3:Eu3+ phosphors was investigated. The structural, surface morphology characteristics and chemical states of the phosphors were analyzed by using X-ray diffraction (XRD), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS), respectively. The crystallinity, the surface morphology, and the cathodoluminescence (CL) of phosphors highly depended on the Li doping. The relationship between the crystalline and morphological structures and the luminescent properties was studied, and Li+ doping affected not only the crystallinity but also the luminescent brightness of Y2O3:Eu3+ phosphors. In particular, the incorporation of the Li+ ion into the Y2O3 lattice could induce remarkable increase in the CL intensity. The enhanced photoluminescence brightness with Li doping may result both from the improved crystallinity leading to higher oscillating strengths for the optical transitions, and the increased surface area due to the larger particle sizes. The strongest emission intensity was observed with Li doped Y2O3:Eu3+ ceramics whose brightness was increased by a factor of 1.8 in comparison with that of Y2O3:Eu3+ ceramics.

  2. Quadratic nonlinear optical parameters of 7% MgO-doped LiNbO3 crystal

    NASA Astrophysics Data System (ADS)

    Kulyk, B.; Kapustianyk, V.; Figà, V.; Sahraoui, B.

    2016-06-01

    Pure and 7% MgO-doped lithium niobate (LiNbO3) single crystals were grown by the Czochralski technique. The shift of optical absorption edge in 7% MgO-doped crystal in direction of shorter wavelength compared to undoped crystal was observed. The second harmonic generation measurements of 7% MgO-doped LiNbO3 crystal were performed at room temperature by means of the rotational Maker fringe technique using Nd:YAG laser generating at 1064 nm in picoseconds regime. Experimentally obtained value of nonlinear optical coefficient d33 for 7% MgO-doped LiNbO3 was found to be less than for undoped crystal but higher than for 5% MgO-doped. I-type phase-matched second harmonic generation was achieved and the value of phase-matched angle was calculated. High quadratic nonlinearity together with tolerance to intensive laser irradiation makes 7% MgO-doped LiNbO3 crystal interesting for application in optoelectronics.

  3. Temperature Dependence of Aliovalent-vanadium Doping in LiFePO4 Cathodes

    SciTech Connect

    Harrison, Katharine L; Bridges, Craig A; Paranthaman, Mariappan Parans; Idrobo Tapia, Juan C; Manthiram, Arumugam; Goodenough, J. B.; Segre, C; Katsoudas, John; Maroni, V. A.

    2013-01-01

    Vanadium-doped olivine LiFePO4 cathode materials have been synthesized by a novel low-temperature microwave-assisted solvothermal (MW-ST) method at 300 oC. Based on chemical and powder neutron/X-ray diffraction analysis, the compositions of the synthesized materials were found to be LiFe1-3x/2Vx x/2PO4 (0 x 0.2) with the presence of a small number of lithium vacancies charge-compensated by V4+, not Fe3+, leading to an average oxidation state of ~ 3.2+ for vanadium. Heating the pristine 15 % V-doped sample in inert or reducing atmospheres led to a loss of vanadium from the olivine lattice with the concomitant formation of a Li3V2(PO4)3 impurity phase; after phase segregation, a partially V-doped olivine phase remained. For comparison, V-doped samples were also synthesized by conventional ball milling and heating, but only ~ 10 % V could be accommodated in the olivine lattice in agreement with previous studies. The higher degree of doping realized with the MW-ST samples demonstrates the temperature dependence of the aliovalent-vanadium doping in LiFePO4.

  4. Niobium-doped titanium oxide anode and ionic liquid electrolyte for a safe sodium-ion battery

    NASA Astrophysics Data System (ADS)

    Usui, Hiroyuki; Domi, Yasuhiro; Shimizu, Masahiro; Imoto, Akinobu; Yamaguchi, Kazuki; Sakaguchi, Hiroki

    2016-10-01

    The anode properties of Nb-doped rutile TiO2 electrodes were investigated in an ionic liquid electrolyte comprised of N-methyl-N-propylpyrrolidinium cation and bis(fluorosulfonyl)amide anion for use in a safe Na-ion battery. Although the electrolyte's conductivity was lower than that of a conventional organic electrolyte at 30 °C, it showed high conductivity comparable to that of the organic electrolyte at 60 °C. The Nb-doped TiO2 electrode showed excellent cyclability in the ionic liquid electrolyte at 60 °C: a high capacity retention of 97% was observed even at the 350th cycle, which is comparable to value in the organic electrolyte (91%). In a non-flammability test in a closed system, no ignition was observed with the ionic liquid electrolyte even at 300 °C. These results indicate that combination of a Nb-doped TiO2 anode and ionic liquid electrolyte gives not only an excellent cyclability but also high safety for a Na-ion battery operating at a temperature below the sodium's melting point of 98 °C.

  5. Direct measurement of the chemical reactivity of silicon electrodes with LiPF6-based battery electrolytes

    SciTech Connect

    Veith, Gabriel M; Baggetto, Loic; Sacci, Robert L; Unocic, Raymond R; Tenhaeff, Wyatt E; Browning, Jim

    2014-01-01

    We report the first direct measurement of the chemistry and extent of reactivity between a lithium ion battery electrode surface (Si) and a liquid electrolyte (1.2M LiPF6-3:7 wt% ethylene carbonate:dimethyl carbonate). This layer is estimated to be 3.6 nm thick and partially originates from the consumption of the silicon surface.

  6. Investigation on the Charging Process of Li2O2-Based Air Electrodes in Li-O2 Batteries with Organic Carbonate Electrolytes

    SciTech Connect

    Xu, Wu; Viswanathan, Vilayanur V.; Wang, Deyu; Towne, Silas A.; Xiao, Jie; Nie, Zimin; Hu, Dehong; Zhang, Jiguang

    2011-04-15

    The charge processes of Li-O2 batteries were investigated by analyzing the gas evolution by in situ gas chromatography-mass spectroscopy (GC/MS) technique. The mixture of Li2O2/Fe3O4/Super P carbon/polyvinylidene fluoride (PVDF) was used as the starting air electrode material and 1M LiTFSI in carbonate-based solvents was used as electrolyte. It was found that Li2O2 is reactive to 1-methyl-2-pyrrolidinone and PVDF binder used in the electrode preparation. During the 1st charge (up to 4.6 V), O2 was the main component in the gases released. The amount of O2 measured by GC/MS was consistent with the amount of Li2O2 decomposed in the electrochemical process as measured by the charge capacity, indicative of the good chargeability of Li2O2. However, after the cell was discharged to 2.0 V in O2 atmosphere and re-charged to ~ 4.6 V in the second cycle, CO2 was dominant in the released gases. Further analysis of the discharged air electrode by X-ray diffraction and Fourier transform infrared spectroscopy indicated that lithium-containing carbonate species (lithium alkyl carbonate and/or Li2CO3) were the main reaction products. Therefore, compatible electrolyte and electrodes as well as the electrode preparation procedures need to be developed for long term operation of rechargeable Li-O2 or Li-air batteries.

  7. Nitrile functionalized disiloxanes with dissolved LiTFSI as lithium ion electrolytes with high thermal and electrochemical stability

    NASA Astrophysics Data System (ADS)

    Pohl, Benjamin; Hiller, Martin M.; Seidel, Sarah M.; Grünebaum, Mariano; Wiemhöfer, Hans-Dieter

    2015-01-01

    Liquid disiloxanes functionalized with terminal nitrile groups are introduced as alternative non-volatile solvents for lithium-ion battery electrolytes in combination with LiTFSI as lithium salt. Two series of disiloxanes were investigated differing with respect to the attachment of the nitrile containing side group to silicon, i.e. via a Si-C or a Si-O bond. Total conductivities up to 1 mS cm-1 at 30 °C were measured by impedance spectroscopy. Electrochemical characterization was done on half cells using LiFePO4 cathodes by cyclic voltammetry and constant current cycling. Attractive issues and advantages of the investigated LiTFSI containing disiloxanes in comparison to current electrolyte solvents are: a) In spite of the presence of LiTFSI, the aluminum pitting corrosion is suppressed, b) the electrochemical stability window is extended on the cathode side up to 5.6 V vs. Li/Li+, for a LiTFSI concentration of 0.7 mol kg-1, c) the reported nitrile functionalized disiloxanes show excellent thermal stability with a boiling point up to 106 °C (0.1 mbar), a rather low glass transition temperature of -107 °C, while no melting/crystallization was observed.

  8. Optical and surface properties of optically transparent Li3 PO4 solid electrolyte layer for transparent solid batteries.

    PubMed

    Pat, Suat; Özen, Soner; Şenay, Volkan; Korkmaz, Şadan

    2016-07-01

    In this study, optical and surface properties of the optically transparent Li3 PO4 solid electrolyte layer for transparent solid battery have been investigated for the first time. To determine the optical properties, transmittance, absorbance, reflection, refractive index spectra, and optical band gap were determined by UV-Vis spectrophotometer and optical interferometer. The surface property of the transparent Li3 PO4 solid electrolyte was analyzed using atomic force microscopy. One another important parameter is contact angle (CA) surface free energy (SFE). CA and SFE were determined by optical tensiometer. These values probably are a most important parameter for polymer and hybrid battery performance. For the best performance, value of CA should be low. As a result, solid electrolyte layer is a highly transparent and it has a high wettability. SCANNING 38:317-321, 2016. © 2015 Wiley Periodicals, Inc.

  9. Characterization of conducting cellulose acetate based polymer electrolytes doped with "green" ionic mixture.

    PubMed

    Ramesh, S; Shanti, R; Morris, Ezra

    2013-01-01

    Polymer electrolytes were developed by solution casting technique utilizing the materials of cellulose acetate (CA), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and deep eutectic solvent (DES). The DES is synthesized from the mixture of choline chloride and urea of 1:2 ratios. The increasing DES content well plasticizes the CA:LiTFSI:DES matrix and gradually improves the ionic conductivity and chemical integrity. The highest conducting sample was identified for the composition of CA:LiTFSI:DES (28 wt.%:12 wt.%:60 wt.%), which has the greatest ability to retain the room temperature ionic conductivity over the entire 30 days of storage time. The changes in FTIR cage peaks upon varying the DES content in CA:LiTFSI:DES prove the complexation. This complexation results in the collapse of CA matrix crystallinity, observed from the reduced intensity of XRD diffraction peaks. The DES-plasticized sample is found to be more heat-stable compared to pure CA. Nevertheless, the addition of DES diminishes the CA:LiTFSI matrix's heat-resistivity but at the minimum addition the thermal stability is enhanced. PMID:23044100

  10. Nanoscale imaging of fundamental li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters.

    PubMed

    Sacci, Robert L; Black, Jennifer M; Balke, Nina; Dudney, Nancy J; More, Karren L; Unocic, Raymond R

    2015-03-11

    The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase (SEI) formation and to track Li nucleation and growth mechanisms from a standard organic battery electrolyte (LiPF6 in EC:DMC), we used in situ electrochemical scanning transmission electron microscopy (ec-S/TEM) to perform controlled electrochemical potential sweep measurements while simultaneously imaging site-specific structures resulting from electrochemical reactions. A combined quantitative electrochemical measurement and STEM imaging approach is used to demonstrate that chemically sensitive annular dark field STEM imaging can be used to estimate the density of the evolving SEI and to identify Li-containing phases formed in the liquid cell. We report that the SEI is approximately twice as dense as the electrolyte as determined from imaging and electron scattering theory. We also observe site-specific locations where Li nucleates and grows on the surface and edge of the glassy carbon electrode. Lastly, this report demonstrates the investigative power of quantitative nanoscale imaging combined with electrochemical measurements for studying fluid-solid interfaces and their evolving chemistries.

  11. Ab initio molecular dynamics simulations of organic electrolytes, electrodes, and lithium ion transport for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Kent, P. R. C.; Ganesh, P.; Jiang, De-En; Borodin, O.

    2012-02-01

    Optimizing the choice of electrolyte in lithium ion batteries and an understanding of the solid-electrolyte interphase (SEI) is required to optimize the balance between high-energy storage, high rate capability, and lifetime. We perform accurate ab initio molecular-dynamics simulations of common cyclic carbonates and LiPF6 to build solvation models which explain available Neutron and NMR spectroscopies. Our results corroborate why ethylene carbonate is a preferred choice for battery applications over propylene carbonate and how mixtures with dimethyl carbonate improve Li-ion diffusion. We study the role of functionalization of graphite-anode edges on the reducibility of the electrolyte and the ease of Li-ion intercalation at the initial stages of SEI formation. We find that oxygen terminated edges readily act as strong reductive sites, while hydrogen terminated edges are less reactive and allow faster Li diffusion. Orientational ordering of the solvent molecules precedes reduction at the interphase. Inorganic reductive components are seen to readily migrate to the anode edges, leading to increased surface passivation of the anode. We are currently quantifying Li-intercalation barriers across realistic SEI models, and progress along these lines will be presented.

  12. LiAl/Cl/sub 2/ battery with a four-component alkali-metal chloride electrolyte

    SciTech Connect

    Thomas, D.L.

    1986-01-01

    A LiAl/Cl/sub 2/ cell operating at 280/sup 0/ was demonstrated. The electrolyte is a mixture of LiCl, KCl, RbCl, and CsCL with a eutectic melting point of 258/sup 0/C. Physical properties of the melt and the Cl/sub 2/-melt system were measured. Two types of Cl/sub 2/ electrodes were tested. The discharge current in the flow-through Cl/sub 2/ electrode was limited by the high viscosity of the electrolyte (40 cP), which limited the flow rate and Cl/sub 2/ supply through the graphite cloth electrode. Currents as high as 50 mA/cm/sup 2/ were observed with the gas-diffusion Cl/sub 2/ electrode. The capacity of the cell was limited by the LiAl electrode. The gas-diffusion electrode reaction volume was modeled as a meniscus film in a cylindrical pore. The model indicates that high polarization of the positive electrode is caused by the small ratio of film cross-sectional area to pore cross-sectional area, necessitating high film currents to support modest bulk electrolyte currents. Modeling indicated that the negative electrode rate was limited by solid-state diffusion of Li through the LiAl.

  13. A systematic study of well-known electrolyte additives in LiCoO2/graphite pouch cells

    NASA Astrophysics Data System (ADS)

    Wang, David Yaohui; Sinha, N. N.; Petibon, R.; Burns, J. C.; Dahn, J. R.

    2014-04-01

    The effectiveness of well-known electrolyte additives singly or in combination on LiCoO2/graphite pouch cells has been systematically investigated and compared using the ultra high precision charger (UHPC) at Dalhousie University and electrochemical impedance spectroscopy (EIS). UHPC studies are believed to identify the best electrolyte additives singly or in combination within a short time period (several weeks). Three parameters: 1) the coulombic efficiency (CE); 2) the charge endpoint capacity slippage (slippage) and 3) the charge transfer resistance (Rct), of LiCoO2/graphite pouch cells with different electrolyte additives singly or in combination were measured and the results for over 55 additive sets are compared. The experimental results suggest that a combination of electrolyte additives can be more effective than a single electrolyte additive. However, of all the additive sets tested, simply using 2 wt.% vinylene carbonate yielded cells very competitive in CE, slippage and Rct. It is hoped that this comprehensive report can be used as a guide and reference for the study of other electrolyte additives singly or in combination.

  14. Charge Saturation and Intrinsic Doping in Electrolyte-Gated Organic Semiconductors.

    PubMed

    Atallah, Timothy L; Gustafsson, Martin V; Schmidt, Elliot; Frisbie, C Daniel; Zhu, X-Y

    2015-12-01

    Electrolyte gating enables low voltage operation of organic thin film transistors, but little is known about the nature of the electrolyte/organic interface. Here we apply charge-modulation Fourier transform infrared spectroscopy, in conjunction with electrical measurements, on a model electrolyte gated organic semiconductor interface: single crystal rubrene/ion-gel. We provide spectroscopic signature for free-hole like carriers in the organic semiconductor and unambiguously show the presence of a high density of intrinsic doping of the free holes upon formation of the rubrene/ion-gel interface, without gate bias (Vg = 0 V). We explain this intrinsic doping as resulting from a thermodynamic driving force for the stabilization of free holes in the organic semiconductor by anions in the ion-gel. Spectroscopy also reveals the saturation of free-hole like carrier density at the rubrene/ion-gel interface at Vg < -0.5 V, which is commensurate with the negative transconductance seen in transistor measurements. PMID:26588805

  15. Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters

    DOE PAGESBeta

    Sacci, Robert L; Black, Jennifer M.; Wisinger, Nina; Dudney, Nancy J.; More, Karren Leslie; Unocic, Raymond R.

    2015-02-23

    The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase formation and Li electrodeposition from a standard battery electrolyte, we use in situ electrochemical scanning transmission electron microscopy for controlled potential sweep-hold electrochemical measurements with simultaneous BF and ADF STEM image acquisition. Through a combined quantitative electrochemical measurement and quantitative STEM imaging approach, based upon electron scattering theory, we show that chemically sensitive ADF STEM imaging can be used to estimate the density of evolving SEI constituents and distinguish contrast mechanisms of Li-bearing components in the liquidmore » cell.« less

  16. Conductive surface modification of LiFePO4 with nitrogen doped carbon layers for lithium-ion batteries

    SciTech Connect

    Yoon, Sukeun; Liao, Chen; Sun, Xiao-Guang; Bridges, Craig A; Unocic, Raymond R; Nanda, Jagjit; Dai, Sheng; Paranthaman, Mariappan Parans

    2012-01-01

    The LiFePO4 rod surface modified with nitrogen doped carbon layer has been prepared using hydrothermal processing followed by post-annealing in the presence of an ionic liquid. The coated LiFePO4 rod exhibits good capacity retention and high rate capability as the nitrogen doped carbon improves conductivity and prevents aggregation of the rod during cycling.

  17. Energetics of a Li Atom adsorbed on B/N doped graphene with monovacancy

    NASA Astrophysics Data System (ADS)

    Rani, Babita; Jindal, V. K.; Dharamvir, Keya

    2016-08-01

    We use density functional theory (DFT) to study the adsorption properties and diffusion of Li atom across B/N-pyridinic graphene. Regardless of the dopant type, B atoms of B-pyridinic graphene lose electron density. On the other hand, N atoms (p-type dopants) have tendency to gain electron density in N-pyridinic graphene. Higher chemical reactivity and electronic conductivity of B/N-pyridinic graphene are responsible for stronger binding of Li with the substrates as compared to pristine graphene. The binding energy of Li with B/N-pyridinic graphene exceeds the cohesive energy of bulk Li, making it energetically unfavourable for Li to form clusters on these substrates. Li atom gets better adsorbed on N-pyridinic graphene due to an additional p-p hybridization of the orbitals while Li on B-pyridinic prefers the ionic bonding. Also, significant distortion of N-pyridinic graphene upon Li adsorption is a consequence of the change in bonding mechanism between Li atom and the substrate. Our results show that bonding character and hence binding energies between Li and graphene can be tuned with the help of B/N doping of monovacancy defects. Further, the sites for most stable adsorption are different for the two types of doped and defective graphene, leading to greater Li uptake capacity of B-pyridinic graphene near the defect. In addition, B-pyridinic graphene offering lower diffusion barrier, ensures better Li kinetics. Thus, B-pyridinic graphene presents itself as a better anode material for LIBs as compared to N-pyridinic graphene.

  18. Mechanistic insights for the development of Li-O2 battery materials: addressing Li2O2 conductivity limitations and electrolyte and cathode instabilities.

    PubMed

    McCloskey, Bryan D; Burke, Colin M; Nichols, Jessica E; Renfrew, Sara E

    2015-08-18

    The Li-air battery has received significant attention over the past decade given its high theoretical specific energy compared to competing energy storage technologies. Yet, numerous scientific challenges remain unsolved in the pursuit of attaining a battery with modest Coulombic efficiency and high capacity. In this Feature Article, we provide our current perspective on challenges facing the development of nonaqueous Li-O2 battery cathodes. We initially present a review on our understanding of electrochemical processes occurring at the nonaqueous Li-O2 cathode. Electrolyte and cathode instabilities and Li2O2 conductivity limitations are then discussed, and suggestions for future materials research development to alleviate these issues are provided. PMID:26179598

  19. A hybrid Li-air battery with buckypaper air cathode and sulfuric acid electrolyte

    SciTech Connect

    Li, YF; Huang, K; Xing, YC

    2012-10-30

    We demonstrate a type of carbon nanotube based buckypaper cathode in a hybrid electrolyte Li-air battery (HyLAB) that showed outstanding discharging performances. The HyLAB has sulfuric acid as the catholyte and a large active electrode area (10 cm(2)). The active cathode layer was made from a buckypaper with 5 wt.% Pt supported on carbon nanotubes (Pt/CNTs) for oxygen reduction and evolution. A similar cathode was constructed with a catalyst of 5 wt.% Pt supported on carbon black (Pt/CB). It is demonstrated that sulfuric acid can achieve high discharging current densities while maintaining relatively high cell potentials. The cell with Pt/CNTs showed a much better performance than with Pt/CB at high current densities. The HyLAB with Pt/CNTs achieved a discharging capacity of 306 mAh/g and a cell voltage of 3.15 V at 0.2 mA/cm(2). The corresponding specific energy is 1067 Wh/kg based on the total weight of the sulfuric acid. Slow decrease in performance was observed, but it can be recovered by refilling the cell with new electrolyte after continuous discharging of more than 75 h. A charge-discharge experiment at 0.2 mA/cm(2) showed that the cell was rechargeable with a capacity of more than 300 mAh/g. (c) 2012 Elsevier Ltd. All rights reserved.

  20. Improved performance of Co-doped Li2O cathodes for lithium-peroxide batteries using LiCoO2 as a dopant source

    NASA Astrophysics Data System (ADS)

    Kobayashi, Hiroaki; Hibino, Mitsuhiro; Ogasawara, Yoshiyuki; Yamaguchi, Kazuya; Kudo, Tetsuichi; Okuoka, Shin-ichi; Yonehara, Koji; Ono, Hironobu; Sumida, Yasutaka; Oshima, Masaharu; Mizuno, Noritaka

    2016-02-01

    We recently proposed a new battery system based on the redox of lithium peroxide (Li2O2)/lithium oxide (Li2O) at the cathode (lithium-peroxide battery system). In this system, the use of Li2O with cobalt ions partially substituted for lithium ions (Co-doped Li2O) is key to its realization. In this study, to further improve the cell performance, we prepare various Co-doped Li2O samples by a mechanochemical process using different cobalt source materials (e.g., LiCoO2, Co3O4, and CoO) and comparatively investigate them. Amongst the investigated cathode materials, the Co-doped Li2O sample prepared using LiCoO2 with a Co/(Co + Li) ratio of 0.09 exhibits the best performance. Monitoring of the pressure in the cell reveals that this Co-doped Li2O cathode can be charged to 270 mAh g-1 without O2 evolution involving its decomposition. Charge and discharge at 270 mAh g-1 is repeated more than 50 times. In addition, the rate-capability tests reveals that the redox reaction between peroxide and oxide ions is fast and that the cathode can be discharged at a high current density of 1000 mA g-1.

  1. Deposition of LiF onto Films of Fullerene Derivatives Leads to Bulk Doping.

    PubMed

    Torabi, Solmaz; Liu, Jian; Gordiichuk, Pavlo; Herrmann, Andreas; Qiu, Li; Jahani, Fatemeh; Hummelen, Jan C; Koster, L Jan Anton

    2016-08-31

    One of the most commonly used cathode interlayers for increasing the efficiency of electron injection/extraction in organic electronic devices is an ultrathin layer of LiF. Our capacitance measurements and electrical conductivity analysis show that thin films of fullerene derivatives and their mixtures with polymers are unintentionally doped upon deposition of LiF. The level of doping depends on the chemical structure of the fullerene derivatives. The doping effect on polymer/fullerene mixtures is significant only for blends in which the fullerene content is greater than the polymer content by weight. Our finding has profound implications for the development and characterization of organic photovoltaic devices, including a negative impact of doping on the stability of the device and erroneous estimations of properties such as charge carrier mobility and the dielectric constant. PMID:27526262

  2. Rigid-flexible coupling high ionic conductivity polymer electrolyte for an enhanced performance of LiMn2O4/graphite battery at elevated temperature.

    PubMed

    Hu, Pu; Duan, Yulong; Hu, Deping; Qin, Bingsheng; Zhang, Jianjun; Wang, Qingfu; Liu, Zhihong; Cui, Guanglei; Chen, Liquan

    2015-03-01

    LiMn2O4-based batteries exhibit severe capacity fading during cycling or storage in LiPF6-based liquid electrolytes, especially at elevated temperatures. Herein, a novel rigid-flexible gel polymer electrolyte is introduced to enhance the cyclability of LiMn2O4/graphite battery at elevated temperature. The polymer electrolyte consists of a robust natural cellulose skeletal incorporated with soft segment poly(ethyl α-cyanoacrylate). The introduction of the cellulose effectively overcomes the drawback of poor mechanical integrity of the gel polymer electrolyte. Density functional theory (DFT) calculation demonstrates that the poly(ethyl α-cyanoacrylate) matrices effectively dissociate the lithium salt to facilitate ionic transport and thus has a higher ionic conductivity at room temperature. Ionic conductivity of the gel polymer electrolyte is 3.3 × 10(-3) S cm(-1) at room temperature. The gel polymer electrolyte remarkably improves the cycling performance of LiMn2O4-based batteries, especially at elevated temperatures. The capacity retention after the 100th cycle is 82% at 55 °C, which is much higher than that of liquid electrolyte (1 M LiPF6 in carbonate solvents). The polymer electrolyte can significantly suppress the dissolution of Mn(2+) from surface of LiMn2O4 because of strong interaction energy of Mn(2+) with PECA, which was investigated by DFT calculation.

  3. Ultraviolet photorefractive effect in Mg-doped near-stoichiometric LiNbO 3

    NASA Astrophysics Data System (ADS)

    Zhu, Dengsong; Xu, Jingjun; Qiao, Haijun; Shi, Yanli; Gao, Feng; Li, Wei; Fu, Bo; Zhang, Guaquan; Zheng, Ke

    2006-10-01

    The ultraviolet photorefractive effect of Mg-doped near-stoichiometric LiNbO3 crystals prepared by vapor transport equilibration (VTE) technique was studied at 351 nm. It was found in the near-stoichiometric LiNbO3 crystals that the ultraviolet photorefractive effect could be enhanced greatly with the increase of Mg concentration. Based on the activation energy of dark decay of the photorefractive grating, possible centers responsible for the ultraviolet photorefractive effect were also discussed.

  4. Citrate gel synthesis of aluminum-doped lithium lanthanum titanate solid electrolyte for application in organic-type lithium-oxygen batteries

    NASA Astrophysics Data System (ADS)

    Le, Hang T. T.; Kalubarme, Ramchandra S.; Ngo, Duc Tung; Jang, Seong-Yong; Jung, Kyu-Nam; Shin, Kyoung-Hee; Park, Chan-Jin

    2015-01-01

    Aluminium doped lithium lanthanum titanate (A-LLTO) powders with various excess Li2O content are synthesized using a simple citrate gel method. The obtained A-LLTO powders show an agglomerated form, composed of nano-sized particles of 20-50 nm. The morphology and conductivity of the A-LLTO ceramics are largely affected by the content of excess Li2O. The highest total ionic conductivity of 3.17 × 10-4 S cm-1 is achieved for the A-LLTO sample containing 20% excess Li2O, exhibiting a vacancy content of 6%, and a total activation energy of 0.358 eV. The A-LLTO can act as a membrane to protect lithium metal from oxygen and other contaminants diffused through the oxygen electrode part. The Li-O2 cell employing the A-LLTO solid electrolyte shows a good cycle life of longer than 100 discharge-charge cycles, under the constant capacity mode of 300 mAh g-1.

  5. Photoelectrochemical properties of highly mobilized Li-doped ZnO thin films.

    PubMed

    Shinde, S S; Bhosale, C H; Rajpure, K Y

    2013-03-01

    Li-doped ZnO thin films with preferred (002) orientation have been prepared by spray pyrolysis technique in aqueous medium on to the corning glass substrates. The effect of Li-doping on to the photoelectrochemical, structural, morphological, optical, luminescence, electrical and thermal properties has been investigated. XRD and Raman study indicates that the films have hexagonal crystal structure. The transmittance, reflectance, refractive index, extinction coefficient and bandgap have been analyzed by optical study. PL spectra consist of a near band edge and visible emission due to the electronic defects, which are related to deep level emissions, such as oxide antisite (OZn), interstitial zinc (Zni), interstitial oxygen (Oi) and zinc vacancy (VZn). The Li-doped ZnO films prepared for 1at% doping possesses the highest electron mobility of 102cm(2)/Vs and carrier concentration of 3.62×10(19)cm(-3). Finally, degradation of 2,4,6-Trinitrotoluene using Li-doped ZnO thin films has been reported. PMID:23416707

  6. A study of suppressed formation of low-conductivity phases in doped Li7La3Zr2O12 garnets by in situ neutron diffraction

    DOE PAGESBeta

    Chen, Yan; Rangasamy, Ezhiylmurugan; dela Cruz, Clarina R.; Liang, Chengdu; An, Ke

    2015-09-28

    Doped Li7La3Zr2O12 garnets, oxide-based solids with good Li+ conductivity and compatibility, show great potential as leading electrolyte material candidates for all-solid-state lithium ion batteries. Still yet, the conductive bulk usually suffers from the presence of secondary phases and the transition towards a low-conductivity tetragonal phase during synthesis. Dopants are designed to stabilize the high-conductive cubic phase and suppress the formation of the low-conductivity phases. In situ neutron diffraction enables a direct observation of the doping effects by monitoring the phase evolutions during garnet synthesis. It reveals the reaction mechanism involving the temporary presence of intermediate phases. The off-stoichiometry due tomore » the liquid Li2CO3 evaporation leads to the residual of the low-conductivity intermediate phase in the as-synthesized bulk. Appropriate doping of an active element may alter the component of the intermediate phases and promote the completion of the reaction. While the dopants aid to stabilize most of the cubic phase, a small amount of tetragonal phase tends to form under a diffusion process. Lastly, the in situ observations provide the guideline of process optimization to suppress the formation of unwanted low-conductivity phases.« less

  7. Performance of Wide Operating Temperature Range Electrolytes in Quallion Prototype Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Tomcsi, M. R.; Nagata, M.; Visco, V.; Tsukamoto, H.

    2010-01-01

    For a number of applications, there is a continued interest in the development of rechargeable lithium-based batteries that can effectively operate over a wide temperature range (i.e., -40 to +70 deg C). These applications include powering future planetary rovers for NASA, enabling the next generation of automotive batteries for DOE, and supporting many DOD applications. Li-ion technology has been demonstrated to have good performance over a reasonably wide temperature range with many systems; however, there is still a desire to improve the low temperature rate capacity as well as the high temperature resilience. In the current study, we would like to present recent results obtained with prototype Li-Ion cells (manufactured by Quallion, LLC) which include various wide operating temperature range electrolytes developed by both JPL and Quallion. To demonstrate the viability of the technology, a number of performance tests were carried out, including: (a) discharge rate characterization over a wide temperature range (down to -60 deg C) using various rates (up to 20C rates), (b) discharge rate characterization at low temperatures with low temperature charging, (c) variable temperature cycling over a wide temperature range (-40 to +70 deg C), and (d) cycling at high temperature (50 deg C). As will be discussed, impressive rate capability was observed at low temperatures with many systems, as well as good resilience to high temperature cycling. To augment the performance testing on the prototype cells, a number of experimental three electrodes cells were fabricated (including Li reference electrodes) to allow the determination of the lithium kinetics of the respective electrodes and interfacial properties as a function of temperatures.

  8. Improved Li storage performance in SnO2 nanocrystals by a synergetic doping

    DOE PAGESBeta

    Wan, Ning; Lu, Xia; Wang, Yuesheng; Zhang, Weifeng; Bai, Ying; Hu, Yong -Sheng; Dai, Sheng

    2016-01-06

    Tin dioxide (SnO2) is a widely investigated lithium (Li) storage material because of its easy preparation, two-step storage mechanism and high specific capacity for lithium-ion batteries (LIBs). In this contribution, a phase-pure cobalt-doped SnO2 (Co/SnO2) and a cobalt and nitrogen co-doped SnO2 (Co-N/SnO2) nanocrystals are prepared to explore their Li storage behaviors. It is found that the morphology, specific surface area, and electrochemical properties could be largely modulated in the doped and co-doped SnO2 nanocrystals. Gavalnostatic cycling results indicate that the Co-N/SnO2 electrode delivers a specific capacity as high as 716 mAh g–1 after 50 cycles, and the same outstandingmore » rate performance can be observed in subsequent cycles due to the ionic/electronic conductivity enhancement by co-doping effect. Further, microstructure observation indicates the existence of intermediate phase of Li3N with high ionic conductivity upon cycling, which probably accounts for the improvements of Co-N/SnO2 electrodes. Furthermore, we find that the method of synergetic doping into SnO2 with Co and N, with which the electrochemical performances is enhanced remarkably, undoubtedly, will have an important influence on the material itself and community of LIBs as well.« less

  9. Improved Li storage performance in SnO2 nanocrystals by a synergetic doping

    PubMed Central

    Wan, Ning; Lu, Xia; Wang, Yuesheng; Zhang, Weifeng; Bai, Ying; Hu, Yong-Sheng; Dai, Sheng

    2016-01-01

    Tin dioxide (SnO2) is a widely investigated lithium (Li) storage material because of its easy preparation, two-step storage mechanism and high specific capacity for lithium-ion batteries (LIBs). In this contribution, a phase-pure cobalt-doped SnO2 (Co/SnO2) and a cobalt and nitrogen co-doped SnO2 (Co-N/SnO2) nanocrystals are prepared to explore their Li storage behaviors. It is found that the morphology, specific surface area, and electrochemical properties could be largely modulated in the doped and co-doped SnO2 nanocrystals. Gavalnostatic cycling results indicate that the Co-N/SnO2 electrode delivers a specific capacity as high as 716 mAh g−1 after 50 cycles, and the same outstanding rate performance can be observed in subsequent cycles due to the ionic/electronic conductivity enhancement by co-doping effect. Further, microstructure observation indicates the existence of intermediate phase of Li3N with high ionic conductivity upon cycling, which probably accounts for the improvements of Co-N/SnO2 electrodes. The method of synergetic doping into SnO2 with Co and N, with which the electrochemical performances is enhanced remarkably, undoubtedly, will have an important influence on the material itself and community of LIBs as well. PMID:26733355

  10. Study of gadolinia-doped ceria solid electrolyte surface by XPS

    SciTech Connect

    Datta, Pradyot Majewski, Peter; Aldinger, Fritz

    2009-02-15

    Gadolinia-doped ceria (CGO) is an important material to be used as electrolyte for solid oxide fuel cell for intermediate temperature operation. Ceria doped with 10 mol% gadolinia (Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95}) was prepared by conventional solid state synthesis and found to be single phase by room temperature X-ray diffraction (XRD). The chemical states of the surface of the prepared sample were analyzed by X-ray photoelectron spectroscopy (XPS). Though Gd was present in its characteristic chemical state, Ce was found in both Ce{sup 4+} and Ce{sup 3+} states. Presence of Ce{sup 3+} state was ascribed to the differential yield of oxygen atoms in the sputtering process.

  11. Preparation, characterization and application of Nano CdS doped with alum composite electrolyte

    NASA Astrophysics Data System (ADS)

    Singh, Pramod K.; Kumar, Pawan; Seth, Tanay; Rhee, Hee-Woo; Bhattacharya, B.

    2012-09-01

    A new composite electrolyte has been developed for electrochemical application and studied in details. The system contains Alum doped with nanosize cadmium sulphide (CdS) particles in the desire ratio. The structural studies were carried out by using X-ray diffraction (XRD) as well as infrared spectroscopy (IR) which affirms the composite nature of the system. The electrical properties, including ion transport studies and complex impedance spectra confirm the ionic nature of sample as well as enhancement in ionic conductivity by CdS doping. The temperature dependence measurement confirms the Arrhenius nature of sample, which is commonly observed in the ionic composite system. The dielectric constant varies with temperature, and this data is used to calculate the number of charge carrier (n/no) contributing to conductivity and fits well with emf variation. A cell was fabricated by sandwiching the composite between graphite and stainless steel electrodes, which shows an emf of 7 mV.

  12. Rechargeability of Li-air cathodes pre-filled with discharge products using an ether-based electrolyte solution: implications for cycle-life of Li-air cells.

    PubMed

    Meini, Stefano; Tsiouvaras, Nikolaos; Schwenke, K Uta; Piana, Michele; Beyer, Hans; Lange, Lukas; Gasteiger, Hubert A

    2013-07-21

    The instability of currently used electrolyte solutions and of the carbon support during charge-discharge in non-aqueous lithium-oxygen cells can lead to discharge products other than the desired Li2O2, such as Li2CO3, which is believed to reduce cycle-life. Similarly, discharge in an O2 atmosphere which contains H2O and CO2 impurities would lead to LiOH and Li2CO3 discharge products. In this work we therefore investigate the rechargeability of model cathodes pre-filled with four possible Li-air cell discharge products, namely Li2O2, Li2CO3, LiOH, and Li2O. Using Online Electrochemical Mass Spectrometry (OEMS), we determined the charge voltages and the gases evolved upon charge of pre-filled electrodes, thus determining the reversibility of the formation/electrooxidation reactions. We show that Li2O2 is the only reversible discharge product in ether-based electrolyte solutions, and that the formation of Li2CO3, LiOH, or Li2O is either irreversible and/or reacts with the electrolyte solution or the carbon during its oxidation.

  13. Rechargeability of Li-air cathodes pre-filled with discharge products using an ether-based electrolyte solution: implications for cycle-life of Li-air cells.

    PubMed

    Meini, Stefano; Tsiouvaras, Nikolaos; Schwenke, K Uta; Piana, Michele; Beyer, Hans; Lange, Lukas; Gasteiger, Hubert A

    2013-07-21

    The instability of currently used electrolyte solutions and of the carbon support during charge-discharge in non-aqueous lithium-oxygen cells can lead to discharge products other than the desired Li2O2, such as Li2CO3, which is believed to reduce cycle-life. Similarly, discharge in an O2 atmosphere which contains H2O and CO2 impurities would lead to LiOH and Li2CO3 discharge products. In this work we therefore investigate the rechargeability of model cathodes pre-filled with four possible Li-air cell discharge products, namely Li2O2, Li2CO3, LiOH, and Li2O. Using Online Electrochemical Mass Spectrometry (OEMS), we determined the charge voltages and the gases evolved upon charge of pre-filled electrodes, thus determining the reversibility of the formation/electrooxidation reactions. We show that Li2O2 is the only reversible discharge product in ether-based electrolyte solutions, and that the formation of Li2CO3, LiOH, or Li2O is either irreversible and/or reacts with the electrolyte solution or the carbon during its oxidation. PMID:23748698

  14. High Performance C/S Composite Cathodes with Conventional Carbonate-Based Electrolytes in Li-S Battery

    NASA Astrophysics Data System (ADS)

    Zheng, Shiyou; Han, Pan; Han, Zhuo; Zhang, Huijuan; Tang, Zhihong; Yang, Junhe

    2014-04-01

    High stable C/S composites are fabricated by a novel high-temperature sulfur infusion into micro-mesoporous carbon method following with solvent cleaning treatment. The C/S composite cathodes show high Coulombic efficiency, long cycling stability and good rate capability in the electrolyte of 1.0 M LiPF6 + EC/DEC (1:1 v/v), for instance, the reversible capacity of the treated C/S-50 (50% S) cathode retains around 860 mAh/g even after 500 cycles and the Coulombic efficiency is close to 100%, which demonstrates the best electrochemical performance of carbon-sulfur composite cathodes using the carbonate-based electrolyte reported to date. It is believed that the chemical bond of C-S is responsible for the superior electrochemical properties in Li-S battery, that is, the strong interaction between S and carbon matrix significantly improves the conductivity of S, effectively buffers the structural strain/stress caused by the large volume change during lithiation/delithiation, completely eliminates the formation of high-order polysulfide intermediates, and substantially avoids the shuttle reaction and the side reaction between polysulfide anions and carbonate solvent, and thus enables the C/S cathode to use conventional carbonate-based electrolytes and achieve outstanding electrochemical properties in Li-S battery. The results may substantially contribute to the progress of the Li-S battery technology.

  15. Accurate static and dynamic properties of liquid electrolytes for Li-ion batteries from ab initio molecular dynamics.

    PubMed

    Ganesh, P; Jiang, De-en; Kent, P R C

    2011-03-31

    Lithium-ion batteries have the potential to revolutionize the transportation industry, as they did for wireless communication. A judicious choice of the liquid electrolytes used in these systems is required to achieve a good balance among high-energy storage, long cycle life and stability, and fast charging. Ethylene-carbonate (EC) and propylene-carbonate (PC) are popular electrolytes. However, to date, almost all molecular-dynamics simulations of these fluids rely on classical force fields, while a complete description of the functionality of Li-ion batteries will eventually require quantum mechanics. We perform accurate ab initio molecular-dynamics simulations of ethylene- and propylene-carbonate with LiPF(6) at experimental concentrations to build solvation models which explain available neutron scattering and nuclear magnetic resonance (NMR) results and to compute Li-ion solvation energies and diffusion constants. Our results suggest some similarities between the two liquids as well as some important differences. Simulations also provide useful insights into formation of solid-electrolyte interphases in the presence of electrodes in conventional Li-ion batteries.

  16. Cycle stability of the electrochemical capacitors patterned with vertically aligned carbon nanotubes in an LiPF6-based electrolyte

    NASA Astrophysics Data System (ADS)

    Chiou, Yi-Deng; Tsai, Dah-Shyang; Lam, Hoa Hung; Chang, Chuan-Hua; Lee, Kuei-Yi; Huang, Ying-Sheng

    2013-08-01

    The miniature ultracapacitors, with interdigitated electrodes of vertically aligned carbon nanotubes (VACNTs) and an inter-electrode gap of 20 μm, have been prepared in the LiPF6 organic electrolyte with and without PVdF-HFP gel. PVdF-HFP between two opposing electrodes enhances the device reliability, but lessens its power performance because of the extra diffusion resistance. Also noteworthy are the gel influences on the cycle stability. When the applied voltage is 2.0 or 2.5 V, both the LiPF6 and the gel capacitors exhibit excellent stability, typified by a retention ratio of >=95% after 10 000 cycles. Their coulombic efficiencies quickly rise up, and hold steady at 100%. Nonetheless, when the applied voltage is 3.5 or 4.0 V, the cycle stability deteriorates, since the negative electrode potential descends below 0.9 V (vs. Li), leading to electrolyte decomposition and SEI formation. For the LiPF6 capacitor, its retention ratio could be around 60% after 10 000 cycles and the coulombic efficiency of 100% is difficult to reach throughout its cycle life. On the other hand, the gel capacitor cycles energy with a much higher retention ratio, >80% after 10 000 cycles, and a better coulombic efficiency, even though electrolyte decomposition still occurs. We attribute the superior stability of the gel capacitor to its extra diffusion resistance which slows down the performance deterioration.

  17. High Performance C/S Composite Cathodes with Conventional Carbonate-Based Electrolytes in Li-S Battery

    PubMed Central

    Zheng, Shiyou; Han, Pan; Han, Zhuo; Zhang, Huijuan; Tang, Zhihong; Yang, Junhe

    2014-01-01

    High stable C/S composites are fabricated by a novel high-temperature sulfur infusion into micro-mesoporous carbon method following with solvent cleaning treatment. The C/S composite cathodes show high Coulombic efficiency, long cycling stability and good rate capability in the electrolyte of 1.0 M LiPF6 + EC/DEC (1:1 v/v), for instance, the reversible capacity of the treated C/S-50 (50% S) cathode retains around 860 mAh/g even after 500 cycles and the Coulombic efficiency is close to 100%, which demonstrates the best electrochemical performance of carbon-sulfur composite cathodes using the carbonate-based electrolyte reported to date. It is believed that the chemical bond of C-S is responsible for the superior electrochemical properties in Li-S battery, that is, the strong interaction between S and carbon matrix significantly improves the conductivity of S, effectively buffers the structural strain/stress caused by the large volume change during lithiation/delithiation, completely eliminates the formation of high-order polysulfide intermediates, and substantially avoids the shuttle reaction and the side reaction between polysulfide anions and carbonate solvent, and thus enables the C/S cathode to use conventional carbonate-based electrolytes and achieve outstanding electrochemical properties in Li-S battery. The results may substantially contribute to the progress of the Li-S battery technology. PMID:24776750

  18. X-ray absorption spectroscopy of LiBF 4 in propylene carbonate. A model lithium ion battery electrolyte

    DOE PAGESBeta

    Smith, Jacob W.; Lam, Royce K.; Sheardy, Alex T.; Shih, Orion; Rizzuto, Anthony M.; Borodin, Oleg; Harris, Stephen J.; Prendergast, David; Saykally, Richard J.

    2014-08-20

    Since their introduction into the commercial marketplace in 1991, lithium ion batteries have become increasingly ubiquitous in portable technology. Nevertheless, improvements to existing battery technology are necessary to expand their utility for larger-scale applications, such as electric vehicles. Advances may be realized from improvements to the liquid electrolyte; however, current understanding of the liquid structure and properties remains incomplete. X-ray absorption spectroscopy of solutions of LiBF4 in propylene carbonate (PC), interpreted using first-principles electronic structure calculations within the eXcited electron and Core Hole (XCH) approximation, yields new insight into the solvation structure of the Li+ ion in this model electrolyte.more » By generating linear combinations of the computed spectra of Li+-associating and free PC molecules and comparing to the experimental spectrum, we find a Li+–solvent interaction number of 4.5. This result suggests that computational models of lithium ion battery electrolytes should move beyond tetrahedral coordination structures.« less

  19. Performance Demonstration of Mcmb-LiNiCoO2 Cells Containing Electrolytes Designed for Wide Operating Temperature Range

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Whicanack, L. D.; Smith, K. A.; Santee, S.; Puglia, F. J.; Gitzendanner, R.

    2009-01-01

    With the intent of improving the performance of Li-ion cells over a wide operating temperature range, we have investigated the use of co-solvents to improve the properties of electrolyte formulations. In the current study, we have focused upon evaluating promising electrolytes which have been incorporated into large capacity (7 Ah) prototype Li-ion cells, fabricated by Yardney Technical Products, Inc. The electrolytes selected for performance evaluation include the use of a number of esters as co-solvents, including methyl propionate (MP), ethyl propionate (EP), ethyl butyrate (EB), propyl butyrate (PB), and 2,2,2-trifluoroethyl butyrate (TFEB). The performance of the prototype cells containing the ester-based electrolytes was compared with an extensive data base generated on cells containing previously developed all carbonate-based electrolytes. A number of performance tests were performed, including determining (i) the discharge rate capacity over a wide range of temperatures, (ii) the charge characteristics, (iii) the cycle life characteristics under various conditions, and (iv) the impedance characteristics.

  20. Chemical stability and Ce doping of LiMgAlF6 neutron scintillator

    SciTech Connect

    Du, M. H.

    2014-11-13

    We perform density functional calculations to investigate LiMgAlF6 as a potential neutron scintillator material. The calculations of enthalpy of formation and phase diagram show that single-phase LiMgAlF6 can be grown but it should be more difficult than growing LiCaAlF6 and LiSrAlF6. Moreover, the formation energy calculations for substitutional Ce show that the concentration of Ce on the Al site is negligible but a high concentration (>1 at.%) of Ce on the Mg site is attainable provided that the Fermi level is more than 5 eV lower than the conduction band minimum. Acceptor doping should promote Ce incorporation in LiMgAlF6.

  1. Chemical stability and Ce doping of LiMgAlF6 neutron scintillator

    DOE PAGESBeta

    Du, M. H.

    2014-11-13

    We perform density functional calculations to investigate LiMgAlF6 as a potential neutron scintillator material. The calculations of enthalpy of formation and phase diagram show that single-phase LiMgAlF6 can be grown but it should be more difficult than growing LiCaAlF6 and LiSrAlF6. Moreover, the formation energy calculations for substitutional Ce show that the concentration of Ce on the Al site is negligible but a high concentration (>1 at.%) of Ce on the Mg site is attainable provided that the Fermi level is more than 5 eV lower than the conduction band minimum. Acceptor doping should promote Ce incorporation in LiMgAlF6.

  2. Electrolytes

    MedlinePlus

    ... body fluids that carry an electric charge. Electrolytes affect how your body functions in many ways, including: The amount of water in your body The acidity of your blood (pH) Your muscle function Other important processes You lose ...

  3. Defect assisted saturable absorption characteristics in Al and Li doped ZnO thin films

    NASA Astrophysics Data System (ADS)

    K. M., Sandeep; Bhat, Shreesha; S. M., Dharmaprakash; P. S., Patil; Byrappa, K.

    2016-09-01

    The influence of different doping ratios of Al and Li on the nonlinear optical properties, namely, a two-photon absorption and a nonlinear refraction using single beam Z-scan technique, of nano-crystalline ZnO thin films has been investigated in the present study. A sol-gel spin-coated pure ZnO, Al-doped ZnO (AZO), and Li-doped ZnO (LZO) thin films have been prepared. The stoichiometric deviations induced by the occupancy of Al3+ and Li+ ions at the interstitial sites injects the compressive stress in the AZO and LZO thin films, respectively, while the extended defect states below the conduction band leads to a redshift of energy band gap in the corresponding films as compared to pure ZnO thin film. Switching from an induced absorption in ZnO and 1 at. wt. % doped AZO and LZO films to a saturable absorption (SA) in 2 at. wt. % doped AZO and LZO films has been observed, and it is attributed to the saturation of a linear absorption of the defect states. The closed aperture Z-scan technique revealed the self-focusing (a positive nonlinear refractive index) in all the films, which emerge out of the thermo-optical effects due to the continuous illumination of laser pulses. A higher third-order nonlinear optical susceptibility χ(3) of the order 10-3 esu has been observed in all the films.

  4. Effect of LiNO3 additive and pyrrolidinium ionic liquid on the solid electrolyte interphase in the lithium-sulfur battery

    NASA Astrophysics Data System (ADS)

    Barghamadi, Marzieh; Best, Adam S.; Bhatt, Anand I.; Hollenkamp, Anthony F.; Mahon, Peter J.; Musameh, Mustafa; Rüther, Thomas

    2015-11-01

    The lithium-sulfur (Li-S) battery in which the ionic liquid (IL) C4mpyr-TFSI is a major component of the electrolyte has attracted much attention by researchers due to the ability of the IL to suppress the polysulfide shuttle effect, combined with advantageous properties of thermal, chemical and electrochemical stability. In a largely parallel stream of research, LiNO3 has come to be known as an additive for improving Li-S battery performance through its influence on protecting the lithium anode and beneficial interaction with the polysulfide shuttle. In this work a deeper understanding is sought of the combined effects of LiNO3 and C4mpyr-TFSI on the factors that impact Li-S cell performance. Specifically, we investigate the formation of the protective surface film on lithium anode and results are compared with those for a typical organic electrolyte for the Li-S battery, DOL:DME. Electrochemical impedance spectroscopy (EIS) confirms that the LiNO3 additive is vital to achieving acceptable levels of performance with the organic electrolyte. Although LiNO3 improves the performance of a battery assembled with IL containing electrolyte, it shows a higher impact in the organic electrolyte based battery. Furthermore X-ray photoelectron spectroscopy (XPS) spectra confirm the participation of C4mpyr-TFSI on the formation of the interphase layer on the anode.

  5. The anomaly Cu doping effects on LiFeAs superconductors.

    PubMed

    Xing, L Y; Miao, H; Wang, X C; Ma, J; Liu, Q Q; Deng, Z; Ding, H; Jin, C Q

    2014-10-29

    The Cu substitution effect on the superconductivity of LiFeAs has been studied in comparison with Co/Ni substitution. It is found that the shrinking rate of the lattice parameter c for Cu substitution is much smaller than that of Co/Ni substitution. This is in conjugation with the observation of ARPES that shows almost the same electron and hole Fermi surfaces (FSs) size for undoped and Cu substituted LiFeAs sample, except for a very small hole band sinking below Fermi level with doping. This indicates that there is little doping effect at Fermi surface by Cu substitution, in sharp contrast to the more effective carrier doping effect by Ni or Co. PMID:25299428

  6. In situ Electrochemical-AFM Study of LiFePO4 Thin Film in Aqueous Electrolyte

    NASA Astrophysics Data System (ADS)

    Wu, Jiaxiong; Cai, Wei; Shang, Guangyi

    2016-04-01

    Lithium-ion (Li-ion) batteries have been widely used in various kinds of electronic devices in our daily life. The use of aqueous electrolyte in Li-ion battery would be an alternative way to develop low cost and environmentally friendly batteries. In this paper, the lithium iron phosphate (LiFePO4) thin film cathode for the aqueous rechargeable Li-ion battery is prepared by radio frequency magnetron sputtering deposition method. The XRD, SEM, and AFM results show that the film is composed of LiFePO4 grains with olivine structure and the average size of 100 nm. Charge-discharge measurements at current density of 10 μAh cm-2 between 0 and 1 V show that the LiFePO4 thin film electrode is able to deliver an initial discharge capacity of 113 mAh g-1. Specially, the morphological changes of the LiFePO4 film electrode during charge and discharge processes were investigated in aqueous environment by in situ EC-AFM, which is combined AFM with chronopotentiometry method. The changes in grain area are measured, and the results show that the size of the grains decreases and increases during the charge and discharge, respectively; the relevant mechanism is discussed.

  7. The effect of porosity on performance of phosphoric acid doped polybenzimidazole polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Celik, Muhammet; Genc, Gamze; Elden, Gulsah; Yapici, Huseyin

    2016-03-01

    A polybenzimidazole (PBI) based polymer electrolyte fuel cells, which called high temperature polymer electrolyte fuel cells (HT-PEMS), operate at higher temperatures (120-200°C) than conventional PEM fuel cells. Although it is known that HT-PEMS have some of the significant advantages as non-humidification requirements for membrane and the lack of liquid water at high temperature in the fuel cell, the generated water as a result of oxygen reduction reaction causes in the degradation of these systems. The generated water absorbed into membrane side interacts with the hydrophilic PBI matrix and it can cause swelling of membrane, so water transport mechanism in a membrane electrode assembly (MEA) needs to be well understood and water balance must be calculated in MEA. Therefore, the water diffusion transport across the electrolyte should be determined. In this study, various porosity values of gas diffusion layers are considered in order to investigate the effects of porosity on the water management for two phase flow in fuel cell. Two-dimensional fuel cell with interdigitated flow-field is modelled using COMSOL Multiphysics 4.2a software. The operating temperature and doping level is selected as 160°C and 6.75mol H3PO4/PBI, respectively.

  8. Role of Ce and In doping in the performance of LiFePO4 cathode material for Li ion Batteries

    NASA Astrophysics Data System (ADS)

    Mandal, Balaji; Nazri, Mariam; Vaishnava, Prem P.; Naik, Vaman M.; Nazri, Gholam A.; Naik, Ratna

    2012-02-01

    Recently, the olivine LiFePO4 has attracted attention as a promising cathode material for Li ion batteries. However, its poor electronic conductivity is a major challenge for its industrial applications. Different approaches have been taken to address this problem. Here, we report a method of improving its conductivity by doping In and Ce ions at the Fe site. We prepared the samples by sol-gel method followed by annealing at 650 C in Ar (95%) +H2(5%) atmosphere for 5 hrs. XRD and Raman spectroscopy confirm that the olivine structure remains unchanged upon doping with In and Ce up to 5 wt%. XRD analysis shows the values of the lattice parameters increase with doping as the ionic radii of Ce and In ions are larger than that of the Fe^2+ ion. This observation also suggests that both Ce and In ions replace Fe ions and not the Li ions in the material. Upon doping, ionic conductivity was found to increase from 10-9 to 10-4 Ohm-1cm-1. Interestingly, Ce doped LiFePO4 showed a higher conductivity than In doped LiFePO4. SEM measurements show a bigger grain size of ˜300-500 nm in doped LiFePO4 which decreased to ˜50 nm when the materials were synthesized using 0.25M lauric acid as a precursor. The electrochemical characteristics of the doped LiFePO4 along with conductivity and Raman data will be presented.

  9. Direct measurement of the chemical reactivity of silicon electrodes with LiPF6-based battery electrolytes.

    PubMed

    Veith, Gabriel M; Baggetto, Loïc; Sacci, Robert L; Unocic, Raymond R; Tenhaeff, Wyatt E; Browning, James F

    2014-03-21

    We report the first direct measurement of the extent of the spontaneous non-electrochemically driven reaction between a lithium ion battery electrode surface (Si) and a liquid electrolyte (1.2 M LiPF6-3 : 7 wt% ethylene carbonate : dimethyl carbonate). This layer is estimated to be 35 Å thick with a SLD of ∼ 4 × 10(-6) Å(-2) and likely originates from the consumption of the silicon surface. PMID:24513965

  10. Ionically conducting PVA-LiClO4 gel electrolyte for high performance flexible solid state supercapacitors.

    PubMed

    Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Lokhande, Chandrakant D

    2015-12-15

    The synthesis of polymer gel electrolyte having high ionic conductivity, excellent compatibility with active electrode material, mechanical tractability and long life is crucial to obtain majestic electrochemical performance for flexible solid state supercapacitors (FSS-SCs). Our present work describes effect of different polymers gel electrolytes on electrochemical properties of MnO2 based FSS-SCs device. It is revealed that, MnO2-FSS-SCs with polyvinyl alcohol (PVA)-Lithium perchlorate (LiClO4) gel electrolyte demonstrate excellent electrochemical features such as maximum operating potential window (1.2V), specific capacitance of 112Fg(-1) and energy density of 15Whkg(-1) with extended cycling stability up to 2500CV cycles. Moreover, the calendar life suggests negligible decrease in the electrochemical performance of MnO2-FSS-SCs after 20days. PMID:26397234

  11. Ionically conducting PVA-LiClO4 gel electrolyte for high performance flexible solid state supercapacitors.

    PubMed

    Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Lokhande, Chandrakant D

    2015-12-15

    The synthesis of polymer gel electrolyte having high ionic conductivity, excellent compatibility with active electrode material, mechanical tractability and long life is crucial to obtain majestic electrochemical performance for flexible solid state supercapacitors (FSS-SCs). Our present work describes effect of different polymers gel electrolytes on electrochemical properties of MnO2 based FSS-SCs device. It is revealed that, MnO2-FSS-SCs with polyvinyl alcohol (PVA)-Lithium perchlorate (LiClO4) gel electrolyte demonstrate excellent electrochemical features such as maximum operating potential window (1.2V), specific capacitance of 112Fg(-1) and energy density of 15Whkg(-1) with extended cycling stability up to 2500CV cycles. Moreover, the calendar life suggests negligible decrease in the electrochemical performance of MnO2-FSS-SCs after 20days.

  12. Synthesis of polymer electrolyte membranes from cellulose acetate/poly(ethylene oxide)/LiClO{sub 4} for lithium ion battery application

    SciTech Connect

    Nurhadini, Arcana, I Made

    2015-09-30

    This study was conducted to determine the effect of cellulose acetate on poly(ethylene oxide)-LiClO{sub 4} membranes as the polymer electrolyte. Cellulose acetate is used as an additive to increase ionic conductivity and mechanical property of polymer electrolyte membranes. The increase the percentage of cellulose acetate in membranes do not directly effect on the ionic conductivity, and the highest ionic conductivity of membranes about 5,7 × 10{sup −4} S/cm was observed in SA/PEO/LiClO{sub 4} membrane with cellulose ratio of 10-25% (w/w). Cellulose acetate in membranes increases mechanical strength of polymer electrolyte membranes. Based on TGA analysis, this polymer electrolyte thermally is stable until 270 °C. The polymer electrolyte membrane prepared by blending the cellulose acetate, poly(ethylene oxide), and lithium chlorate could be potentially used as a polymer electrolyte for lithium ion battery application.

  13. Synthesis of polymer electrolyte membranes from cellulose acetate/poly(ethylene oxide)/LiClO4 for lithium ion battery application

    NASA Astrophysics Data System (ADS)

    Nurhadini, Arcana, I. Made

    2015-09-01

    This study was conducted to determine the effect of cellulose acetate on poly(ethylene oxide)-LiClO4 membranes as the polymer electrolyte. Cellulose acetate is used as an additive to increase ionic conductivity and mechanical property of polymer electrolyte membranes. The increase the percentage of cellulose acetate in membranes do not directly effect on the ionic conductivity, and the highest ionic conductivity of membranes about 5,7 × 10-4 S/cm was observed in SA/PEO/LiClO4 membrane with cellulose ratio of 10-25% (w/w). Cellulose acetate in membranes increases mechanical strength of polymer electrolyte membranes. Based on TGA analysis, this polymer electrolyte thermally is stable until 270 °C. The polymer electrolyte membrane prepared by blending the cellulose acetate, poly(ethylene oxide), and lithium chlorate could be potentially used as a polymer electrolyte for lithium ion battery application.

  14. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte.

    PubMed

    Zhuang, Zhongbin; Giles, Stephen A; Zheng, Jie; Jenness, Glen R; Caratzoulas, Stavros; Vlachos, Dionisios G; Yan, Yushan

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.

  15. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte.

    PubMed

    Zhuang, Zhongbin; Giles, Stephen A; Zheng, Jie; Jenness, Glen R; Caratzoulas, Stavros; Vlachos, Dionisios G; Yan, Yushan

    2016-01-01

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

  16. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    PubMed Central

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-01

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

  17. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    DOE PAGESBeta

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizesmore » the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.« less

  18. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    NASA Astrophysics Data System (ADS)

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-01

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.

  19. Electrical Conductivity Study of Polymer Electrolyte Magnetic Nanocomposite Based Poly(Vinyl) Alcohol (PVA) Doping Lithium and Nickel Salt

    NASA Astrophysics Data System (ADS)

    Aji, Mahardika Prasetya; Rahmawati, Silvia, Bijaksana, Satria; Khairurrijal, Abdullah, Mikrajuddin

    2010-10-01

    Composite polymer electrolyte magnetic systems composed of poly(vinyl) alcohol (PVA) as the host polymer, lithium and nickel salt as dopant were studied. The effect upon addition of lithium ions in polimer PVA had been enhanced conductivity with the increase of lithium concentration. The conductivity values were 1.19x10-6, 1.25x10-5, 4.89x-5, 1.88x10-4, and 1.33x10-3 Sṡcm-1 for pure PVA and 1%, 3%, 5% and 7% LiOH complexed PVA, respectively. Meanwhile, the addition nickel salt into polymer electrolyte PVA-LiOH does not significantly change of conductivity value, on order 10-3 Sṡcm-1. The ionic transport is dominantly regarded by Li+ ions present in polymer electrolyte magnetic because the atomic mass Li+ is smaller than Ni2+. The absence of external magnetic field in polimer electrolyte magnetic causes the existence Ni2+ ions not significantly affected of conductivity.

  20. Promising Cell Configuration for Next-Generation Energy Storage: Li2S/Graphite Battery Enabled by a Solvate Ionic Liquid Electrolyte.

    PubMed

    Li, Zhe; Zhang, Shiguo; Terada, Shoshi; Ma, Xiaofeng; Ikeda, Kohei; Kamei, Yutaro; Zhang, Ce; Dokko, Kaoru; Watanabe, Masayoshi

    2016-06-29

    Lithium-ion sulfur batteries with a [graphite|solvate ionic liquid electrolyte|lithium sulfide (Li2S)] structure are developed to realize high performance batteries without the issue of lithium anode. Li2S has recently emerged as a promising cathode material, due to its high theoretical specific capacity of 1166 mAh/g and its great potential in the development of lithium-ion sulfur batteries with a lithium-free anode such as graphite. Unfortunately, the electrochemical Li(+) intercalation/deintercalation in graphite is highly electrolyte-selective: whereas the process works well in the carbonate electrolytes inherited from Li-ion batteries, it cannot take place in the ether electrolytes commonly used for Li-S batteries, because the cointercalation of the solvent destroys the crystalline structure of graphite. Thus, only very few studies have focused on graphite-based Li-S full cells. In this work, simple graphite-based Li-S full cells were fabricated employing electrolytes beyond the conventional carbonates, in combination with highly loaded Li2S/graphene composite cathodes (Li2S loading: 2.2 mg/cm(2)). In particular, solvate ionic liquids can act as a single-phase electrolyte simultaneously compatible with both the Li2S cathode and the graphite anode and can further improve the battery performance by suppressing the shuttle effect. Consequently, these lithium-ion sulfur batteries show a stable and reversible charge-discharge behavior, along with a very high Coulombic efficiency. PMID:27282172

  1. A Cross-Linking Succinonitrile-Based Composite Polymer Electrolyte with Uniformly Dispersed Vinyl-Functionalized SiO2 Particles for Li-Ion Batteries.

    PubMed

    Liu, Kai; Ding, Fei; Liu, Jiaquan; Zhang, Qingqing; Liu, Xingjiang; Zhang, Jinli; Xu, Qiang

    2016-09-14

    A cross-linking succinonitrile (SN)-based composite polymer electrolyte (referred to as "CLPC-CPE"), in which vinyl-functionalized SiO2 particles connect with trimethylolpropane propoxylate triacrylate (TPPTA) monomers by covalent bonds, was prepared by an ultraviolet irradiation (UV-curing) process successfully. Vinyl-functionalized SiO2 particles may react with TPPTA monomers to form a cross-linking network within the SN-based composite polymer electrolyte under ultraviolet irradiation. Vinyl-functionalized SiO2 particles as the fillers of polymer electrolyte may improve both the thermal stability of CLPC-CPE and interfacial compatibility between CLPC-CPE and electrodes effectively. There is no weight loss for CLPC-CPE until above 230 °C. The ionic conductivity of CLPC-CPE may reach 7.02 × 10(-4) S cm(-1) at 25 °C. CLPC-CPE has no significant oxidation current until up to 4.6 V (vs Li/Li(+)). The cell of LiFePO4/CLPC-CPE/Li has presented superior cycle performance and rate capability. The cell of LiFePO4/CLPC-CPE/Li may deliver a high discharge capacity of 154.4 mAh g(-1) at a rate of 0.1 C after 100 charge-discharge cycles, which is similar than that of the control cell of LiFePO4/liquid electrolyte/Li. Furthermore, the cell of LiFePO4/CLPC-CPE/Li can display a high discharge capacity of 112.7 mAh g(-1) at a rate of 2 C, which is higher than that of the cells assembled with other plastic crystal polymer electrolyte reported before obviously. PMID:27561892

  2. A Cross-Linking Succinonitrile-Based Composite Polymer Electrolyte with Uniformly Dispersed Vinyl-Functionalized SiO2 Particles for Li-Ion Batteries.

    PubMed

    Liu, Kai; Ding, Fei; Liu, Jiaquan; Zhang, Qingqing; Liu, Xingjiang; Zhang, Jinli; Xu, Qiang

    2016-09-14

    A cross-linking succinonitrile (SN)-based composite polymer electrolyte (referred to as "CLPC-CPE"), in which vinyl-functionalized SiO2 particles connect with trimethylolpropane propoxylate triacrylate (TPPTA) monomers by covalent bonds, was prepared by an ultraviolet irradiation (UV-curing) process successfully. Vinyl-functionalized SiO2 particles may react with TPPTA monomers to form a cross-linking network within the SN-based composite polymer electrolyte under ultraviolet irradiation. Vinyl-functionalized SiO2 particles as the fillers of polymer electrolyte may improve both the thermal stability of CLPC-CPE and interfacial compatibility between CLPC-CPE and electrodes effectively. There is no weight loss for CLPC-CPE until above 230 °C. The ionic conductivity of CLPC-CPE may reach 7.02 × 10(-4) S cm(-1) at 25 °C. CLPC-CPE has no significant oxidation current until up to 4.6 V (vs Li/Li(+)). The cell of LiFePO4/CLPC-CPE/Li has presented superior cycle performance and rate capability. The cell of LiFePO4/CLPC-CPE/Li may deliver a high discharge capacity of 154.4 mAh g(-1) at a rate of 0.1 C after 100 charge-discharge cycles, which is similar than that of the control cell of LiFePO4/liquid electrolyte/Li. Furthermore, the cell of LiFePO4/CLPC-CPE/Li can display a high discharge capacity of 112.7 mAh g(-1) at a rate of 2 C, which is higher than that of the cells assembled with other plastic crystal polymer electrolyte reported before obviously.

  3. Interface-enhanced Li ion conduction in a LiBH4-SiO2 solid electrolyte.

    PubMed

    Choi, Yong Seok; Lee, Young-Su; Oh, Kyu Hwan; Cho, Young Whan

    2016-08-10

    We have developed a fast solid state Li ion conductor composed of LiBH4 and SiO2 by means of interface engineering. A composite of LiBH4-SiO2 was simply synthesized by high energy ball-milling, and two types of SiO2 (MCM-41 and fumed silica) having different specific surface areas were used to evaluate the effect of the LiBH4/SiO2 interface on the ionic conductivity enhancement. The ionic conductivity of the ball-milled LiBH4-MCM-41 and LiBH4-fumed silica mixture is as high as 10(-5) S cm(-1) and 10(-4) S cm(-1) at room temperature, respectively. In particular, the conductivity of the latter is comparable to the LiBH4 melt-infiltrated into MCM-41. The conductivities of the LiBH4-fumed silica mixtures at different mixing ratios were analyzed employing a continuum percolation model, and the conductivity of the LiBH4/SiO2 interface layer is estimated to be 10(5) times higher than that of pure bulk LiBH4. The result highlights the importance of the interface and indicates that significant enhancement in ionic conductivity can be achieved via interface engineering. PMID:27468702

  4. Effect of Cu doping on room temperature ferromagnetic behavior of Mn doped LiNbO3 films

    NASA Astrophysics Data System (ADS)

    Bu, Dechong; Fu, Yuting; Sun, Ning; Li, Chunjing; Li, Yanghua; An, Yukai; Liu, Jiwen

    2016-11-01

    Cu and Mn co-doped LiNbO3 films were deposited on Si (111) substrates by rf-magnetron sputtering. XRD shows a randomly oriented polycrystalline R3C structure of LiNbO3 was formed in the films annealed at 1000 °C for 1 h in air. XPS and XAFS determine that Mn2+ substitutes on the Li site with a Li vacancy and Cu2+ substitutes on the Nb site with an oxygen vacancy in the LiNbO3 lattice. SQUID measurements indicate that all the films exhibit room temperature ferromagnetism, attributed to a strong d-d electron interaction between Mn and Nb and the bound magnetic polarons resulting from the oxygen vacancies. The saturated magnetization increases but the atom magnetic moment decreases with increasing Cu content in the films. The drop of the atom magnetic moment may arise from the antiferromagnetic coupling among adjacent Cu ions and an antiparallel configuration between Cu2+ ions and their trapped electrons.

  5. Hydrogen storage in Li-doped fullerene-intercalated hexagonal boron nitrogen layers

    NASA Astrophysics Data System (ADS)

    Cheng, Yi-Han; Zhang, Chuan-Yu; Ren, Juan; Tong, Kai-Yu

    2016-10-01

    New materials for hydrogen storage of Li-doped fullerene (C20, C28, C36, C50, C60, C70)-intercalated hexagonal boron nitrogen ( h-BN) frameworks were designed by using density functional theory (DFT) calculations. First-principles molecular dynamics (MD) simulations showed that the structures of the C n -BN ( n = 20, 28, 36, 50, 60, and 70) frameworks were stable at room temperature. The interlayer distance of the h-BN layers was expanded to 9.96-13.59 Å by the intercalated fullerenes. The hydrogen storage capacities of these three-dimensional (3D) frameworks were studied using grand canonical Monte Carlo (GCMC) simulations. The GCMC results revealed that at 77 K and 100 bar (10 MPa), the C50-BN framework exhibited the highest gravimetric hydrogen uptake of 6.86 wt% and volumetric hydrogen uptake of 58.01 g/L. Thus, the hydrogen uptake of the Li-doped C n -intercalated h-BN frameworks was nearly double that of the non-doped framework at room temperature. Furthermore, the isosteric heats of adsorption were in the range of 10-21 kJ/mol, values that are suitable for adsorbing/desorbing the hydrogen molecules at room temperature. At 193 K (-80 °C) and 100 bar for the Li-doped C50-BN framework, the gravimetric and volumetric uptakes of H2 reached 3.72 wt% and 30.08 g/L, respectively.

  6. High-Rate LiTi2(PO4)3@N-C Composite via Bi-nitrogen Sources Doping.

    PubMed

    Sun, Dan; Xue, Xia; Tang, Yougen; Jing, Yan; Huang, Bin; Ren, Yu; Yao, Yan; Wang, Haiyan; Cao, Guozhong

    2015-12-30

    Mesoporous LiTi2(PO4)3@nitrogen-rich doped carbon composites have been synthesized by a novel bi-nitrogen sources doping strategy. Tripolycyanamide (C3H6N6) and urea are proposed for the first time as both nitrogen and carbon sources to achieve a homogeneous nitrogen-doped carbon coating layer via an in situ method. The electrode delivers ultrahigh rate performance and outstanding cycling stability in lithium ion batteries (LIBs). In an organic electrolyte system, the electrode demonstrates high discharge capacities of 120 mAh g(-1) and 87 mAh g(-1) at 20C and 50C, respectively. Moreover, 89.5% of initial discharge capacity is retained after 1000 cycles at 10C. When used as an anode for aqueous LIBs, the electrode also demonstrates superior rate capability with the discharge capacity of 103 mAh g(-1) at 10C, corresponding to 84% of that at 1C. Outstanding cycling stability with capacity retention of 91.2% after 100 cycles at 30 mA g(-1) and 90.4% over 400 cycles at 150 mA g(-1) are also demonstrated. The uniform nitrogen-rich carbon coating and unique mesoporous structure play important roles in effectively suppressing the charge-transfer resistance and facilitating Li ion/electron diffusion, thus leading to the superior electrochemical properties. PMID:26633580

  7. Thin hybrid electrolyte based on garnet-type lithium-ion conductor Li7La3Zr2O12 for 12 V-class bipolar batteries

    NASA Astrophysics Data System (ADS)

    Yoshima, Kazuomi; Harada, Yasuhiro; Takami, Norio

    2016-01-01

    Thin hybrid electrolytes based on lithium-ion conducting ceramics with a few micrometers thickness have been studied in order to be practically applied to 12 V-class bipolar battery with liquid-free and separator-free. A cubic garnet-type Li7La3Zr2O12 (LLZ)-based hybrid electrolyte composed of LLZ particles coated with 4 wt% polyacrylonitrile (PAN)-based gel polymer electrolyte was prepared as the thin electrolyte layer, which reduced the internal resistance of LiMn0.8Fe0.2PO4(LMFP)/Li4Ti5O12(LTO) cells and enabled discharge at low temperatures. The conductivity of the LLZ-based hybrid electrolyte at 25°C was one order of magnitude higher than that of the LLZ solid electrolyte and comparable to that of the PAN-based gel polymer. The activation energy for ionic conductivity of the hybrid electrolyte was significantly smaller than that of the gel polymer electrolyte. The fabricated 12 V-class bipolar LMFP/LTO battery using the thin LLZ-based hybrid electrolyte layer exhibited good performance in terms of discharge rate capability, operating in the wide temperature range of -40°C to 80°C, and charge-discharge cycling comparable to those of conventional lithium-ion batteries.

  8. Influence of annealing on ionic transfer and storage stability of Li2S-P2S5 solid electrolyte

    NASA Astrophysics Data System (ADS)

    Wei, Junjun; Kim, Hyea; Lee, Dong-Chan; Hu, Renzhong; Wu, FeiXiang; Zhao, Hailei; Alamgir, Faisal M.; Yushin, Gleb

    2015-10-01

    In this study, the impact of annealing treatment on the ionic transfer and storage stability of 70Li2S-30P2S5 glass-ceramic solid electrolyte (SE) pellets are investigated. The ionic conductivity is enhanced from 1 to 1.5 mS cm-1, while the total interfacial resistance of Li/SE/Li cell is reduced by over an order of magnitude with increasing annealing temperature up to 250 °C. Higher annealing temperature induced formation of a low conductivity Li4P2S6 phase, which increased ionic and interfacial resistances. Storage stability is also improved by annealing treatments. Preparation of exemplary Li4Ti5O12 (LTO) electrodes involving mechanical milling with SE particles undesirably induces formation of a TiS2 phase at the interfaces. Annealing the cells at 250 °C induces further reaction between LTO and SE, increasing TiS2 content and reducing cell rate performance. High reactivity between metal oxides and sulfide-based SE may be an obstacle for the preparation of high performance rechargeable solid state Li ion batteries.

  9. Structural and spectroscopic properties of pure and doped LiCe(PO{sub 3}){sub 4}

    SciTech Connect

    Abdelhedi, M.; Horchani-Naifer, K.; Dammak, M.; Ferid, M.

    2015-10-15

    Graphical abstract: Emission and excitation and spectra of Eu{sup 3+} doped LiCe(PO{sub 3}){sub 4} host lattice with 1, 2, 3 and 4 mol%. - Highlights: • Europium–doped LiCe(PO{sub 3}){sub 4} were prepared by flux method. • It was analyzed by infrared and Raman spectroscopy, and luminescence spectroscopy. • LiCe(PO{sub 3}){sub 4} doped with Eu{sup 3+} ions as luminophore host materials to produce an intense red. - Abstract: Single crystals of LiCe(PO{sub 3}){sub 4} polyphosphate have been synthesized by the flux method and its structural and luminescence properties have been investigated. This compound crystallizes in the space group C2/c with unit cell dimensions a = 16.52(7) Å, b = 7.09(4) Å, c = 9.83 (4)Å, β = 126.29(4)°, Z = 8 and V = 927.84(3) Å{sup 3}. The obtained polytetraphosphate exhibits very small crystals and the dopant Eu{sup 3+} ions were successfully incorporated into the sites of Ce{sup 3+} ions of the host lattice. The spectroscopy properties confirm the potentiality of present LiCe(PO{sub 3}){sub 4} doped with Eu{sup 3+} ions as luminophore host materials to produce an intense red luminescence at 628 nm corresponding to {sup 5}D{sub 0} → {sup 7}F{sub 2} emission level and have significant importance in the development of emission optical systems.

  10. Electric Field Induced Reversible Phase Transition in Li Doped Phosphorene: Shape Memory Effect and Superelasticity.

    PubMed

    Deng, Junkai; Chang, Zhenyue; Zhao, Tong; Ding, Xiangdong; Sun, Jun; Liu, Jefferson Zhe

    2016-04-13

    Phosphorene, the single-layer form of black phosphorus, as a new member of atomically thin material family, has unique puckered atomistic structure and remarkable physical and chemical properties. In this paper, we report a discovery of an unexpected electromechanical energy conversion phenomenon-shape memory effect-in Li doped phosphorene P4Li2, using ab initio density functional theory simulations. Two stable phases are found for the two-dimensional (2D) P4Li2 crystal. Applying an external electric field can turn on or off the unique adatom switches in P4Li2 crystals, leading to a reversible structural phase transition and thereby the shape memory effect with an tunable strain output as high as 2.06%. Our results demonstrate that multiple temporary shapes are attainable in one piece of P4Li2 material, offering programmability that is particularly useful for device designs. Additionally, the P4Li2 displays superelasticity that can generate a pseudoelastic tensile strain up to 6.2%. The atomic thickness, superior flexibility, excellent electromechanical strain output, the special shape memory phenomenon, and the programmability feature endow P4Li2 with great application potential in high-efficient energy conversion at nanoscale and flexible nanoelectromechanical systems. PMID:27043220

  11. Electric Field Induced Reversible Phase Transition in Li Doped Phosphorene: Shape Memory Effect and Superelasticity.

    PubMed

    Deng, Junkai; Chang, Zhenyue; Zhao, Tong; Ding, Xiangdong; Sun, Jun; Liu, Jefferson Zhe

    2016-04-13

    Phosphorene, the single-layer form of black phosphorus, as a new member of atomically thin material family, has unique puckered atomistic structure and remarkable physical and chemical properties. In this paper, we report a discovery of an unexpected electromechanical energy conversion phenomenon-shape memory effect-in Li doped phosphorene P4Li2, using ab initio density functional theory simulations. Two stable phases are found for the two-dimensional (2D) P4Li2 crystal. Applying an external electric field can turn on or off the unique adatom switches in P4Li2 crystals, leading to a reversible structural phase transition and thereby the shape memory effect with an tunable strain output as high as 2.06%. Our results demonstrate that multiple temporary shapes are attainable in one piece of P4Li2 material, offering programmability that is particularly useful for device designs. Additionally, the P4Li2 displays superelasticity that can generate a pseudoelastic tensile strain up to 6.2%. The atomic thickness, superior flexibility, excellent electromechanical strain output, the special shape memory phenomenon, and the programmability feature endow P4Li2 with great application potential in high-efficient energy conversion at nanoscale and flexible nanoelectromechanical systems.

  12. Glass transition temperature and conductivity in Li2O and Na2O doped borophosphate glasses

    NASA Astrophysics Data System (ADS)

    Ashwajeet, J. S.; Sankarappa, T.; Ramanna, R.; Sujatha, T.; Awasthi, A. M.

    2015-08-01

    Two alkali doped Borophosphate glasses in the composition, (B2O3)0.2. (P2O5)0.3. (Na2O)(0.5-x). (Li2O)x, where x = 0.05 to 0.50 were prepared by standard melt quenching method at 1200K. Non-crystalline nature was confirmed by XRD studies. Room temperature density was measured by Archimedes principle. DC conductivity in the temperature range from 300K to 575K has been measured. Samples were DSC studied in the temperature range from 423K to 673K and glass transition temperature was determined. Glass transition temperature passed through minima for Li2O con.2centration between 0.25 and 0.30 mole fractions. Activation energy of conduction has been determined by analyzing temperature variation of conductivity determining Arrhenius law. Conductivity passed through minimum and activation passed through maximum for Li2O content from 0.25 to 0.30 mole fractions. Glass transition temperature passed through minimum for the same range of Li2O content. These results revealed mixed alkali effect taking place in these glasses. It is for the first time borophosphate glasses doped with Li2O and Na2O have been studied for density and dc conductivity and, the mixed alkali effect (MAE) has been observed.

  13. Probing the Degradation Mechanisms in Electrolyte Solutions for Li-ion Batteries by In-Situ Transmission Electron Microscopy

    SciTech Connect

    Abellan Baeza, Patricia; Mehdi, Beata L.; Parent, Lucas R.; Gu, Meng; Park, Chiwoo; Xu, Wu; Zhang, Yaohui; Arslan, Ilke; Zhang, Jiguang; Wang, Chong M.; Evans, James E.; Browning, Nigel D.

    2014-02-21

    One of the goals in the development of new battery technologies is to find new electrolytes with increased electrochemical stability. In-situ (scanning) transmission electron microscopy ((S)TEM) using an electrochemical fluid cell provides the ability to rapidly and directly characterize electrode/electrolyte interfacial reactions under battery relevant electrochemical conditions. Furthermore, as the electron beam itself causes a localized electrochemical reaction when it interacts with the electrolyte, the breakdown products that occur during the first stages of battery operation can potentially be simulated and characterized using a straightforward in-situ liquid stage (without electrochemical biasing capabilities). In this paper, we have studied the breakdown of a range of inorganic/salt complexes that are used in state-of-the-art Li-ion battery systems. The results of the in-situ (S)TEM experiments matches with previous stability tests performed during battery operation and the breakdown products and mechanisms are also consistent with known mechanisms. This analysis indicates that in-situ liquid stage (S)TEM observations can be used to directly test new electrolyte designs and provide structural insights into the origin of the solid electrolyte interphase (SEI) formation mechanism.

  14. Ab initio calculations of the electronic structure of silicon nanocrystals doped with shallow donors (Li, P)

    SciTech Connect

    Kurova, N. V. Burdov, V. A.

    2013-12-15

    The results of ab initio calculations of the electronic structure of Si nanocrystals doped with shallow donors (Li, P) are reported. It is shown that phosphorus introduces much more significant distortions into the electronic structure of the nanocrystal than lithium, which is due to the stronger central cell potential of the phosphorus ion. It is found that the Li-induced splitting of the ground state in the conduction band of the nanocrystal into the singlet, doublet, and triplet retains its inverse structure typical for bulk silicon.

  15. Magnetic and dielectric studies of Li-Cu co-doped ZnO nanoparticles

    NASA Astrophysics Data System (ADS)

    Vivek, S.; Ajith, S. K.; Chitralekha, C. S.; Nair, Swapna S.

    2016-05-01

    Room temperature ferromagnetism has been observed in Li-Cu co-doped ZnO nanoparticles prepared by sol-gel route. Our studies indicated that the observed ferromagnetism is a surface phenomenon which depends on oxygen vacancy and the nature of the dopants. Dependence of ferromagnetism on the annealing temperature indicated the role of oxygen vacancy, and the decrease in coercivity as the particle size increases indicates the surface dependence of ferromagnetism. It is found that the addition of dopants also enhanced ferromagnetism. Dielectric studies indicated an increase in dielectric constant as the doping concentration is increased.

  16. Development of zirconia electrolyte films on porous doped lanthanum manganite cathodes by electrophoretic deposition

    SciTech Connect

    Basu, R.N.; Randall, C.A.; Mayo, M.J.

    2000-07-01

    Electrophoretic deposition (EPD) was explored as an inexpensive route for fabricating the 8 mol% yttria stabilized zirconia electrolyte in solid oxide fuel cells (SOFCs). Normally, deposition of particulate ceramic powders onto a sintered porous surface yields a non uniform coating which, after sintering, results in porosity, surface roughness and cracking in the coating. To overcome this problem, the present study used a fugitive graphite interlayer between the porous air electrode supported (AES) cathode tube (doped-LaMnO{sub 3}) and the deposited zirconia film. By this approach, a fairly dense green coating ({approximately}60%) was obtained, which yielded a smooth surface and pore-free microstructure after sintering. Preliminary results on the effect of a fugitive interlayer on the unfired (green) and fired zirconia coatings are discussed.

  17. Dynamic in situ fourier transform infrared measurements of chemical bonds of electrolyte solvents during the initial charging process in a Li ion battery

    NASA Astrophysics Data System (ADS)

    Hongyou, Kenichi; Hattori, Takashi; Nagai, Youko; Tanaka, Toshihiro; Nii, Hiroyuki; Shoda, Kaoru

    2013-12-01

    Solvation/desolvation and the solid electrolyte interphase (SEI) formation at a graphite electrode during the initial charging process were investigated using in situ Fourier transform infrared spectroscopy (FTIR) measurements. These measurements were developed by applying a diamond attenuated total reflectance (ATR) crystal, which probed the electrolyte solvents at the surface of the graphite electrode and provided successive FTIR spectra with high signal-to-noise ratio. The charging process was performed in the Li(reference)/electrolyte/graphite(working)/Cu cell at a voltage ranging from 3.2 to 0.0001 V vs. Li/Li+. The measurement elucidated the change in the chemical bond of the electrolyte solvents. In an early stage, the amounts of solvated and desolvated solvents changed, providing evidence that the Li+ ions were intercalated into the graphite layer. The formation of the Li alkyl carbonate that forms the SEI layer was facilitated toward the end of the charging process. Measurements were also obtained of the electrolyte with a vinylene carbonate additive, and the contribution of the additive to the electrolyte solvent reduction was investigated.

  18. Toward 5 V Li-Ion Batteries: Quantum Chemical Calculation and Electrochemical Characterization of Sulfone-Based High-Voltage Electrolytes.

    PubMed

    Wu, Feng; Zhou, Hang; Bai, Ying; Wang, Huali; Wu, Chuan

    2015-07-15

    In seeking new sulfone-based electrolytes to meet the demand of 5 V lithium-ion batteries, we have combined the theoretical quantum chemistry calculation and electrochemical characterization to explore several sulfone/cosolvent systems. Tetramethylene sulfone (TMS), dimethyl sulfite (DMS), and diethyl sulfite (DES) were used as solvents, and three kinds of lithium salts including LiBOB, LiTFSI, and LiPF6 were added into TMS/DMS [1:1, (v)] and TMS/DES [1:1, (v)] to form high-voltage electrolyte composites, respectively. All of these electrolytes display wide electrochemical windows of more than 5.4 V, with the high electrolyte conductivities being more than 3 mS/cm at room temperature. It is indicated that to achieve the best ionic conductivity in TMS/DMS cosolvent, the optimized concentrations of lithium salts LiBOB, LiTFSI, and LiPF6 were 0.8, 1, and 1 M, respectively. Furthermore, the vibrational changes of the molecular functional groups in the cosolvents were evaluated by Fourier transform infrared spectroscopy. It is found that lithium salts show strong interaction with the main functional sulfone groups and sulfonic acid ester group, thus playing a vital role in the enhancement of the ionic conductivity and electrochemical stability of the solvent system. These sulfone-based solvents with high electrochemical stability are expected to become a new generation of a high-voltage organic electrolytic liquid system for lithium-ion batteries. PMID:26087246

  19. Toward 5 V Li-Ion Batteries: Quantum Chemical Calculation and Electrochemical Characterization of Sulfone-Based High-Voltage Electrolytes.

    PubMed

    Wu, Feng; Zhou, Hang; Bai, Ying; Wang, Huali; Wu, Chuan

    2015-07-15

    In seeking new sulfone-based electrolytes to meet the demand of 5 V lithium-ion batteries, we have combined the theoretical quantum chemistry calculation and electrochemical characterization to explore several sulfone/cosolvent systems. Tetramethylene sulfone (TMS), dimethyl sulfite (DMS), and diethyl sulfite (DES) were used as solvents, and three kinds of lithium salts including LiBOB, LiTFSI, and LiPF6 were added into TMS/DMS [1:1, (v)] and TMS/DES [1:1, (v)] to form high-voltage electrolyte composites, respectively. All of these electrolytes display wide electrochemical windows of more than 5.4 V, with the high electrolyte conductivities being more than 3 mS/cm at room temperature. It is indicated that to achieve the best ionic conductivity in TMS/DMS cosolvent, the optimized concentrations of lithium salts LiBOB, LiTFSI, and LiPF6 were 0.8, 1, and 1 M, respectively. Furthermore, the vibrational changes of the molecular functional groups in the cosolvents were evaluated by Fourier transform infrared spectroscopy. It is found that lithium salts show strong interaction with the main functional sulfone groups and sulfonic acid ester group, thus playing a vital role in the enhancement of the ionic conductivity and electrochemical stability of the solvent system. These sulfone-based solvents with high electrochemical stability are expected to become a new generation of a high-voltage organic electrolytic liquid system for lithium-ion batteries.

  20. Electrochemical Windows of Sulfone-Based Electrolytes for High-Voltage Li-Ion Batteries

    SciTech Connect

    Shao, Nan; Sun, Xiao-Guang; Dai, Sheng; Jiang, Deen

    2011-01-01

    Further development of high-voltage lithium-ion batteries requires electrolytes with electrochemical windows greater than 5 V. Sulfone-based electrolytes are promising for such a purpose. Here we compute the electrochemical windows for experimentally tested sulfone electrolytes by different levels of theory in combination with various solvation models. The MP2 method combined with the polarizable continuum model is shown to be the most accurate method to predict oxidation potentials of sulfone-based electrolytes with mean deviation less than 0.29 V. Mulliken charge analysis shows that the oxidation happens on the sulfone group for ethylmethyl sulfone and tetramethylene sulfone, and on the ether group for ether functionalized sulfones. Large electrochemical windows of sulfone-based electrolytes are mainly contributed by the sulfone group in the molecules which helps lower the HOMO level. This study can help understand the voltage limits imposed by the sulfone-based electrolytes and aid in designing new electrolytes with greater electrochemical windows.

  1. DFT STUDY OF HYDROGEN STORAGE ON Li- AND Na-DOPED C59B HETEROFULLERENE

    NASA Astrophysics Data System (ADS)

    Zahedi, Ehsan; Mozaffari, Majid

    2014-05-01

    Effect of light alkali metal (Li and Na) decorated on the C59B heterofullerene for hydrogen storage is considered using DFT-MPW1PW91 method. Results show that Li and Na atoms strongly prefer to adsorb on top of five-member and six-member ring where a carbon atom is replaced by a boron atom. Significant charge transfer from the alkali metal to the C59B compensates for the electron deficiency of C59B and makes the latter aromatic in nature. Corrected binding energies of hydrogen molecule on the alkali-doped C59B using counterpoise method, structural properties and NBO analysis indicate that first hydrogen molecule is adsorbed physically and does not support minimal conditions of DOE requirement. Finally, positive values of binding energies for the adsorption of a second hydrogen molecule show that alkali doped C59B are capable of storing a maximum of one hydrogen molecule.

  2. The correlation of the properties of pyrrolidinium-based ionic liquid electrolytes with the discharge-charge performances of rechargeable Li-O2 batteries

    NASA Astrophysics Data System (ADS)

    Li, Yu; Zhang, Zhonglin; Duan, Donghong; Sun, Yanbo; Wei, Guoqiang; Hao, Xiaogang; Liu, Shibin; Han, Yunxia; Meng, Weijuan

    2016-10-01

    Pyrrolidinium-based ionic liquids (ILs), such as PYR13TFSI, PYR14TFSI, and PYR1(2O1)TFSI, exhibit high thermal and electrochemical stability with wide electrochemical windows as electrolytes for application to rechargeable Li-O2 batteries. In this work, several fundamental properties of three ILs are measured: the ionic conductivity, oxygen solubility, and oxygen diffusion coefficient. The oxygen electro-reduction kinetics is characterized using cyclic voltammetry. The performances of Li-O2 batteries with these IL electrolytes are also investigated using electrochemical impedance spectroscopy and galvanostatic discharge-charge tests. The results demonstrate that the PYR1(2O1)TFSI electrolyte battery has a higher first-discharge voltage than the PYR13TFSI electrolyte and PYR14TFSI electrolyte batteries. Both PYR13TFSI- and PYR1(2O1)TFSI-based batteries exhibit higher first-discharge capacities and better cycling stabilities than the PYR14TFSI-based battery for 30 cycles. A theoretical analysis of the experimental results shows that the diffusion coefficient and solubility of oxygen in the electrolyte remarkably affect the discharge capacity and cycling stability of the batteries. Particularly, the oxygen diffusion coefficient of the IL electrolyte can effectively facilitate the electrochemical oxygen electro-reduction reaction and oxygen concentration distribution in the catalyst layers of air electrodes. The oxygen diffusion coefficient and oxygen solubility improvements of IL electrolytes can enhance the discharge-charge performances of Li-O2 batteries.

  3. Ionic relaxation in PEO/PVDF-HFP-LiClO4 blend polymer electrolytes: dependence on salt concentration

    NASA Astrophysics Data System (ADS)

    Das, S.; Ghosh, A.

    2016-06-01

    In this paper, we have studied the effect of LiClO4 salt concentration on the ionic conduction and relaxation in poly ethylene oxide (PEO) and poly (vinylidene fluoride hexafluoropropylene) (PVDF-HFP) blend polymer electrolytes, in which the molar ratio of ethylene oxide segments to lithium ions (R  =  EO: Li) has been varied between 3 and 35. We have observed two phases in the samples containing low salt concentrations (R  >  9) and single phase in the samples containing high salt concentrations (R  ⩽  9). The scanning electron microscopic images indicate that there exists no phase separation in the blend polymer electrolytes. The temperature dependence of the ionic conductivity shows two slopes corresponding to high and low temperatures and follows Arrhenius relation for the samples containing low salt concentrations (R  >  9). The conductivity relaxation as well as the structural relaxation has been clearly observed at around 104 Hz and 106 Hz for these concentrations of the blended electrolytes. However, a single conductivity relaxation peak has been observed for the compositions with R  ⩽  9. The scaling of the conductivity spectra shows that the relaxation mechanism is independent of temperature, but depends on salt concentration.

  4. Study of SEI layer formed on graphite anodes in PC/LiBOB electrolyte using IR spectroscopy

    SciTech Connect

    Zhuang, G.V.; Xu, K.; Jow, T.R.; Ross Jr., P.N.

    2003-10-30

    Formation of the SEI layer on graphite anodes cycled in propylene carbonate (PC) lithium bis(oxolato)borate (LiBOB) electrolyte was studied by ex-situ Fourier Transform Infrared Spectroscopy (FTIR) analysis in the attenuated total reflection (ATR) mode. The results provide a more refined description of the composition than earlier analyses with x-ray photoelectron spectroscopy (XPS). The vibrational spectra clearly show that electrochemical reduction of the BOB anion is a part of the SEI formation chemistry. Carboxylate and/or oxalate functional groups derived from the BOB anion were the components assigned as the ''semicarbonate'' species in the C 1s XPS spectra of the SEI layer formed in LiBOB electrolyte. Reduction of the BOB anion changes the oxygen coordination around the B atom from tetrahedral BO4 to trigonal BO3, e.g., meta- or orthoborate. Based on the combination of electrochemical and FTIR data, we propose that the preferential reduction of the BOB anion versus the PC solvent molecule is responsible for the cyclability of graphite anodes in purely PC-based electrolyte.

  5. Solid-State Li-Ion Batteries Using Fast, Stable, Glassy Nanocomposite Electrolytes for Good Safety and Long Cycle-Life.

    PubMed

    Tan, Guoqiang; Wu, Feng; Zhan, Chun; Wang, Jing; Mu, Daobin; Lu, Jun; Amine, Khalil

    2016-03-01

    The development of safe, stable, and long-life Li-ion batteries is being intensively pursued to enable the electrification of transportation and intelligent grid applications. Here, we report a new solid-state Li-ion battery technology, using a solid nanocomposite electrolyte composed of porous silica matrices with in situ immobilizing Li(+)-conducting ionic liquid, anode material of MCMB, and cathode material of LiCoO2, LiNi1/3Co1/3Mn1/3O2, or LiFePO4. An injection printing method is used for the electrode/electrolyte preparation. Solid nanocomposite electrolytes exhibit superior performance to the conventional organic electrolytes with regard to safety and cycle-life. They also have a transparent glassy structure with high ionic conductivity and good mechanical strength. Solid-state full cells tested with the various cathodes exhibited high specific capacities, long cycling stability, and excellent high temperature performance. This solid-state battery technology will provide new avenues for the rational engineering of advanced Li-ion batteries and other electrochemical devices. PMID:26862941

  6. Characterization of pore and crystal structure of synthesized LiBOB with varying quality of raw materials as electrolyte for lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Lestariningsih, Titik; Ratri, Christin Rina; Wigayati, Etty Marty; Sabrina, Qolby

    2016-02-01

    Characterization of pore structure and crystal structure of the LiB(C2O4)2H2O or LIBOB compound has been performed in this study. These recent years, research regarding LiBOB electrolyte salt have been performed using analytical-grade raw materials, therefore this research was aimed to synthesized LiBOB electrolyte salt using the cheaper and abundant technical-grade raw materials. Lithium hydroxide (LiOH), oxalic acid dihydrate (H2C2O4.2H2O), and boric acid (H3BO3) both in technical-grade and analytical-grade quality were used as raw materials for the synthesis of LiBOB. Crystal structure characterization results of synthesized LiBOB from both technical-grade and analytical-grade raw materials have shown the existence of LiBOB and LiBOB hydrate phase with orthorombic structure. These results were also confirmed by FT-IR analysis, which showed the functional groups of LiBOB compounds. SEM analysis results showed that synthesized LiBOB has spherical structure, while commercial LiBOB has cylindrical structure. Synthesized LiBOB has a similar pore size of commercial LiBOB, i.e. 19 nm (mesoporous material). Surface area of synthesized LiBOB from analytical-grade raw materials and technical-grade materials as well as commercial LIBOB were 88.556 m2/g, 41.524 m2/g, and 108.776 m2/g, respectively. EIS analysis results showed that synthesized LiBOB from technical-grade raw materials has lower conductivity than synthesized LiBOB from analytical-grade raw materials.

  7. Thermoluminescence Study of Gamma Irradiated Cr-Doped LiF Phosphors

    NASA Astrophysics Data System (ADS)

    Kumar, Satinder; Gathania, A. K.; Vij, Ankush; Kumar, Ravi

    2016-06-01

    We have synthesized Cr-doped LiF phosphors by using modified co-precipitation. X-ray diffraction study confirms the single-phase cubic structure up to 0.05 mol.% of Cr in LiF; afterwards, a secondary phase of formation was observed. The field emission scanning electron microscope (FESEM) images revealed micro-cubic surface morphology of samples. The thermoluminescent (TL) behavior of the samples studied after irradiating them with gamma rays in the dose range 0.1-30 kGy. The TL glow curve of Cr-doped LiF comprises a prominent peak observed at 407 K and a broad band ranging from 448 K to 512 K at a fixed gamma dose of 10 kGy. The shape of the TL glow curve remained similar at all concentrations of Cr in LiF; however, TL intensity was found to vary with Cr concentration, and Cr (0.02 mol.%)-doped LiF sample exhibit highest TL response. The glow curve of the optimized sample as a function of gamma irradiation dose within the range 0.1-30 kGy shows an almost linear increase in TL intensity of the main glow peak up to 10 kGy, and afterwards it decreases. Further, at the high dose of 30 kGy, the intensity of the prominent TL glow peak at 407 K decreases and another broad peak starts growing at 468 K signifying the formation of new trapping sites. The kinetic parameters, namely activation energy, order of kinetics, and frequency factor of the optimized sample were evaluated by using Chen's peak shape method and glow curve deconvolution (GCD) functions based on Kitti's equations.

  8. Uranium doped LiSAF as a precursor for a 229 Th nuclear clock experiment

    NASA Astrophysics Data System (ADS)

    Meyer, Edmund; Hehlen, Markus; Barker, Beau; Collins, Lee; Zhao, Xinxin

    2016-05-01

    We experimentally and numerically study the simple idea of growing 233 U doped LiSAF crystals. The micro-pulling-down technique is used to grow U:LiSAF single crystals with a high number density of U ions. The crystals are in the shape of rods that are geometrically well matched for imaging onto the spectrophotometer input slit. Growth is performed in an RF-heated chamber under argon inert atmosphere at elevated pressure. This reduces the evaporation of LiF and AlF3 from the melt and crystal surface during growth which otherwise tends to degrade the crystal quality. Through physical arguments and robust numerical calculation we determine the oxidation state of the U ion to likely be trivalent and occupying the Sr site. Charge compensation is numerically studied through F interstitials and Li vacancies. We determine the energetically most favorable state for U:LiSAF and investigate the effects upon α-decay of 233 U to 229 Th, which ~ 2% of the time is in the excited isomeric state. Additional charge compensation mechanisms are needed to accommodate the Th4+ ground oxidation state and we investigate F interstitial as well as Li vacancy. The band structure is calculated and analyzed for select cases.

  9. A structured three-dimensional polymer electrolyte with enlarged active reaction zone for Li-O2 batteries.

    PubMed

    Bonnet-Mercier, Nadège; Wong, Raymond A; Thomas, Morgan L; Dutta, Arghya; Yamanaka, Keisuke; Yogi, Chihiro; Ohta, Toshiaki; Byon, Hye Ryung

    2014-01-01

    The application of conventional solid polymer electrolyte (SPE) to lithium-oxygen (Li-O2) batteries has suffered from a limited active reaction zone due to thick SPE and subsequent lack of O2 gas diffusion route in the positive electrode. Here we present a new design for a three-dimensional (3-D) SPE structure, incorporating a carbon nanotube (CNT) electrode, adapted for a gas-based energy storage system. The void spaces in the porous CNT/SPE film allow an increased depth of diffusion of O2 gas, providing an enlarged active reaction zone where Li(+) ions, O2 gas, and electrons can interact. Furthermore, the thin SPE layer along the CNT, forming the core/shell nanostructure, aids in the smooth electron transfer when O2 gas approaches the CNT surface. Therefore, the 3-D CNT/SPE electrode structure enhances the capacity in the SPE-based Li-O2 cell. However, intrinsic instability of poly(ethylene oxide) (PEO) of the SPE matrix to superoxide (O2(·-)) and high voltage gives rise to severe side reactions, convincing us of the need for development of a more stable electrolyte for use in this CNT/SPE design.

  10. 7Li NMR spectroscopy and ion conduction mechanism in mesoporous silica (SBA-15) composite poly(ethylene oxide) electrolyte

    NASA Astrophysics Data System (ADS)

    Reddy, M. Jaipal; Chu, Peter P.

    A composite of mesoporous silica (SBA-15) with a polyethylene oxide (PEO) polymer electrolyte is examined for use in various electrochemical devices. Incorporation of SBA-15 in a PEO:LiClO 4 polymer electrolyte facilitates salt dissociation, enhances ion conductivity, and improves miscibility between organic and inorganic moieties. Optimized conductivity is found at 10 wt.% SBA-15 composition, above this concentration the conductivity is reduced due to aggregation of a SBA-15:Li rich phase. Heating above melt temperature of PEO allows more of the polymer segments to interact with SBA-15. This results in a greater degree of disorder upon cooling, and the ion conductivity is enhanced. A 7Li MAS NMR study reveals three types of lithium-ion coordination. Two major types of conduction mechanism can be identified: one through conventional amorphous PEO; a second via hopping in a sequential manner by replacing the nearby vacancies ('holes') on the surface (both interior and exterior) of the SBA-15 channels.

  11. Identity of Passive Film Formed on Aluminum in Li-ion BatteryElectrolytes with LiPF6

    SciTech Connect

    Zhang, Xueyuan; Devine, T.M.

    2006-09-01

    The passive film that forms on aluminum in 1:1 ethylene carbonate + ethylmethyl carbonate with 1.2M LiPF{sub 6} and 1:1 ethylene carbonate + dimethyl carbonate with 1.0M LiPF{sub 6} was investigated by a combination of electrochemical quartz crystal microbalance measurements (EQCM), electrochemical impedance spectroscopy (EIS), and x-ray photoelectron spectroscopy. During anodic polarization of aluminum a film of AlF{sub 3} forms on top of the air-formed oxide, creating a duplex, or two-layered film. The thickness of the AlF{sub 3} increases with the applied potential. Independent measurements of film thickness by EQCM and EIS indicate that at a potential of 5.5V vs. Li/Li{sup +}, the thickness of the AlF{sub 3} is approximately 1 nm.

  12. 3D Nanoporous Nitrogen-Doped Graphene with Encapsulated RuO2 Nanoparticles for Li-O2 Batteries.

    PubMed

    Guo, Xianwei; Liu, Pan; Han, Jiuhui; Ito, Yoshikazu; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei

    2015-10-28

    Freestanding nanoporous N-doped graphene with encapsulated RuO2 nanoparticles is developed as a cathode for rechargeable Li-O2 batteries. The stabilized metal oxide catalyst reduces charge overpotentials enabling high-efficiency rechargeable Li-O2 batteries with a long cycling lifetime. This has important implications for the development of highly stable and catalytically active graphene-based cathodes for rechargeable Li-O2 batteries.

  13. Life of superoxide in aprotic Li-O₂ battery electrolytes: simulated solvent and counter-ion effects.

    PubMed

    Scheers, J; Lidberg, D; Sodeyama, K; Futera, Z; Tateyama, Y

    2016-04-21

    Li-air batteries ideally make use of oxygen from the atmosphere and metallic lithium to reversibly drive the reaction 2Li + O2↔ Li2O2. Conceptually, energy throughput is high and material use is efficient, but practically many material challenges still remain. It is of particular interest to control the electrolyte environment of superoxide (O2*(-)) to promote or hinder specific reaction mechanisms. By combining density functional theory based molecular dynamics (DFT-MD) and DFT simulations we probe the bond length and the electronic properties of O2*(-) in three aprotic solvents - in the presence of Li(+) or the much larger cation alternative tetrabutylammonium (TBA(+)). Contact ion pairs, LiO2*, are favoured over solvent-separated ion pairs in all solvents, but particularly in low permittivity dimethoxyethane (DME), which makes O2*(-) more prone to further reduction. The Li(+)-O2*(-) interactions are dampened in dimethyl sulfoxide (DMSO), in relation to those in DME and propylene carbonate (PC), which is reflected by smaller changes in the electronic properties of O2*(-) in DMSO. The additive TBA(+) offers an alternative, more weakly interacting partner to O2*(-), which makes it easier to remove the unpaired electron and oxidation more feasible. In DMSO, TBA(+) has close to no effect on O2*(-), which behaves as if no cation is present. This is contrasted by a much stronger influence of TBA(+) on O2*(-) in DME - comparable to that of Li(+) in DMSO. An important future goal is to compare and rank the effects of different additives beyond TBA(+). Here, the results of DFT calculations for small-sized cluster models are in qualitative agreement with those of the DFT-MD simulations, which suggests the cluster approach to be a cost-effective alternative to the DFT-MD simulations for a more extensive comparison of additive effects in future studies. PMID:26947132

  14. Li-doped B2C graphene as potential hydrogen storage medium

    NASA Astrophysics Data System (ADS)

    An, Hui; Liu, Chun-sheng; Zeng, Zhi; Fan, Chao; Ju, Xin

    2011-04-01

    Based on first-principles density functional theory, we show that Li-doped B2C graphene can serve as a high-capacity hydrogen storage medium with the gravimetric density of 7.54 wt %. The present results indicate that the strong binding of Li onto the substrate comes from the hybridizations of B 2p and C 2p orbitals with the partial occupancy of Li 2p orbitals. Both the polarization mechanism and the orbital hybridizations contribute to the adsorption of H2 molecules and the resulting adsorption energy is in the range of 0.12-0.22 eV/H2. The system reported here is favorable for the reversible hydrogen adsorption/desorption at the room temperature.

  15. Effect of bismuth doping on the physical properties of La-Li-Mn-O manganite

    NASA Astrophysics Data System (ADS)

    Yanapu, Kalyana Lakshmi; Samatham, S. Shanmukharao; Kumar, Devendra; Ganesan, V.; Reddy, P. Venugopal

    2016-03-01

    The effects of bismuth doping at La site on magnetic, electrical and thermopower properties of LaLiMnO3 manganites have been investigated. The substitution of Bi ion leads to the weakening of ferromagnetic ordering at low temperature, and Curie temperature ( T C) decreases with increase in Bi content. Interestingly, a dramatic increase in the magnitude of Seebeck coefficient at low temperature is observed in Bi-doped samples which might find potential application as thermoelectric. The results are attributed to the combined effect of the disorder and antiferromagnetic interaction induced by Bi doping. Both ρ( T) and S( T) data in the high-temperature region are discussed using small polaron hopping model.

  16. Evaluation of the physi- and chemisorption of hydrogen in alkali (Na, Li) doped fullerenes

    SciTech Connect

    Ward, Patrick A.; Teprovich, Jr., Jospeph A.; Compton, Robert N.; Schwartz, Viviane; Veith, Gabriel M.; Zidan, Ragiay

    2015-01-11

    Here, alkali doped fullerenes synthesized by two different solvent assisted mixing techniques are compared for their hydrogen uptake activity. In this study we investigated the interaction of hydrogen with alkali doped fullerenes via physisorption. In addition, we present the first mass spectrometric evidence for the formation of C60H60 via chemisorption. Hydrogen physisorption isotherms up to 1 atm at temperatures ranging from 77-303 K were measured demonstrating an increase in hydrogen uptake versus pure C60 and increased isosteric heats of adsorption for the lithium doped fullerene Li12C60. However, despite these improvements the low amount of physisorbed hydrogen at 1 atm and 77 K in these materials suggests that fullerenes do not possess enough accessible surface area to effectively store hydrogen due to their close packed crystalline nature.

  17. Evaluation of the physi- and chemisorption of hydrogen in alkali (Na, Li) doped fullerenes

    DOE PAGESBeta

    Ward, Patrick A.; Teprovich, Jr., Jospeph A.; Compton, Robert N.; Schwartz, Viviane; Veith, Gabriel M.; Zidan, Ragiay

    2015-01-11

    Here, alkali doped fullerenes synthesized by two different solvent assisted mixing techniques are compared for their hydrogen uptake activity. In this study we investigated the interaction of hydrogen with alkali doped fullerenes via physisorption. In addition, we present the first mass spectrometric evidence for the formation of C60H60 via chemisorption. Hydrogen physisorption isotherms up to 1 atm at temperatures ranging from 77-303 K were measured demonstrating an increase in hydrogen uptake versus pure C60 and increased isosteric heats of adsorption for the lithium doped fullerene Li12C60. However, despite these improvements the low amount of physisorbed hydrogen at 1 atm andmore » 77 K in these materials suggests that fullerenes do not possess enough accessible surface area to effectively store hydrogen due to their close packed crystalline nature.« less

  18. Induced Li-site vacancies and non-linear optical behavior of doped lithium niobate crystals

    NASA Astrophysics Data System (ADS)

    Xue, D.; Betzler, K.; Hesse, H.

    2001-04-01

    Second-order non-linear optical (NLO) properties of doped lithium niobate (LN) crystals (abbreviated as M:LN, where M=Mg 2+,Zn 2+, and In 3+, respectively) have been quantitatively studied from the chemical bond viewpoint. Our results show that the second-order NLO response of doped LN crystals decreases remarkably with increasing dopant concentration in the crystal. The approximately linear composition-property correlation in these doped LN crystals is quantitatively expressed in the current work. A comparison of the different influences of Mg, Zn and In dopants, respectively, shows that these dopants affect the NLO properties of LN crystals mainly via the number of Li-site vacancies induced.

  19. Li2S encapsulated by nitrogen-doped carbon for lithium sulfur batteries

    SciTech Connect

    Chen, Lin; Liu, Yuzi; Ashuri, Maziar; Liu, Caihong; Shaw, Leon L.

    2014-09-26

    Using high-energy ball milling of the Li2S plus carbon black mixture followed by carbonization of pyrrole, we have established a facile approach to synthesize Li2S-plus-C composite particles of average size 400 nm, encapsulated by a nitrogen-doped carbon shell. Such an engineered core–shell structure exhibits an ultrahigh initial discharge specific capacity (1029 mAh/g), reaching 88% of the theoretical capacity (1,166 mAh/g of Li2S) and thus offering the highest utilization of Li2S in the cathode among all of the reported works for the encapsulated Li2S cathodes. This Li2S/C composite core with a nitrogen-doped carbon shell can still retain 652 mAh/g after prolonged 100 cycles. These superior properties are attributed to the nitrogen-doped carbon shell that can improve the conductivity to enhance the utilization of Li2S in the cathode. As a result, fine particle sizes and the presence of carbon black within the Li2S core may also play a role in high utilization of Li2S in the cathode.

  20. AC ionic conductivity and DC polarization method of lithium ion transport in PMMA-LiBF4 gel polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Osman, Z.; Mohd Ghazali, M. I.; Othman, L.; Md Isa, K. B.

    2012-01-01

    Polymethylmethacrylate (PMMA)-based gel polymer electrolytes comprising ethylene carbonate-propylene carbonate (EC/PC) mixed solvent plasticizer and various concentrations of lithium tetrafluoroborate (LiBF4) salt are prepared using a solvent casting technique. Electrical conductivity and transference number measurements were carried out to investigate conductivity and charge transport in the gel polymer electrolytes. The conductivity results show that the ionic conductivity of the samples increases when the amount of salt is increased, however decreases after reaching the optimum value. This result is consistent with the transference number measurements. The conductivity-frequency dependence plots show two distinct regions; i.e. at lower frequencies the conductivity increases with increasing frequency and the frequency independent plateau region at higher frequencies. The temperature-dependence conductivity of the films seems to obey the Arrhenius rule.

  1. Ionic conductivity studies in crystalline PVA/NaAlg polymer blend electrolyte doped with alkali salt KCl

    NASA Astrophysics Data System (ADS)

    Sheela, T.; Bhajantri, R. F.; Ravindrachary, V.; Pujari, P. K.; Rathod, Sunil G.; Naik, Jagadish

    2014-04-01

    Potassium Chloride (KCl) doped poly(vinyl alcohol) (PVA)/sodium alginate (NaAlg) in 60:40 wt% polymer blend electrolytes were prepared by solution casting method. The complexation of KCl with host PVA/NaAlg blend is confirmed by FTIR and UV-Vis spectra. The XRD studies show that the crystallinity of the prepared blends increases with increase in doping. The dc conductivity increases with increase in dopant concentration. Temperature dependent dc conductivity shows an Arrhenius behavior. The dielectric properties show that both the dielectric constant and dielectric loss increases with increase in KCl doping concentration and decreases with frequency. The cole-cole plots show a decrease in bulk resistance, indicates the increase in ac conductivity, due to increase in charge carrier mobility. The doping of KCl enhances the mechanical properties of PVA/NaAlg, such as Young's modulus, tensile strength, stiffness.

  2. Dehydrogenation kinetics and reversibility of LiAlH4-LiBH4 doped with Ti-based additives and MWCNT

    NASA Astrophysics Data System (ADS)

    Thaweelap, Natthaporn; Utke, Rapee

    2016-11-01

    Dehydrogenation kinetics and reversibility of LiAlH4-LiBH4 doped with Ti-based additives (TiCl3 and Ti-isopropoxide), multiwall carbon nanotubes (MWCNT), and MWCNT impregnated with Ti-based additives are proposed. Reduction of dehydrogenation temperature as well as improvements of kinetics and reversibility, especially decomposition of thermodynamically stable hydride (LiBH4) is obtained from the samples doped with Ti-isopropoxide and MWCNT. This can be due to the fact that the formations of LixAl(1-x)B2 and LiH-Al containing phase during dehydrogenation favor decomposition of LiH, leading to increment of hydrogen capacity, and stabilization of boron in solid state, resulting in improvement of reversibility. Besides, the curvatures and thermal conductivity of MWCNT benefit hydrogen diffusion and heat transfer during de/rehydrogenation. Nevertheless, deficient hydrogen content reversible is observed in all samples due to the irreversible of LiAlH4 and/or Li3AlH6 as well as the formation of stable phase (Li2B12H12) during de/rehydrogenation.

  3. Characterization of LiF-doped TiO{sub 2} and its photocatalytic activity for decomposition of trichloromethane

    SciTech Connect

    Jiang Hongfu; Song Haiyan; Zhou Zuoxing; Liu Xingqin; Meng Guangyao

    2008-11-03

    LiF-doped TiO{sub 2} was prepared by hydrolysis of tetrabutyl titanate in a mixed LiF-H{sub 2}O-alcohol solution. The prepared LiF-doped TiO{sub 2} powders were characterized by X-ray diffraction (XRD), differential thermal analysis-thermogravimetry (DTA-TG), X-ray photoelectron spectroscopy (XPS), UV-vis absorption spectroscopy and photoluminescence spectra (PL). The photocatalytic activity was evaluated by the decomposition of trichloromethane (CHCl{sub 3}). The results showed that LiF-doping increased the amount of O{sub OH} and oxygen vacancy (OV) on the surface of TiO{sub 2}, which were beneficial to photocatalytic activity. LiF-doping inducted the new isolated energy band located above the valence band of TiO{sub 2}, which extended the absorption region of TiO{sub 2} to visible light. The results of photocatalytic reaction showed that the photocatalytic activity of LiF-doped TiO{sub 2} was 2.5 times higher than that of pure TiO{sub 2}.

  4. Transport Properties of LiTFSI-Acetamide Room Temperature Molten Salt Electrolytes Applied in an Li-Ion Battery

    NASA Astrophysics Data System (ADS)

    Yang, Chao-Chen; Hsu, Hsin-Yi; Hsu, Chen-Ruei

    2007-11-01

    In the present work some transport properties of the binary room temperature molten salt (RTMS) lithium bis(trifluoromethane sulfone)imide (LiTFSI)-acetamide [LiN(SO2CF3)2-CH3CONH2], applied in an Li-ion battery, have been investigated. The phase diagram was determined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The result reveals that the binary RTMS has an eutectic point at 201 K and the 30 mol% LiTFSI composition. The electric conductivity was measured using a direct current computerized method. The result shows that the conductivities of the melts increase with increasing temperature and acetamide content. The densities of all melts decrease with increasing temperature and acetamide content. The equivalent conductivities were fitted by the Arrhenius equation, where the activation energies were 18.15, 18.52, 20.35, 25.08 kJ/mol for 10, 20, 30, 40 mol% LiTFSI, respectively. Besides the relationships between conductivity, density composition and temperature, of the ion interaction is discussed.

  5. First Principles Study of Electrochemical and Chemical Stability of the Solid Electrolyte-Electrode Interfaces in All-Solid-State Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Zhu, Yizhou; He, Xingfeng; Mo, Yifei

    All-solid-state Li-ion battery is a promising next-generation energy-storage technology. Using novel ceramic solid electrolyte materials, all-solid-state battery has advantages of intrinsic safety and high energy density compared to current Li-ion batteries based on organic liquid electrolyte. However, the power density achieved in all-solid-state battery is still unsatisfactory. The high interfacial resistance at electrode-electrolyte interface is one of the major limiting factors. Here we demonstrated a computational approach based on first principles calculation to systematically investigate the chemical and electrochemical stability of solid electrolyte materials, and provide insightful understanding of the degradation and passivation mechanisms at the interface. Our calculation revealed that the intrinsic stability of solid electrolyte materials and solid electrolyte-electrode interfaces is limited and the formation of interphase layers are thermodynamically favorable. Our study demonstrated a computational scheme to evaluate the electrochemical and chemical stability of the solid interfaces. Our newly gained understanding provided principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries. This work was supported by Office of Energy Efficiency and Renewable Energy (DE-EE0006860).

  6. Investigations on the electrochemical decomposition of the electrolyte additive vinylene carbonate in Li metal half cells and lithium ion full cells

    NASA Astrophysics Data System (ADS)

    Qian, Yunxian; Schultz, Carola; Niehoff, Philip; Schwieters, Timo; Nowak, Sascha; Schappacher, Falko M.; Winter, Martin

    2016-11-01

    In this study, the decomposition of vinylene carbonate (VC) additive and its effect on the aging behavior is investigated in Li metal half cells and lithium ion full cells. Four electrolyte systems, the reference electrolyte with three VC additive amounts, i.e., 1, 5 and 10 vol% are examined with commercial LiNi1/3Mn1/3Co1/3O2 (NMC 111) cathode material and mesophase carbon microbeads (MCMB) anode material. The thickness changes of the cathode electrolyte interphase (CEI) and of the solid electrolyte interphase (SEI) after 5 constant current cycles at 0.1C and 200 constant current/constant voltage (potential) cycles at 1C are investigated for cells containing different amounts of VC. With the help of X-ray photoelectron spectroscopy (XPS) and high-performance liquid chromatography (HPLC), a correlation between CEI thickness change and electrolyte decomposition is figured out. The addition of VC leads to a thin CEI layer and a high capacity retention in a lithium metal half cell. A strong dependence of the performance on the VC concentration is found for half cells that results from the continuous consumption of electrolyte and the electrolyte additive at the Li metal counter electrode. In contrast, for full cells, even 1 vol% of VC helps to form both a stable CEI and SEI, while a larger amount of VC increases the CEI thickness, electric contact loss and the internal resistance.

  7. Re-dispersible Li+ and Eu3+ co-doped nanocrystalline ZnO: luminescence and EPR studies.

    PubMed

    Ningthoujam, R S; Gajbhiye, N S; Ahmed, Asar; Umre, S S; Sharma, S J

    2008-06-01

    Nano-crystals of ZnO, Eu3+ doped ZnO, and Li+, Eu3+ co-doped ZnO have been prepared by urea hydrolysis in ethylene glycol medium at 150 degrees C. Ethylene glycol acts as capping agent for nanoparticles. Three colors 437 (blue), 540 (green) and 615 nm (red) from 2 at.% Li+ and 5 at.% Eu3+ co-doped ZnO have been observed from luminescence studies compared to that from 5 at.%. Eu3+ doped ZnO, which shows emission at 437 and 615 nm. It is established that green light is originated from the oxygen vacancy brought by Li+ incorporation into ZnO. Particles are redispersible in organic solvent such as ethanol, and are able to incorporate into polymer-based material such as SiO2 matrix.

  8. Conducting polymer-doped polyprrrole as an effective cathode catalyst for Li-O{sub 2} batteries

    SciTech Connect

    Zhang, Jinqiang; Sun, Bing; Ahn, Hyo-Jun; Wang, Chengyin; Wang, Guoxiu

    2013-12-15

    Graphical abstract: - Highlights: • Doped polypyrrole as cathode catalysts for Li-O{sub 2} batteries. • Polypyrrole has an excellent redox capability to activate oxygen reduction. • Chloride doped polypyrrole demonstrated an improved catalytic performance in Li-O{sub 2} batteries. - Abstract: Polypyrrole conducting polymers with different dopants have been synthesized and applied as the cathode catalyst in Li-O{sub 2} batteries. Polypyrrole polymers exhibited an effective catalytic activity towards oxygen reduction in lithium oxygen batteries. It was discovered that dopant significantly influenced the electrochemical performance of polypyrrole. The polypyrrole doped with Cl{sup −} demonstrated higher capacity and more stable cyclability than that doped with ClO{sub 4}{sup −}. Polypyrrole conducting polymers also exhibited higher capacity and better cycling performance than that of carbon black catalysts.

  9. Computational modeling of the structure and the ionic conductivity of the solid electrolyte materials Li3AsS4 and its Ge substitutions

    NASA Astrophysics Data System (ADS)

    Al-Qawasmeh, Ahmad; Holzwarth, N. A. W.

    Oak Ridge National Laboratory (G. Sahu et al.) reported that the substitution of Ge into Li3AsS4 leads to the composition Li3.334Ge0.334As0.666S4 with impressively high ionic conductivity . We use ab initio calculations to examine the structural relationships and the ionic conductivity mechanisms for pure Li3AsS4, Li3.334Ge0.334As0.666S4, and other compositions of these electrolytes. Supported by NSF Grant DMR-1105485 and 1507942 and WFU's DEAC cluster.

  10. Structure and Stoichiometry in Supervalent Doped Li7La3 Zr2O12

    SciTech Connect

    Mukhopadhyay, Saikat; Thompson, Travis; Sakamoto, Jeff; Huq, Ashfia; Wolfenstine, Jeff; Allen, Jan L.; Bernstein, Noam; Stewart, Derek A.; Johannes, M. D.

    2015-04-20

    The oxide garnet material Li7La3 Zr2O12 shows remarkably high ionic conductivity when doped with supervalent ions that are charge compensated by Li vacancies and is currently one of the best candidates for development of a technologically relevant solid electrolyte. Determination of optimal dopant concentration, however, has remained a persistent problem due to the extreme difficulty of establishing the actual (as compared to nominal) stoichiometry of intentionally doped materials and by the fact that it is still not entirely clear what level of lattice expansion/contraction best promotes. ionic diffusion. By combining careful synthesis, neutron diffraction, high-resolution X-ray diffraction (XRD), Raman measurements, and density functional theory calculations, we show that structure and stoichiometry are intimately related such that the former can in many cases be used as a gauge of the latter. We show that different Li-vacancy creating supervalent ions (Al3+ vs Ta5+) affect the structure very differently, both in terms of the lattice constant, which is easily measurable, and hi terms of the local structure, which can be difficult or impossible to access experimentally but may have important ramifications for conduction. We carefully correlate the lattice constant to dopant type/concentration via Vegard's law and then further correlate these quantities to relevant local structural parameters. In conclusion, our work opens the possibility of developing a codopant scheme that optimizes the Li vacancy concentration and the lattice size simultaneously.

  11. Observation of non-Fermi liquid behavior in hole-doped LiFe1 -xVxAs

    NASA Astrophysics Data System (ADS)

    Xing, L. Y.; Shi, X.; Richard, P.; Wang, X. C.; Liu, Q. Q.; Lv, B. Q.; Ma, J.-Z.; Fu, B. B.; Kong, L.-Y.; Miao, H.; Qian, T.; Kim, T. K.; Hoesch, M.; Ding, H.; Jin, C. Q.

    2016-09-01

    We synthesized a series of V-doped LiFe1 -xVxAs single crystals. The superconducting transition temperature Tc of LiFeAs decreases rapidly at a rate of 7 K per 1% V. The Hall coefficient of LiFeAs switches from negative to positive with 4.2% V doping, showing that V doping introduces hole carriers. This observation is further confirmed by the evaluation of the Fermi surface volume measured by angle-resolved photoemission spectroscopy (ARPES), from which a 0.3 hole doping per V atom introduced is deduced. Interestingly, the introduction of holes does not follow a rigid band shift. We also show that the temperature evolution of the electrical resistivity as a function of doping is consistent with a crossover from a Fermi liquid to a non-Fermi liquid. Our ARPES data indicate that the non-Fermi liquid behavior is mostly enhanced when one of the hole dx z/dy z Fermi surfaces is well nested by the antiferromagnetic wave vector to the inner electron Fermi surface pocket with the dx y orbital character. The magnetic susceptibility of LiFe1 -xVxAs suggests the presence of strong magnetic impurities following V doping, thus providing a natural explanation to the rapid suppression of superconductivity upon V doping.

  12. Dual-doping to suppress cracking in spinel LiMn2O4: a joint theoretical and experimental study.

    PubMed

    Zhang, Zhifeng; Chen, Zhenlian; Wang, Guangjin; Ren, Heng; Pan, Mu; Xiao, Lingli; Wu, Kuicheng; Zhao, Liutao; Yang, Jianqing; Wu, Qingguo; Shu, Jie; Wang, Dongjie; Zhang, Hongli; Huo, Ni; Li, Jun

    2016-03-01

    Electrochemical cycling stabilities were compared for undoped and Al/Co dual-doped spinel LiMn2O4 synthesized by solid state reactions. We observed the suppression of particle fracture in Al/Co dual-doped LiMn2O4 during charge/discharge cycling and its distinguishable particle morphology with respect to the undoped material. Systematic first-principles calculations were performed on undoped, Al or Co single-doped, and Al/Co dual-doped LiMn2O4 to investigate their structural differences at the atomistic level. We reveal that while Jahn-Teller distortion associated with the Mn(3+)O6 octahedron is the origin of the lattice strain, the networking -i.e. the distribution of mixed valence Mn ions - is much more important to release the lattice strain, and thus to alleviating particle cracking. The calculations showed that the lattice mismatching between Li(+) intercalation and deintercalation of LiMn2O4 can be significantly reduced by dual-doping, and therefore also the volumetric shrinkage during delithiation. This may account for the near disappearance of cracks on the surface of Al/Co-LiMn2O4 after 350 cycles, while some obvious cracks have developed in undoped LiMn2O4 at similar particle size even after 50 cycles. Correspondingly, Al/Co dual-doped LiMn2O4 showed a good cycling stability with a capacity retention of 84.1% after 350 cycles at a rate of 1C, 8% higher than the undoped phase.

  13. Electrochemical performance of 0.5Li2MnO3-0.5Li(Mn0.375Ni0.375Co0.25)O2 composite cathode in pyrrolidinium-based ionic liquid electrolytes

    NASA Astrophysics Data System (ADS)

    Patra, Jagabandhu; Dahiya, Prem Prakash; Tseng, Chung-Jen; Fang, Jason; Lin, Yu-Wei; Basu, S.; Majumder, S. B.; Chang, Jeng-Kuei

    2015-10-01

    High-energy-density 0.5Li2MnO3-0.5Li(Mn0.375Ni0.375Co0.25)O2 composite cathodes for lithium rechargeable batteries are synthesized using an auto-combustion method. The electrode charge-discharge properties are studied at 25 and 50 °C in Li+-containing N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP-TFSI) and N-propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PMP-TFSI) ionic liquid (IL) electrolytes. The IL electrolytes have a high decomposition temperature (∼400 °C) and thus are ideal for high-safety applications. Compared to Li+/BMP-TFSI IL, Li+/PMP-TFSI IL exhibits higher ionic conductivity and lower viscosity. As a result, the composite cathode shows superior electrochemical performance in Li+/PMP-TFSI IL electrolyte. With the increase in cell temperature from 25 to 50 °C, the maximum capacities and rate capabilities of both IL cells improve significantly. Thus at 50 °C, discharge capacities of 304 mAh g-1 (@10 mA g-1) and 223 mAh g-1 (@100 mA g-1) are obtained for the Li+/PMP-TFSI cell. These capacities are superior to those for a control cell made with the same composite cathode and a conventional organic electrolyte. At elevated temperature, the cyclability of the composite cathode in the IL electrolytes is markedly higher than that obtained in a conventional organic electrolyte.

  14. A new potentiometric SO2 sensor based on Li3PO4 electrolyte film and its response characteristics

    NASA Astrophysics Data System (ADS)

    Wang, H.; Liu, Z.; Chen, D.; Jiang, Z.

    2015-07-01

    A potentiometric SO2 gas sensor based on Li3PO4 solid electrolyte has been developed using Au as the reference electrode and Li2SO4/V2O5 as the sensing electrode. The Li3PO4 film was deposited on Al2O3 substrate by resistance heating evaporation. Two Au films with designed patterns were formed on the Li3PO4 film by micro-fabrication technologies. The sensing electrode covers one electrode partly using thick-film technology. The electromotive force values between the sensing electrode and the reference electrode were measured and various characteristics were studied including sensitivity, response characteristics, and stability and selectivity. According to the results, we conclude that an optimal working temperature of the SO2 sensor is 500 °C, the measurement range is 0-100 ppm, the sensitivity is about 32.47 mV/dec, the response and the recovery time is about 5 min and 10 min, respectively. And the stability and the selectivity of the sensor are good, making it have potential in SO2 measurement of living environment.

  15. Chrystal structure properties of Al-doped Li4Ti5O12 synthesized by solid state reaction method

    NASA Astrophysics Data System (ADS)

    Sandi, Dianisa Khoirum; Priyono, Slamet; Suryana, Risa

    2016-02-01

    This research aim is to analyze the effect of Aluminum (Al) doping in the structural properties of Al-doped Li4Ti5O12 as anode in lithium ion battery. Al-doped Li4Ti5O12 powders were synthesized by solid state reaction method. LiOH.H2O, TiO2, and Al2O3 were raw materials. These materials were milled for 15 h, calcined at temperature of 750oC and sintered at temperature of 800oC. Mole percentage of doping Al (x) was varied at x=0; x=0.025; and x =0.05. Al-doped Li4Ti5O12 powders were synthesized by solid state reaction method. X-ray diffraction was employed to determine the structure of Li4Ti5O12. The PDXL software was performed on the x-ray diffraction data to estimate the phase percentage, the lattice parameter, the unit cell volume, and the crystal density. Al-doped Li4Ti5O12 has cubic crystal structure. Al-doping at x=0 and x=0.025 does not change the phase as Li4Ti5O12 while at x=0.050 the phase changes to the LiTiAlO4. The diffraction patterns show that the angle shifted to the right as the increase of x which indicated that Al substitute Ti site. Percentage of Li4Ti5O12 phase at x=0 and x=0.025 was 97.8% and 96.8%, respectively. However, the lattice parameters, the unit cell volume, and the crystal density does not change significantly at x=0; x=0.025; and x=0.050. Based on the percentage of Li4Ti5O12 phase, the Al-doped Li at x=0 and x=0.025 is promising as a lithium battery anode.

  16. Stability of the LiMn2O4 surface in a LiPF6-based non-aqueous electrolyte studied by in-situ atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Kitta, Mitsunori; Kohyama, Masanori

    2016-06-01

    Investigation of the surface stability of electrode materials in a liquid electrolyte is significantly important for understanding the deterioration of stored Li-ion battery cells. Here, we examined LiMn2O4 surfaces in a LiPF6-based non-aqueous electrolyte by in-situ atomic force microscopy. A LiMn2O4(111) surface sample with a well-defined atomically-flat structure was prepared from a MnO(111) wafer. Although the surfaces of non-exposed or dry-air-exposed samples did not change in a typical electrolyte such as LiPF6 dissolved in propylene carbonate, the surface morphology of an air-exposed sample greatly changed under the same condition. Transmission electron microscopy observation revealed that the surface roughness is increased by the dissolution of one or two atomic layers of LiMn2O4-crystal surfaces in the electrolyte. The adsorbed water on the air-exposed surface is the origin of this phenomenon.

  17. Neutron scattering study on cathode LiMn{sub 2}O{sub 4} and solid electrolyte 5(Li{sub 2}O)(P{sub 2}O{sub 5})

    SciTech Connect

    Kartini, E. Putra, Teguh P. Jahya, A. K. Insani, A.; Adams, S.

    2014-09-30

    Neutron scattering is very important technique in order to investigate the energy storage materials such as lithium-ion battery. The unique advantages, neutron can see the light atoms such as Hydrogen, Lithium, and Oxygen, where those elements are negligible by other corresponding X-ray method. On the other hand, the energy storage materials, such as lithium ion battery is very important for the application in the electric vehicles, electronic devices or home appliances. The battery contains electrodes (anode and cathode), and the electrolyte materials. There are many challenging to improve the existing lithium ion battery materials, in order to increase their life time, cyclic ability and also its stability. One of the most scientific challenging is to investigate the crystal structure of both electrode and electrolyte, such as cathodes LiCoO{sub 2}, LiMn{sub 2}O{sub 4} and LiFePO{sub 4}, and solid electrolyte Li{sub 3}PO{sub 4}. Since all those battery materials contain Lithium ions and Oxygen, the used of neutron scattering techniques to study their structure and related properties are very important and indispensable. This article will review some works of investigating electrodes and electrolytes, LiMn{sub 2}O{sub 4} and 5(Li{sub 2}O)(P{sub 2}O{sub 5}), by using a high resolution powder diffraction (HRPD) at the multipurpose research reactor, RSG-Sywabessy of the National Nuclear Energy Agency (BATAN), Indonesia.

  18. Electrolytic reduction of a simulated oxide spent fuel and the fates of representative elements in a Li2O-LiCl molten salt

    NASA Astrophysics Data System (ADS)

    Park, Wooshin; Choi, Eun-Young; Kim, Sung-Wook; Jeon, Sang-Chae; Cho, Young-Hwan; Hur, Jin-Mok

    2016-08-01

    A series of electrolytic reduction experiments were carried out using a simulated oxide spent fuel to investigate the reduction behavior of elements in a mixed oxide condition and the fates of elements in the reduction process with 1.0 wt% Li2O-LiCl. It was found out that 155% of the theoretical charge was enough to reduce the simulated. Te and Eu were expected to possibly exist in the precipitate and on the anode surface, whereas Ba and Sr showed apparent dissolution behaviors. Rare earths showed relatively low metal fractions from 28.2 to 34.0% except for Y. And the solubility of rare earths was observed to be low due to the low concentration of Li2O. The reduction of U was successful as expected showing 99.8% of a metal fraction. Also it was shown that the reduction of ZrO2 would be effective when a relatively small amount was included in a metal oxide mixture.

  19. Thermal Stability of LiPF6 Salt and Li-ion Battery Electrolytes Containing LiPF6

    SciTech Connect

    Yang, Hui; Zhuang, Guorong V; Ross, Jr, Philip N

    2006-03-08

    The thermal stability of the neat LiPF6 salt and of 1 molal solutions of LiPF6 in prototypical Li-ion battery solvents was studied with thermogravimetric analysis (TGA) and on-line FTIR. Pure LiPF6 salt is thermally stable up to 380 K in a dry inert atmosphere, and its decomposition path is a simple dissociation producing LiF as solid and PF5 as gaseous products. In the presence of water (300 ppm) in the carrier gas, its decomposition onset temperature is lowered as a result of direct thermal reaction between LiPF6 and water vapor to form POF3 and HF. No new products were observed in 1 molal solutions of LiPF6 in EC, DMC and EMC by on-line TGA-FTIR analysis. The storage of the same solutions in sealed containers at 358 K for 300 420 hrs. did not produce any significant quantity of new products as well. In particular, noalkylflurophosphates were found in the solutions after storage at elevated temperature. In the absence of either an impurity like alcohol or cathode active material that may (or may not) act as a catalyst, there is no evidence of thermally induced reaction between LiPF6 and the prototypical Li-ion battery solvents EC, PC, DMC or EMC.

  20. A new solid polymer electrolyte incorporating Li10GeP2S12 into a polyethylene oxide matrix for all-solid-state lithium batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Yanran; Wu, Chuan; Peng, Gang; Chen, Xiaotian; Yao, Xiayin; Bai, Ying; Wu, Feng; Chen, Shaojie; Xu, Xiaoxiong

    2016-01-01

    Li10GeP2S12 (LGPS) is incorporated into polyethylene oxide (PEO) matrix to fabricate composite solid polymer electrolyte (SPE) membranes. The lithium ion conductivities of as-prepared composite membranes are evaluated, and the optimal composite membrane exhibits a maximum ionic conductivity of 1.21 × 10-3 S cm-1 at 80 °C and an electrochemical window of 0-5.7 V. The phase transition behaviors for electrolytes are characterized by DSC, and the possible reasons for their enhanced ionic conductivities are discussed. The LGPS microparticles, acting as active fillers incorporation into the PEO matrix, have a positive effect on the ionic conductivity, lithium ion transference number and electrochemical stabilities. In addition, two kinds of all-solid-state lithium batteries (LiFeO4/SPE/Li and LiCoO2/SPE/Li) are fabricated to demonstrate the good compatibility between this new SPE membrane and different electrodes. And the LiFePO4/Li battery exhibits fascinating electrochemical performance with high capacity retention (92.5% after 50 cycles at 60 °C) and attractive capacities of 158, 148, 138 and 99 mAh g-1 at current rates of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C, respectively. It is demonstrated that this new composite SPE should be a promising electrolyte applied in solid state batteries based on lithium metal electrode.

  1. The electrochemical reactions of pure In with Li and Na: anomalous electrolyte decomposition, benefits of FEC additive, phase transitions and electrode performance

    SciTech Connect

    Hawks, Samantha A; Baggetto, Loic; Bridges, Craig A; Veith, Gabriel M

    2014-01-01

    Indium thin films are evaluated as an anode material for Li-ion and Na-ion batteries (theoretical capacities of 1012 mAh g-1 for Li and 467 mAh g-1 for Na). The native surface oxides are responsible for the anomalous electrolyte decomposition during the first cycle while oxidized In species are found to be responsible for the electrolyte decomposition during the subsequent cycles. The presence of 5wt% FEC electrolyte additive suppresses the occurrence of the anomalous electrolyte decomposition during the first cycle but is not sufficient to prevent the decomposition upon further cycling from 0 to 2 V. Prevention of the anomalous decomposition can be achieved by restricting the charge cut-off, for instance at 1.1 V, or by using larger amounts of FEC. The In films show moderately good capacity retention with storage capacities when cycled with Li (950 mAh g-1) but significantly less when cycled with Na (125 mAh g-1). XRD data reveal that several known Li-In phases (i.e LiIn, Li3In2, LiIn2 and Li13In3) form during the electrochemical reaction. In contrast, the reaction with Na is severely limited. The largest amount of inserted Na is evidenced for cells short-circuited 40 hrs at 65C, for which the XRD data show the coexistence of NaIn, In, and an unknown phase. During cycling, mechanical degradation due to repeated expansion/shrinkage, evidenced by SEM, coupled with SEI formation is the primary source of the capacity fade. Finally, we show that the In thin films exhibit very high rate capability for both Li (100 C) and Na (30 C).

  2. A new approach: Li2S-P2S5 thin-films prepared by thermal evaporation as solid electrolytes

    NASA Astrophysics Data System (ADS)

    Woo, Sung Pil; Kakati, Nitul; Kim, In Yea; Lee, Seok Hee; Yoon, Young Soo

    2016-08-01

    Li2S-P2S5 thin-film solid electrolytes are synthesized by using room-temperature thermal evaporation for use as lithium-ion conductors for all-solid-state Li-ion batteries. The local structures of 75.51Li2S:24.49P2S5 and 77.64Li2S:22.36P2S5 prepared in this way have hetero units that facilitate lithium-ion mobility. The lithium-ion conductivity at room temperature for the 77.64Li2S:22.36P2S5 thin-film (4.0 × 10-6 S cm-1) is higher than that for the 75.51Li2S:24.49P2S5 thin-film (1.2 × 10-6 S cm-1). The increased ion conductivity in the 77.64Li2S:22.36P2S5 film is due to the additional local P2S7 4- structure that forms a glassy state during the thermal evaporation process. The local structure can lead to a high mobility of Li+ ions in the Li2S-P2S5 system due to the non-bridging sulfide ions. Lithium-ion-conducting thin-films prepared by using thermal evaporation, as reported in this study, are promising solid electrolytes.

  3. Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

    PubMed Central

    Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

    2014-01-01

    Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses. PMID:25168309

  4. Structural and Electrochemical Consequences of Al and Ga Cosubstitution in Li7La3Zr2O12 Solid Electrolytes

    PubMed Central

    2016-01-01

    Several “Beyond Li-Ion Battery” concepts such as all solid-state batteries and hybrid liquid/solid systems envision the use of a solid electrolyte to protect Li-metal anodes. These configurations are very attractive due to the possibility of exceptionally high energy densities and high (dis)charge rates, but they are far from being realized practically due to a number of issues including high interfacial resistance and difficulties associated with fabrication. One of the most promising solid electrolyte systems for these applications is Al or Ga stabilized Li7La3Zr2O12 (LLZO) based on high ionic conductivities and apparent stability against reduction by Li metal. Nevertheless, the fabrication of dense LLZO membranes with high ionic conductivity and low interfacial resistances remains challenging; it definitely requires a better understanding of the structural and electrochemical properties. In this study, the phase transition from garnet (Ia3̅d, No. 230) to “non-garnet” (I4̅3d, No. 220) space group as a function of composition and the different sintering behavior of Ga and Al stabilized LLZO are identified as important factors in determining the electrochemical properties. The phase transition was located at an Al:Ga substitution ratio of 0.05:0.15 and is accompanied by a significant lowering of the activation energy for Li-ion transport to 0.26 eV. The phase transition combined with microstructural changes concomitant with an increase of the Ga/Al ratio continuously improves the Li-ion conductivity from 2.6 × 10–4 S cm–1 to 1.2 × 10–3 S cm–1, which is close to the calculated maximum for garnet-type materials. The increase in Ga content is also associated with better densification and smaller grains and is accompanied by a change in the area specific resistance (ASR) from 78 to 24 Ω cm2, the lowest reported value for LLZO so far. These results illustrate that understanding the structure–properties relationships in this class of materials

  5. Study of a Li doped CsI scintillator crystal as a neutron detector

    NASA Astrophysics Data System (ADS)

    Madi Filho, T.; Pereira, M. C. C.; Berretta, J. R.; Cárdenas, J. P. N.

    2015-07-01

    The radiation monitoring system is an important requirement in the premises of a nuclear reactor. A variety of types of radiation (neutrons. gamma. beta and fission products) exist in a reactor. associated to the broad energy spectrum of these radiations. implying the need of detectors to be used in the reactor system and security. as well as radiation monitoring. As the neutron sources are associated to gamma radiation. it is necessary that the neutron detecting system may be capable to discriminate the gamma interference. In our work environment. there are two Nuclear Research Reactors and a neutron irradiator with two AmBe sources (592GBq of Am. each). These conditions warrant the development of new types of detectors. Due to the absence of charge in the neutron. it is necessary to use a converter material that generates radiations capable to produce signals in the detector. Materials with high cross section. like Li or B. are used for this purpose. The CsIcrystal doped with 6Li has been studied. The concentration of the lithium doping element (Li) studied was 10-3M. The detector test was done using an AmBe source (37GBq) and gamma sources. The crystal was coupled to a photomultiplier.

  6. Effect of LiCl doping on dielectric behavior of copper-zinc ferrite system

    NASA Astrophysics Data System (ADS)

    Lipare, A. Y.; Vasambekar, P. N.; Vaingankar, A. S.

    2004-08-01

    Polycrystalline soft ferrite samples were prepared with chemical formula, Zn xCu 1- xFe 2O 4 ( x=0.30,0.50,0.70,0.80 and 0.90) doped with controlled amount of lithium chloride (LiCl) by standard ceramic technique. The samples were characterized by XRD, IR absorption techniques. X-ray diffraction studies of the compositions reveal formation of single-phase cubic structure. The values of lattice constant decrease as doping percentage of LiCl is increased from 0.01% to 0.10%. The presence of chlorine ions is confirmed by IR absorption peak in spectrum near 650 cm-1 for all the samples. The investigation on dielectric constant ( ɛ'), dielectric loss tangent ( tan δ) and AC resistivity ( ρAC) was carried out in the applied field frequency range 100 Hz- 1 MHz, at room temperature. Dielectric constant and loss tangent were found to decrease as the frequency increases. This is attributed to the Maxwell-Wagner polarization. Temperature-dependent DC resistivity was carried out in the temperature range from 300 to 800 K. From the compositional study, it was found that the dielectric constant shows decreasing trend with increasing both zinc concentration as well as doping percentage of lithium chloride. Conduction mechanism in these ferrites is discussed on the basis of electron exchange between Fe 2+ and Fe 3+ ions on the octahedral B-sites.

  7. Surface Reactivity of a Carbonaceous Cathode in a Lithium Triflate/Ether Electrolyte-Based Li-O2 Cell.

    PubMed

    Carboni, Marco; Brutti, Sergio; Marrani, Andrea G

    2015-10-01

    Li-O2 batteries are currently one of the most advanced and challenging electrochemical systems with the potential to largely overcome the performances of any existing technology for energy storage and conversion. However, these optimistic expectations are frustrated by the still inadequate understanding of the fundamentals of the electrochemical/chemical reactions occurring at the cathode side, as well as within the electrolyte and at the three-phase interface. In this work, we illustrate the evolution of the morphology and composition of a carbonaceous cathode in the first discharge/charge in a Li-O2 cell with an ether-based electrolyte by X-ray photoemission spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. Experiments have been carried out ex situ on electrodes recuperated from electrochemical cells stopped at various stages of galvanostatic discharge and charge. Apparently, a reversible accumulation and decomposition of organic and inorganic precipitates occurs upon discharge and charge, respectively. These precipitations and decompositions are likely driven by electrochemical and chemical parasitic processes due to the reactivity of the cathode carbonaceous matrix.

  8. Surface Reactivity of a Carbonaceous Cathode in a Lithium Triflate/Ether Electrolyte-Based Li-O2 Cell.

    PubMed

    Carboni, Marco; Brutti, Sergio; Marrani, Andrea G

    2015-10-01

    Li-O2 batteries are currently one of the most advanced and challenging electrochemical systems with the potential to largely overcome the performances of any existing technology for energy storage and conversion. However, these optimistic expectations are frustrated by the still inadequate understanding of the fundamentals of the electrochemical/chemical reactions occurring at the cathode side, as well as within the electrolyte and at the three-phase interface. In this work, we illustrate the evolution of the morphology and composition of a carbonaceous cathode in the first discharge/charge in a Li-O2 cell with an ether-based electrolyte by X-ray photoemission spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. Experiments have been carried out ex situ on electrodes recuperated from electrochemical cells stopped at various stages of galvanostatic discharge and charge. Apparently, a reversible accumulation and decomposition of organic and inorganic precipitates occurs upon discharge and charge, respectively. These precipitations and decompositions are likely driven by electrochemical and chemical parasitic processes due to the reactivity of the cathode carbonaceous matrix. PMID:26375042

  9. Crystalline Li(sub 3)PO(sub 4)/SiO(sub 4) solid solutions as an electrolyte for film batteries using sputtered cathode layers

    NASA Technical Reports Server (NTRS)

    Whitacre, J. F.; West, W. C.

    2003-01-01

    Crystalline solid solutions of 1:1 Li3PO4/SiO4 were synthesized and tested electrochemically using thin film, physical vapor deposited electrodes. After cathode deposition, the electrolyte/cathode structures were annealed at 700 degrees Celsius for 2 hours, a process that resulted in cathode crystallization without encouraging deleterious interfacial reactions. Results indicate that the electrolyte functioned well in this configuration.

  10. Superior electrochemical performance of LiCoO2 electrodes enabled by conductive Al2O3-doped ZnO coating via magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Dai, Xinyi; Zhou, Aijun; Xu, Jin; Yang, Bin; Wang, Liping; Li, Jingze

    2015-12-01

    A conductive Al2O3-doped ZnO (AZO) layer is coated directly on the LiCoO2 (LCO) porous composite electrode by magnetron sputtering of an AZO target, offering more efficient electron transfer and a stabilized interface layer. Up to 90% of the initial capacity of the AZO-coated electrode can be retained (173 mAh g-1) after 150 cycles between 3.0 and 4.5 V vs. Li/Li+. Meanwhile, the rate performance is remarkably improved showing a reversible capacity of 112 mAh g-1 at 12 C. The formation of amorphous solid electrolyte interface (SEI) observed on the uncoated LCO electrode is effectively impeded on the AZO-coated one. Acting as an intermediate barrier, the AZO layer can prevent chemical dissolution of the active materials by forming a thin passivation layer on the electrode surface containing some metal fluorides which are chemically inactive and ionically conductive. The positive role of the AZO coating is still effective under a more severe condition tested with an upper cut-off potential of 4.7 V.

  11. Investigation of the Decomposition Mechanism of Lithium Bis(oxalate)borate (LiBOB) Salt in the Electrolyte of an Aprotic Li–O2 Battery

    SciTech Connect

    Lau, Kah Chun; Lu, Jun; Low, John; Peng, Du; Wu, Huiming; Albishri, Hassan M.; Al-Hady, D. Abd; Curtiss, Larry A.; Amine, Khalil

    2014-03-13

    The stability of the lithium bis(oxalate) borate (LiBOB) salt against lithium peroxide (Li2O2) formation in an aprotic Li–O2 (Li–air) battery is investigated. From theoretical and experimental findings, we find that the chemical decomposition of LiBOB in electrolytes leads to the formation lithium oxalate during the discharge of a Li–O2 cell. According to density functional theory (DFT) calculations, the formation of lithium oxalate as the reaction product is exothermic and therefore is thermodynamically feasible. This reaction seems to be independent of solvents used in the Li–O2 cell, and therefore LiBOB is probably not suitable to be used as the salt in Li–O2 cell electrolytes.

  12. Ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate

    SciTech Connect

    Das, S.; Ghosh, A.

    2015-02-15

    We have studied ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of free ions with the increase of propylene carbonate content. But for higher content of propylene carbonate, the ionic conductivity decreases due to the increase of concentrations of ion-pairs and ion-aggregates. To get further insights into the ion dynamics, the experimental data for the complex dielectric permittivity have been studied using Havriliak–Negami function. The variation of relaxation time with temperature obtained from this formalism follows Vogel-Tamman-Fulcher equation similar to the ionic conductivity.

  13. Effects of Nb-doped on the structure and electrochemical performance of LiFePO{sub 4}/C composites

    SciTech Connect

    Ma, Zhipeng; Shao, Guangjie; Wang, Guiling; Zhang, Ying; Du, Jianping

    2014-02-15

    The olivine-type niobium doping Li{sub 1−x}Nb{sub x}FePO{sub 4}/C (x=0, 0.005, 0.010, 0.015, 0.025) cathode materials were synthesized via a two-step ball milling solid state reaction. The effects of Nb doping were charactered by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), galvanostatic intermittent titration technique (GITT), cyclic voltammetry (CV), electrochemical impedance spectra (EIS) and galvanostatic charge–discharge. It is found that Nb doping enlarges the interplanar distance of crystal plane parallel to [0 1 0] direction in LiFePO{sub 4}. In other words, it widens the one dimensional diffusion channels of Li{sup +} along the [0 1 0] direction. Electrochemical test results indicate that the Li{sub 0.99}Nb{sub 0.01}FePO{sub 4}/C composite exhibits the best electrochemical performance with initial special discharge capacity of 139.3 mA h g{sup −1} at 1 C rate. The present synthesis route is promising in making the solid state reaction method more practical for preparation of the LiFePO{sub 4} material. - Graphical abstract: The proper amount of Nb doping widens the one dimensional diffusion channels of Li{sup +} along the [0 1 0] direction. Display Omitted - Highlights: • The Nb doping LiFePO{sub 4}/C is prepared by a facile two-step ball milling solid state reaction. • The sample possesses the better high-rate performance. • The tap density of Li{sub 0.99}Nb{sub 0.01}FePO{sub 4}/C sample is 1.76 g cm{sup −3}.

  14. Anomalous thermopower in bismuth doped La-Li-Mn-O manganite

    NASA Astrophysics Data System (ADS)

    Kalyana Lakshmi, Yanapu; Gunadhor Singh, Okram; Venugopal Reddy, Paduru

    2015-01-01

    Two polycrystalline samples, La5/6Li1/6MnO3 and La2/3Bi1/6Li1/6MnO3 having the same Mn3+/Mn4+ ratio were synthesized by the wet chemical method. After characterizing the samples by X-ray powder diffraction studies, dc magnetization, electrical resistivity and thermopower measurements were also carried out. It has been found that bismuth doped sample exhibits huge thermopower of 0.9 V/K in the low temperature region. The observed anomalous behavior is explained on the basis of the coexistence of antiferromagnetic phase in ferromagnetic matrix. The huge thermopower exhibited by these samples might find applications in thermoelectric devices.

  15. Crystal growth, VTE treatment, and characterizations of Nd-doped LiTaO3

    NASA Astrophysics Data System (ADS)

    Wu, C. C.; Hsu, W. T.; Chen, Z. B.; Choubey, R. K.; Lan, C. W.

    2011-03-01

    Congruent 0.2 and 0.5 mol% Nd-doped LiTaO3 single crystals were grown by the conventional Czochralski technique. Near-stoichiometric lithium-tantalate wafers were also produced from these crystals by the vapor-transport equilibration (VTE) process. The crystals were characterized by the measurements of composition (by inductively coupled plasma atomic emission spectroscopy (ICP-AES)), UV absorption edge, Curie temperature, and thermal diffusivity. From the ICP-AES study, we found that Li/Ta ratio increased by the VTE treatment, while Nd/Ta ratio was found to decrease with crystal length. Blue-shift in the absorption edge was observed in the VTE treated crystals as compared with the congruent ones. The Curie temperature decreased with increasing Nd concentration, while thermal diffusivity was found to increase after the VTE treatment.

  16. Fire behavior of carbonates-based electrolytes used in Li-ion rechargeable batteries with a focus on the role of the LiPF6 and LiFSI salts

    NASA Astrophysics Data System (ADS)

    Eshetu, Gebrekidan Gebresilassie; Bertrand, Jean-Pierre; Lecocq, Amandine; Grugeon, Sylvie; Laruelle, Stephane; Armand, Michel; Marlair, Guy

    2014-12-01

    A detailed investigation of the combustion behavior of LiPF6 or LiFSI-based carbonate electrolytes was conducted with the objective of getting better knowledge of lithium-ion battery system fire induced thermal and chemical threats. The well-controlled experimental conditions provided by the Tewarson calorimeter have enabled the accurate evaluation of fire hazard rating parameters such as heat release rate and effective heat of combustion and the quantification of toxic effluents (HF, SO2, NOx…). Results have shown that all the electrolytes tested burn in phases depending on the flammability nature of their mixture constituents. The first stage of combustion is solely governed by the more volatile solvent (linear carbonate) and the influence of adding salt comes into effect predominantly in the second stage. It has been also shown that combustion enthalpy of electrolytes lies in the solvent mixture, irrespective of the salt added. The fire induced toxicity in well-ventilated conditions is found to be mainly dictated by the salt and its chemical structure, showing very limited concerns that emanate from the organic solvents.

  17. H+ diffusion and electrochemical stability of Li1+x+yAlxTi2-xSiyP3-yO12 glass in aqueous Li/air battery electrolytes

    NASA Astrophysics Data System (ADS)

    Ding, Fei; Xu, Wu; Shao, Yuyan; Chen, Xilin; Wang, Zhiguo; Gao, Fei; Liu, Xingjiang; Zhang, Ji-Guang

    2012-09-01

    It is well known that LATP (Li1+x+yAlxTi2-xSiyP3-yO12) glass is a good lithium (Li)-ion conductor. However, the interaction between LATP glass and H+ ions in aqueous electrolytes (including the diffusion and surface adsorption of H+ ions) needs to be well understood before the long-term application of LATP glass in an aqueous electrolyte can be realized. In this work, we investigate H+-ion diffusion in LATP glass and their interactions with the glass surface using both experimental and modeling approaches. Our results indicate that the apparent H+-related current observed in the initial cyclic voltammetry scan should be attributed to the adsorption of H+ ions on the LATP glass rather than the bulk diffusion of H+ ions. Furthermore, density functional theory calculations indicate that the H+-ion diffusion energy barrier (3.21 eV) is much higher than that for Li+ ions (0.79 eV) and Na+ ions (0.79 eV) in a NASICON-type LiTi2(PO4)3 material. As a result, H+-ion conductivity in LATP glass is negligible at room temperature. However, significant surface corrosion was found after the LATP glass in a strong alkaline electrolyte. Therefore, to prevent LATP glass from corrosion, appropriate electrolytes must be developed for long-term operation of LATP in aqueous Li-air batteries.

  18. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li+/H+ exchange in aqueous solutions

    SciTech Connect

    Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu; Sakamoto, Jeffrey; More, Karren Leslie; Chi, Miaofang

    2014-10-21

    Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long-term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7La3Zr2O12 garnet as a Li-stable solid electrolyte. The material underwent a Li+/H+ exchange in aqueous solutions. Nevertheless, its structure remained unchanged even under a high exchange rate of 63.6%. When treated with a 2 M LiOH solution, the Li+/H+ exchange was reversed without any structural change. Furthermore, these observations suggest that cubic Li7La3Zr2O12 is a promising candidate for the separator in aqueous lithium batteries.

  19. Density functional theory study of phonons in graphene doped with Li, Ca and Ba

    NASA Astrophysics Data System (ADS)

    Pešić, Jelena; Damljanović, Vladimir; Gajić, Radoš; Hingerl, Kurt; Belić, Milivoj

    2015-12-01

    Vibrational frequencies and phonon displacement patterns of the H-site doped graphene are calculated by the density functional theory (DFT). DFT calculations, as well as the group theory study, are used to describe these structures as interesting materials for single layer superconductivity. In this paper, graphene doped with Li, Ca and Ba adatoms is systematically analysed and compared. Due to the effect of zone folding, displacement patterns of calculated modes correspond to the ones of the K and Γ point phonons of graphene and this offers the possibility for comparison with the experimental results for graphene. Our objective was to provide compendious and practical guidelines for the experimental research and characterization of these structures.

  20. Enhanced electrochemical performance of LiNi0.5Mn1.5O4 cathode using an electrolyte with 3-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoropropane

    NASA Astrophysics Data System (ADS)

    Luo, Ying; Lu, Taolin; Zhang, Yixiao; Yan, Liqin; Xie, Jingying; Mao, Samuel S.

    2016-08-01

    A new electrolyte based on fluorinated 3-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoropropane (F-EPE) solvent is studied in LiNi0.5Mn1.5O4/Li cells. The electrochemical stability of the electrolyte with 10% F-EPE is carried out by linear sweep voltammetry and electrochemical floating test. These results indicate that the electrolyte with F-EPE has an oxidation potential of more than 5.2 V vs. Li+/Li, which is higher than that without F-EPE and enlarges the oxidative window of electrolyte. A thin and uniform SEI layer is formed on the surface of LiNi0.5Mn1.5O4 cathode by using electrolyte with F-EPE, leads to an improvement in the electrochemical performance, validated by charge-discharge tests, EIS, SEM, TEM, and XPS analysis.

  1. A search for a strong physisorption site for H2 in Li-doped porous carbons.

    PubMed

    Maresca, O; Pellenq, R J-M; Marinelli, F; Conard, J

    2004-12-22

    The mechanism of hydrogen absorption between two coronene molecules has been studied by first principle calculations. Examination of different sites for H(2) molecule confirmed the classical picture of physisorption. We have also considered molecular hydrogen adsorption in a charged carbon structure achieved by doping with lithium at a density corresponding to the intercalate compound LiC(6). We have performed different types of calculations [Hartree-Fock and density functional theory (DFT)] for various atomic basis sets using CRYSTAL98, GAUSSIAN98, and DMOL3 codes. B3LYP-DFT (B3LYP-three-parameter functional of Backe, Lee, Yang and Parr) energy minimization calculations unravel that there is a stable adsorption site for molecular hydrogen in Li-doped sp(2) carbon structure. These calculations also give an insight into the atomic configurations of interlayer species (H(2) and Li) as the interlayer spacing increases. It can be shown that large changes occur in the positions and electronic properties of interlayer species. Hydrogen molecule does not show any tendency for dissociation and adopts a position in the interlayer void that is deeply related to that of lithium ions. We have evidenced a rather large charge transfer from lithium and capping hydrogen species on neighboring slab carbon atoms that induce the stabilization of molecular hydrogen. We have also found that rotating one carbon layer with respect to the other one (at constant interlayer distance) does not change the adsorption energy to a large extent. The best adsorption site is about five times deeper than the physisorption site found in the undoped case and occurs at an interlayer separation of 5.5+/-0.5 A. The corresponding atomic configuration consists in a hydrogen molecule standing (nearly) perpendicular to the plane surface surrounded by the three lithium ions in a configuration close to that of the LiC(6) intercalation compound. PMID:15606276

  2. Component-/structure-dependent elasticity of solid electrolyte interphase layer in Li-ion batteries: Experimental and computational studies

    NASA Astrophysics Data System (ADS)

    Shin, Hosop; Park, Jonghyun; Han, Sangwoo; Sastry, Ann Marie; Lu, Wei

    2015-03-01

    The mechanical instability of the Solid Electrolyte Interphase (SEI) layer in lithium ion (Li-ion) batteries causes significant side reactions resulting in Li-ion consumption and cell impedance rise by forming further SEI layers, which eventually leads to battery capacity fade and power fade. In this paper, the composition-/structure-dependent elasticity of the SEI layer is investigated via Atomic Force Microscopy (AFM) measurements coupled with X-ray Photoelectron Spectroscopy (XPS) analysis, and atomistic calculations. It is observed that the inner layer is stiffer than the outer layer. The measured Young's moduli are mostly in the range of 0.2-4.5 GPa, while some values above 80 GPa are also observed. This wide variation of the observed elastic modulus is elucidated by atomistic calculations with a focus on chemical and structural analysis. The numerical analysis shows the Young's moduli range from 2.4 GPa to 58.1 GPa in the order of the polymeric, organic, and amorphous inorganic components. The crystalline inorganic component (LiF) shows the highest value (135.3 GPa) among the SEI species. This quantitative observation on the elasticity of individual components of the SEI layer must be essential to analyzing the mechanical behavior of the SEI layer and to optimizing and controlling it.

  3. Growth of thin, c-axis oriented Sr-doped LaP3O9 electrolyte membranes in condensed phosphoric acid solutions

    NASA Astrophysics Data System (ADS)

    Hatada, Naoyuki; Takahashi, Kota; Adachi, Yoshinobu; Uda, Tetsuya

    2016-08-01

    Proton-conducting Sr-doped LaP3O9 has potential application as electrolytes in intermediate temperature fuel cells, but reduction of the electrical resistance of the electrolyte membranes is necessary for practical applications. In this study, we focused on reducing the resistance by reducing the electrolyte thickness, while maintaining a preferable microstructure for proton conduction (c-axis orientation and absence of the small-crystal layer). Thin, c-axis oriented Sr-doped LaP3O9 membranes were successfully obtained in condensed phosphoric acid solutions by a novel "two-step precipitation method". In this method, Sr-doped LaP3O9 powder was artificially deposited on the surface of the carbon paper supports as seeds, and then columnar crystals were grown "downward" in the solutions. We expect that this method will be utilized to produce LaP3O9 electrolyte membranes with lower electrical resistance.

  4. Composition determination of off-congruent Li-deficient MgO (5 mol%)-doped LiNbO3 crystals by absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, De-Long; Qi, Li; Hua, Ping-Rang; Pun, Edwin Yue-Bun

    2012-01-01

    Off-congruent Li-deficient MgO:LiNbO3 crystals were prepared by carrying out post-grown Li-poor vapor transport equilibration (VTE) treatments on a number of 0.47 mm thick MgO (5 mol% in growth melt or 6 mol% in crystal)-doped, initially congruent LiNbO3 plates at 1100 °C over different durations ranged in 40-395 h. At first, the VTE-induced Li composition reduction was measured as a function of the VTE duration using the gravimetric method. Then, optical absorption spectroscopy was applied to study the crystal composition effects on the fundamental optical absorption edge and OH absorption characteristic parameters including the peaking position, band width, peaking absorption and band area. These crystal composition effects enable one to establish the optical methods used for determination of the crystal composition from the spectroscopic measurements. These optical methods overcome the demerit that the gravimetric method is limited to a specific VTE temperature or crystal thickness, and can be applied to design and produce an MgO-doped crystal with desired Li composition.

  5. Electrolyte additive to improve performance of MCMB/LiNi 1/3Co 1/3Mn 1/3O 2 Li-ion cell

    NASA Astrophysics Data System (ADS)

    Qin, Yan; Chen, Zonghai; Lu, Wenquan; Amine, Khalil

    The electrolyte additive, 3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5] undecane (TOS), was investigated as a means to improve the life of mesocarbon microbead (MCMB)/Li 1.1[Ni 1/3Co 1/3Mn 1/3] 0.9O 2 (NCM) cells for high-power applications. With the addition of an appropriate amount of TOS (no more than 1 wt%) to MCMB/NCM cells, the capacity retention was significantly improved at 55 °C compared with cells containing pristine electrolyte. Aging tests at 55 °C indicated that the capacity retention of the negative electrode had benefited as a result of the formation of a stable passivation film at the surface of the carbon electrode due to TOS reduction. Electrochemical impedance spectroscopy showed that a TOS addition of more than 0.5 wt% increased the cell interfacial impedance. Differential scanning calorimetry showed that the thermal stability of lithiated MCMB was also improved with the TOS addition.

  6. Solid electrolytes

    DOEpatents

    Abraham, Kuzhikalail M.; Alamgir, Mohamed

    1993-06-15

    This invention pertains to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized (encapsulated) in a solid organic polymer matrix. In particular, this invention relates to solid polymer electrolytes derived by immobilizing complexes (solvates) formed between a Li salt such as LiAsF.sub.6, LiCF.sub.3 SO.sub.3 or LiClO.sub.4 and a mixture of aprotic organic solvents having high dielectric constants such as ethylene carbonate (EC) (dielectric constant=89.6) and propylene carbonate (PC) (dielectric constant=64.4) in a polymer matrix such as polyacrylonitrile, poly(tetraethylene glycol diacrylate), or poly(vinyl pyrrolidinone).

  7. Enhanced ionic conductivity of apatite-type lanthanum silicate electrolyte for IT-SOFCs through copper doping

    NASA Astrophysics Data System (ADS)

    Ding, Xifeng; Hua, Guixiang; Ding, Dong; Zhu, Wenliang; Wang, Hongjin

    2016-02-01

    Apatite-type Lanthanum silicate (LSO) is among the most promising electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs) owing to the high conductivity and low activation energy at lower temperature than traditional doped-zirconia electrolyte. The ionic conductivity as well as the sintering density of lanthanum silicate oxy-apatite, La10Si6-xCuxO27-δ (LSCO, 0 ≤ x ≤ 2), was effectively enhanced through a small amount of doped copper. The phase composition, relative density, ionic conductivity and thermal expansion behavior of La10Si6-xCuxO27-δ was systematically investigated by X-ray diffraction (XRD), Archimedes' drainage method, scanning electron microscope (SEM), electrochemical impedance spectra (EIS) and thermal dilatometer techniques. With increasing copper doping content, the ionic conductivity of La10Si6-xCuxO27-δincreased, reaching a maximum of 4.8 × 10-2 S cm-1 at 800 °C for x = 1.5. The improved ionic conductivity could be primarily associated with the enhanced grain conductivity. The power output performance of NiO-LSCO/LSCO/LSCF single cell was superior to that obtained on NiO-LSO/LSO/LSCF at different temperatures using hydrogen as fuel and oxygen as oxidant, which could be attributed to the enhanced oxygen ionic conductivity as well as the sintering density for the copped doped lanthanum silicate. In conclusion, the apatite La10Si4.5Cu1.5O25.5 is a promising candidate electrolyte for IT-SOFCs.

  8. Spectroscopic characterization of discharge products in Li-Air cells with aprotic carbonate electrolytes

    SciTech Connect

    Veith, Gabriel M; Nanda, Jagjit; Howe, Jane Y; Dudney, Nancy J

    2011-01-01

    Raman, infrared and X-ray photoelectron spectroscopies were used to characterize the thick coating of reaction products on carbon and MnO2 coated carbon cathodes produced during discharge of Li-air cells. The results show that neither Li2O2 or Li2O are major components of the insoluble discharge products; instead the products are largely composed of fluorine, lithium, and carbon, with surprisingly little oxygen. The complex reaction chemistry also appears to involve the formation of ethers or alkoxide products at the expense of the carbonate solvent molecules (ethylene carbonate and dimethylcarbonate). The irreversible discharge reaction is likely electrochemically promoted with Li-anion species and dissolved oxygen. Exactly how the molecular O2 participates in the reaction is unclear and requires further study. The addition of a conformal coating of MnO2 on the carbon lowers the cell s operating voltage, but does not alter the overall discharge chemistry.

  9. In Situ Raman Microscopy of a Single Graphite Microflake Electrode in a Li(+)-containing Electrolyte

    NASA Technical Reports Server (NTRS)

    Shi, Qing-Fang; Dokko, Kaoru; Scherson, Daniel A.

    2003-01-01

    Highly detailed Raman spectra from a single KS-44 graphite microflake electrode as a function of the applied potential have been collected in situ using a Raman microscope and a sealed spectroelectrochemical cell isolated from the laboratory environment. Correlations were found between the Raman spectral features and the various Li(+) intercalation stages while recording in real time Raman spectra during a linear potential scan from 0.7 down ca. 0.0V vs Li/Li(+) at a rate of 0.1 mV/s in a 1M LiClO4 solution in a 1:l (by volume) ethylene carbonate (EC):diethyl carbonate (DEC) mixture. In particular, clearly defined isosbestic points were observed for data collected in the potential range where the transition between dilute phase 1 and phase 4 of lithiated graphite is known to occur, i.e. 0.157 < E < 0.215 vs Li/Li(+). Statistical analysis of the spectroscopic data within this region made it possible to determine independently the fraction of each of the two phases present as a function of potential without relying on coulometric information and then predict, based on the proposed stoichiometry for the transition, a spectrally-derived voltammetric feature.

  10. Novel binary deep eutectic electrolytes for rechargeable Li-ion batteries based on mixtures of alkyl sulfonamides and lithium perfluoroalkylsulfonimide salts

    NASA Astrophysics Data System (ADS)

    Geiculescu, O. E.; DesMarteau, D. D.; Creager, S. E.; Haik, O.; Hirshberg, D.; Shilina, Y.; Zinigrad, E.; Levi, M. D.; Aurbach, D.; Halalay, I. C.

    2016-03-01

    Ionic liquids (IL's) were proposed for use in Li-ion batteries (LIBs), in order to mitigate some of the well-known drawbacks of LiPF6/mixed organic carbonates solutions. However, their large cations seriously decrease lithium transference numbers and block lithium insertion sites at electrode-electrolyte interfaces, leading to poor LIB rate performance. Deep eutectic electrolytes (DEEs) (which share some of the advantages of ILs but possess only one cation, Li+), were then proposed, in order to overcome the difficulties associated with ILs. We report herein on the preparation, thermal properties (melting, crystallization, and glass transition temperatures), transport properties (specific conductivity and viscosity) and thermal stability of binary DEEs based on mixtures of lithium bis(trifluoromethane)sulfonimide or lithium bis(fluoro)sulfonimide salts with an alkyl sulfonamide solvent. Promise for LIB applications is demonstrated by chronoamperometry on Al current collectors, and cycling behavior of negative and positive electrodes. Residual current densities of 12 and 45 nA cm-2 were observed at 5 V vs. Li/Li+ on aluminum, 1.5 and 16 nA cm-2 at 4.5 V vs. Li/Li+, respectively for LiFSI and LiTFSI based DEEs. Capacities of 220, 130, and 175 mAh· g-1 were observed at low (C/13 or C/10) rates, respectively for petroleum coke, LiMn1/3Ni1/3Co1/3O2 (a.k.a. NMC 111) and LiAl0.05Co0.15Ni0.8O2 (a.k.a. NCA).

  11. Microfibrillated cellulose as reinforcement for Li-ion battery polymer electrolytes with excellent mechanical stability

    NASA Astrophysics Data System (ADS)

    Chiappone, A.; Nair, Jijeesh R.; Gerbaldi, C.; Jabbour, L.; Bongiovanni, R.; Zeno, E.; Beneventi, D.; Penazzi, N.

    Methacrylic-based thermo-set gel-polymer electrolyte membranes obtained by a very easy, fast and reliable free radical photo-polymerisation process and reinforced with microfibrillated cellulose particles are here presented. The morphology of the composite electrolytes is investigated by scanning electron microscopy and their thermal behaviour (characteristic temperatures, degradation temperature) are investigated by thermo-gravimetric analysis and differential scanning calorimetry. The composite membranes prepared exhibit excellent mechanical properties, with a Young's modulus as high as about 80 MPa at ambient temperature. High ionic conductivity (approaching 10 -3 S cm -1 at 25 °C) and good overall electrochemical performances are maintained, enlightening that such specific approach would make these hybrid organic, cellulose-based composite polymer electrolyte systems a strong contender in the field of thin and flexible lithium based power sources.

  12. Effect of vapor transport equilibration and Mg doped on the luminescence of Er:LiNbO 3

    NASA Astrophysics Data System (ADS)

    Yao, J. H.; Yan, B. X.; Chen, Y. H.; Xu, J. J.; Zhang, G. Y.; Ruan, Y. F.; Li, W. R.

    2004-12-01

    Luminescence properties of the congruent and vapor transport equilibration (VTE) treated Er:LiNbO3 and Er:Mg:LiNbO3 crystals were recorded at room temperature. It is observed that VTE treatment could enhance the emission intensity of Er3+ ions and doping with MgO would weaken it in the visible spectra. As a result, the luminescence intensity of Er3+ ions in the VTE treated Er:Mg:LiNbO3 crystal increased up to 2.2 times than that in the congruent Er:LiNbO3 crystal. In addition, both VTE treatment and doping with MgO result in some changes of the relative emission intensity of some peaks in the visible emission spectra. In the infrared emission spectra, the luminescence peak at 1540 nm of Er3+ ions shifts towards the larger wavelength when the Er:LiNbO3 crystals were treated using VTE or doped with MgO. The changes in crystalline environment of Er3+ ions due to VTE treatment or doping with Mg2+ play a key role in these phenomena.

  13. Successes and failures of Hubbard-corrected density functional theory. The case of Mg doped LiCoO2

    DOE PAGESBeta

    Santana Palacio, Juan A.; Kim, Jeongnim; Kent, Paul R.; Reboredo, Fernando A.

    2014-10-28

    We have evaluated the successes and failures of the Hubbard-corrected density functional theory approach to study Mg doping of LiCoO2. We computed the effect of the U parameter on the energetic, geometric, and electronic properties of two possible doping mechanisms: (1) substitution of Mg onto a Co (or Li) site with an associated impurity state and (2) formation of impurity-state-free complexes of substitutional Mg and point defects in LiCoO2. We find that formation of impurity states results in changes on the valency of Co in LiCoO2. Variation of the Co U shifts the energy of the impurity state, resulting inmore » energetic, geometric, and electronic properties that depend significantly on the specific value of U. In contrast, the properties of the impurity-state-free complexes are insensitive to U. These results identify reasons for the strong dependence on the doping properties on the chosen value of U and for the overall difficulty of achieving agreement with the experimentally known energetic and electronic properties of doped transition metal oxides such as LiCoO2.« less

  14. Electrical properties of undoped and Li-doped NiO thin films deposited by RF sputtering without intentional heating

    NASA Astrophysics Data System (ADS)

    Sugiyama, Mutsumi; Nakai, Hiroshi; Sugimoto, Gaku; Yamada, Aika; Chichibu, Shigefusa F.

    2016-08-01

    The fundamental transmittance and electrical properties of undoped and Li-doped NiO thin films deposited by conventional RF sputtering without intentional heating were evaluated. Both the transmittance and resistivity of undoped and Li-doped NiO decreased with increasing O2 fraction in the sputtering gas, f(O2) = O2/(Ar + O2). The result is attributed to the increase in the concentration of acceptors of Ni vacancies (VNi) under oxygen-rich growth conditions. In addition to VNi, Li atom on the Ni site (LiNi) likely acts as a shallow accepter, which can explain the experimental finding that the carrier concentration of Li-doped NiO was approximately three orders of magnitude higher than that of the undoped case deposited under the same f(O2). The mobility of NiO was remarkably low (around 0.1–1.0 cm2 V‑1 s‑1) and almost independent of f(O2) or the amount of doping, reflecting the large hole effective mass.

  15. Oligo(ethylene glycol)-functionalized disiloxanes as electrolytes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Zhengcheng; Dong, Jian; West, Robert; Amine, Khalil

    Functionalized disiloxane compounds were synthesized by attaching oligo(ethylene glycol) chains, -(CH 2CH 2O)- n, n = 2-7, via hydrosilation, dehydrocoupling, and nucleophilic substitution reactions and were examined as non-aqueous electrolyte solvents in lithium-ion cells. The compounds were fully characterized by 1H, 13C, and 29Si nuclear magnetic resonance (NMR) spectroscopy. Upon doping with lithium bis(oxalato)borate (LiBOB) or LiPF 6, the disiloxane electrolytes showed conductivities up to 6.2 × 10 -4 S cm -1 at room temperature. The thermal behavior of the electrolytes was studied by differential scanning calorimetry, which revealed very low glass transition temperatures before and after LiBOB doping and much higher thermal stability compared to organic carbonate electrolytes. Cyclic voltammetry measurements showed that disiloxane-based electrolytes with 0.8 M LiBOB salt concentration are stable to 4.7 V. The LiBOB/disiloxane combinations were found to be good electrolytes for lithium-ion cells; unlike LiPF 6, LiBOB can provide a good passivation film on the graphite anode. The LiPF 6/disiloxane electrolyte was enabled in lithium-ion cells by adding 1 wt% vinyl ethylene carbonate (VEC). Full cell performance tests with LiNi 0.80Co 0.15Al 0.05O 2 as the cathode and mesocarbon microbead (MCMB) graphite as the anode show stable cyclability. The results demonstrate that disiloxane-based electrolytes have considerable potential as electrolytes for use in lithium-ion batteries.

  16. Enhanced Electrochemical Stability of Quasi-Solid-State Electrolyte Containing SiO2 Nanoparticles for Li-O2 Battery Applications.

    PubMed

    Kim, Hyunjin; Kim, Tae Young; Roev, Victor; Lee, Heung Chan; Kwon, Hyuk Jae; Lee, Hyunpyo; Kwon, Soonchul; Im, Dongmin

    2016-01-20

    A stable electrolyte is required for use in the open-packing environment of a Li-O2 battery system. Herein, a gelled quasi-solid-state electrolyte containing SiO2 nanoparticles was designed, in order to obtain a solidified electrolyte with a high discharge capacity and long cyclability. We successfully fabricated an organic-inorganic hybrid matrix with a gelled structure, which exhibited high ionic conductivity, thereby enhancing the discharge capacity of the Li-O2 battery. In particular, the improved electrochemical stability of the gelled cathode led to long-term cyclability. The organic-inorganic hybrid matrix with the gelled structure played a beneficial role in improving the ionic conductivity and long-term cyclability and diminished electrolyte evaporation. The experimental and theoretical findings both suggest that the preferential binding between amorphous SiO2 and polyethylene glycol dimethyl ether (PEGDME) solvent led to the formation of the solidified gelled electrolyte and improved electrochemical stability during cycling, while enhancing the stability of the quasi-solid state Li-O2 battery.

  17. Improving the High-Voltage Li2FeMn3O8 Cathode by Chlorine Doping.

    PubMed

    Dai, Jiaqi; Zhou, Lihui; Han, Xiaogang; Carter, Marcus; Hu, Liangbing

    2016-05-01

    High-capacity and high-voltage cathode materials are desirable for high-energy-density lithium ion batteries. Among various cathode materials, Li2FeMn3O8 is attractive due to its high working voltage, low toxicity, and low cost. However, its superior electrochemical properties are significantly limited by the intrinsic defects in the Li2FeMn3O8 cathode, which makes the theoretical working voltage (4.9 V) and capacity (148 mAh/g) hard to reach. In this paper, we demonstrated that Cl doping can effectively increase the capacity and working voltage of the Li2FeMn3O8 cathode. X-ray photoelectron spectroscopy reveals that Cl doping reduced the valence state and increased the electron binding energy in cations and thus increased the voltage and enhanced the capacity of the Li2FeMn3O8 cathode. Our results also indicate that Cl doping can be a promising low-cost method to improve the electrochemical performance of various oxide cathode materials, including LiCoO2 and LiMn2O4.

  18. Performance of electrical double layer capacitors fabricated with gel polymer electrolytes containing Li+ and K+-salts: A comparison

    NASA Astrophysics Data System (ADS)

    Singh, Manoj K.; Hashmi, S. A.

    2015-06-01

    The comparative performance of the solid-state electrical double layer capacitors (EDLCs) based on the multiwalled carbon nanotube (MWCNT) electrodes and poly (vinaylidinefluoride-co-hexafluoropropyline) (PVdF-HFP) based gel polymer electrolytes (GPEs) containing potassium and lithium salts have been studied. The room temperature ionic conductivity of the GPEs have been found to be ˜3.8×10-3 and 5.9×10-3 S cm-1 for lithium and potassium based systems. The performance of EDLC cells studied by impedance spectroscopy, cyclic voltammetry and constant current charge-discharge techniques, indicate that the EDLC with potassium salt containing GPE shows excellent performance almost equivalent to the EDLC with Li-salt-based GPE.

  19. A high precision study of the electrolyte additives vinylene carbonate, vinyl ethylene carbonate and lithium bis(oxalate)borate in LiCoO2/graphite pouch cells

    NASA Astrophysics Data System (ADS)

    Wang, David Yaohui; Sinha, N. N.; Burns, J. C.; Petibon, R.; Dahn, J. R.

    2014-12-01

    The effects of three well-known electrolyte additives, used singly or in combination, on LiCoO2/graphite pouch cells has been investigated using the ultra high precision charger (UHPC) at Dalhousie University, electrochemical impedance spectroscopy (EIS) and long term cycling Vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and lithium bis(oxalato) borate (LiBOB) were chosen for study. The results show that combinations of electrolyte additives that act synergistically can be more effective than a single electrolyte additive. However, simply using 2% VC yielded cells very competitive in coulombic efficiency (CE), charge endpoint capacity slippage and charge transfer resistance (Rct). For cells with 1% LiBOB and VC (1, 2, 4 or 6%), adding VC above 2% does not increase the CE, but increases the electrode charge transfer impedances. Rct for cells containing 1% LiBOB and VEC (0.5, 1 or 4%) decreased after long term cycling (1800 h), compared to that tested after the UHPC cycling (500 h) indicating that VEC might be useful for the design of power cells. However, the opposite behaviour (increasing Rct with cycle number) was observed for the control cells or cells containing LiBOB and/or VC.

  20. Electrochemical Analysis for Enhancing Interface Layer of Spinel Li4Ti5O12: p-Toluenesulfonyl Isocyanate as Electrolyte Additive.

    PubMed

    Wang, Ren-Heng; Li, Xin-Hai; Wang, Zhi-Xing; Guo, Hua-Jun; He, Zhen-Jiang

    2015-10-28

    An electrolyte additive, p-toluenesulfonyl isocyanate (PTSI), is evaluated in our work to overcome the poor cycling performance of spinel lithium titanate (Li4Ti5O12) lithium-ion batteries. We find that the cycling performance of a Li/Li4Ti5O12 cell with 0.5 wt % PTSI after 400 cycles is obviously improved. Remarkably, we also find that a solid electrolyte interface (SEI) film is formed about 1.2 V, which has higher potential to generate a stable SEI film than do carbonate solvents in the voltage range of 3.0-0 V. The stable SEI film derived from PTSI can effectively suppress the decomposition of electrolyte, HF generation, interfacial reaction, and LiF formation upon cycling. These observations are explained in terms of PTSI including SO3. The S═O groups can delocalize the nitrogen core, which acts as the weak base site to hinder the reactivity of PF5. Hence, HF generation and LiF formation are suppressed.

  1. The effect of 0.025 Al-doped in Li4Ti5O12 material on the performance of half cell lithium ion battery

    NASA Astrophysics Data System (ADS)

    Priyono, Slamet; Triwibowo, Joko; Prihandoko, Bambang

    2016-02-01

    The effect of 0.025 Al-doped Li4Ti5O12 as anode material for Lithium Ion battery had been studied. The pure and 0.025 Al-doped Li4Ti5O12 were synthesized through solid state process in air atmosphere. Physical characteristics of all samples were observed by XRD, FTIR, and PSA. The XRD analysis revealed that the obtained particle was highly crystalline and had a face-centered cubic spinel structure. The XRD pattern also showed that the 0.025 Al-doped on the Li4Ti5O12 did not change crystal structure of Li4Ti5O12. FTIR analysis confirmed that the spinel structure in fingerprint region was unchanged when the structure was doped by 0.025 Al. However the doping of 0.025 Al increased particle size significantly. The electrochemical performance was studied by using cyclic voltammetry (CV) and charge-discharge (CD) curves. Electrochemical analysis showed that pure Li4Ti5O12 has higher capacity than 0.025 Al-doped Li4Ti5O12 had. But 0.025 Al-doped Li4Ti5O12 possesses a better cycling stability than pure Li4Ti5O12.

  2. Simultaneous size and luminescence control of NaYF4:Yb3+/RE3+ (RE = Tm, Ho) microcrystals via Li+ doping

    NASA Astrophysics Data System (ADS)

    Lin, Hao; Xu, Dekang; Teng, Dongdong; Yang, Shenghong; Zhang, Yueli

    2015-07-01

    Enhancement of upconversion (UC) luminescence is imperative for the applications of UC microcrystals (MCs). In this work, NaYF4:Yb3+/RE3+ (RE = Tm, Ho) MCs via Li+ doping were successfully prepared by a simple hydrothermal process with the assistance of citric acid. The UC luminescence intensities of NaYF4:Yb3+/RE3+ (RE = Tm, Ho) are significantly enhanced via Li+ doping at different concentrations. Compared to Li+-absent sample, UC luminescence intensities of blue emission (477 nm) and red emission (649 nm) in NaYF4:Yb3+/Tm3+ MCs via 15 mol% Li+ doping are improved by 10 and 9 times, respectively; UC luminescence intensities of green emission (538 nm) and red emission (644 nm) in NaYF4:Yb3+/Ho3+ MCs via 15 mol% Li+ doping are improved by 12 and 3 times, respectively. The mechanism of the enhancement via Li+ doping is discussed in details, which may be attributed to the fact that Li+ doping can cause the distortion of the local symmetry around RE ions. Our results indicate that the enhanced UC luminescence of NaYF4:Yb3+/RE3+ (RE = Tm, Ho) MCs via Li+ doping may have potential applications in optoelectronic devices such as solar cells and plasma display panel.

  3. Effect of sol-gel process parameters on the properties of a Li1.3Ti1.7Al0.3(PO4)3 solid electrolyte for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Lee, Seoung Soo; Lee, Jing; Jung, Yeon-Gil; Kim, Jae-Kwang; Kim, Youngsik

    2016-01-01

    In this study, the influence of the processing parameters, such as the synthesis temperature and the lithium sources on the structure, particle size, morphology and ionic conductivity of Li1+ x Ti2- x Al x (PO4)3 (LTAPO) was investigated. LiNO3, LiCl, and Li acetate were employed as lithium sources for investigating the effects of Li sources on the properties of the solid electrolyte. The morphologies and the particle size distribution of the prepared LTAPO samples were analyzed by using scanning electron microscopy (SEM) and a laser particle size analyzer. Their crystallinities were measured by means of X-ray diffraction (XRD). An increase in the synthesis temperature caused a pronounced growth in the particle size without any impurities, especially at temperatures above 700 °C. In addition, LiCl lithium sources showed the highest particles size. The effect of the processing parameters on the ionic conductivity of the prepared LTAPO was investigated by using electrochemical impedance spectroscopy (EIS). The ionic conductivities of the LTAPO prepared by using an optimized synthesis temperature with different lithium sources were 8.36 × 10-4, 5.73 × 10-4, and 7.18 × 10-4 S/cm for C-LTAPO, A-LTAPO, and N-LTAPO, respectively. The properties of the ceramic solid electrolyte were shown to be affected by the choice of the synthesis temperature and the Li source material.

  4. Ion conduction and relaxation in PEO-LiTFSI-Al{sub 2}O{sub 3} polymer nanocomposite electrolytes

    SciTech Connect

    Das, S.; Ghosh, A.

    2015-05-07

    Ion conduction and relaxation in PEO-LiTFSI-Al{sub 2}O{sub 3} polymer nanocomposite electrolytes have been studied for different concentrations of Al{sub 2}O{sub 3} nanoparticles. X-ray diffraction and differential scanning calorimetric studies show that the maximum amorphous phase of PEO is observed for PEO-LiTFSI embedded with 5 wt. % Al{sub 2}O{sub 3}. The maximum ionic conductivity ∼3.3 × 10{sup −4} S cm{sup −1} has been obtained for this composition. The transmission electron microscopic image shows a distribution of Al{sub 2}O{sub 3} nanoparticles in all compositions with size of <50 nm. The temperature dependence of the ionic conductivity follows Vogel-Tamman-Fulcher nature, indicating a strong coupling between ionic and polymer chain segmental motions. The scaling of the ac conductivity implies that relaxation dynamics follows a common mechanism for different temperatures and Al{sub 2}O{sub 3} concentrations. The imaginary modulus spectra are asymmetric and skewed toward the high frequency sides of the maxima and analyzed using Havriliak-Negami formalism. The temperature dependence of the relaxation time obtained from modulus spectra also exhibits Vogel-Tamman-Fulcher nature. The values of the stretched exponent obtained from Kohlrausch-Williams-Watts fit to the modulus data are fairly low, suggesting highly non-exponential relaxation for all concentrations of Al{sub 2}O{sub 3} in these electrolytes.

  5. Depth profiling the solid electrolyte interphase on lithium titanate (Li4Ti5O12) using synchrotron-based photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Nordh, Tim; Younesi, Reza; Brandell, Daniel; Edström, Kristina

    2015-10-01

    The presence of a surface layer on lithium titanate (Li4Ti5O12, LTO) anodes, which has been a topic of debate in scientific literature, is here investigated with tunable high surface sensitive synchrotron-based photoelectron spectroscopy (PES) to obtain a reliable depth profile of the interphase. Li||LTO cells with electrolytes consisting of 1 M lithium hexafluorophosphate dissolved in ethylene carbonate:diethyl carbonate (LiPF6 in EC:DEC) were cycled in two different voltage windows of 1.0-2.0 V and 1.4-2.0 V. LTO electrodes were characterized after 5 and 100 cycles. Also the pristine electrode as such, and an electrode soaked in the electrolyte were analyzed by varying the photon energies enabling depth profiling of the outermost surface layer. The main components of the surface layer were found to be ethers, P-O containing compounds, and lithium fluoride.

  6. Creation of domains by direct electron beam writing in magnesium-doped LiNbO3 and LiNbO3:Fe single crystals

    NASA Astrophysics Data System (ADS)

    Palatnikov, M. N.; Kokhanchik, L. S.; Emelin, E. V.; Sidorov, N. V.; Manukovskaya, D. V.

    2016-03-01

    Domain structures in the Z-cut of highly doped LiNbO3:Mg and LiNbO3:Mg,Fe single crystals were created by direct electron beam writing (DEBW). It was found that the value and type of electron conductivity influence the shape and number of domains thus created. Controlled electron beam regular domains were created only in samples of the crystal LiNbO3:Mg,Fe [MgO] = 5.16 mol.%, [Fe] = 0.007 mol.%. In highly doped LiNbO3:Mg ([MgO] = 5.19 mol.%) crystal, the domains were formed chaotically and controlled creation of domains did not occur. The domain shapes were analyzed in the framework of the theory of screening of domain nuclei depolarizing electric fields and the influence of screening on the final shape of domains. It was found that screening of intrinsic electric fields is faster in the LiNbO3:Mg,Fe crystal. This crystal has a high electronic conductivity of hopping type with a high mobility of charge carriers. Thus, a small amount of Fe provides equilibrium between the ferroelectric switching velocity and screening of the depolarizing electric field velocity. The results are discussed considering differences in the electron conductivity mechanisms, which control the screening of depolarizing electric field velocity and spatial charge area formed under an electron beam.

  7. The physical properties of Li-doped g-C{sub 3}N{sub 4} monolayer sheet investigated by the first-principles

    SciTech Connect

    Ruan, Linwei; Xu, Gengsheng; Gu, Lina; Li, Cun; Zhu, Yujun; Lu, Yunxiang

    2015-06-15

    Highlights: • Systematically research on Li-doped g-C{sub 3}N{sub 4} monolayer sheets by first-principles calculation. • Optimal dopant concentration for optical absorption is 7.12%. • Thermodynamics stability of the doped substrate g-C{sub 3}N{sub 4} decreased with Li dopant concentration increasing. • The values of work function Φ decreased monotonously with the increasing of Li dopant concentration. - Abstract: The geometric, electronic, optical properties, thermodynamic stability, and work function of Li-doped g-C{sub 3}N{sub 4} monolayer were investigated by the first-principles calculation. It was found that the Li atoms were preferentially substituted the open-hollow sites of g-C{sub 3}N{sub 4}. Interestingly, the “odd” number of Li doped g-C{sub 3}N{sub 4} showed metallic properties, while the “even” number of Li atoms widened the band gap of g-C{sub 3}N{sub 4}. The HOMO and LUMO distributions reveal that the active sites located at edge N and C atoms for both pristine and the Li-doped g-C{sub 3}N{sub 4}. In addition, thermodynamic analysis showed that the doped Li atoms reduced the thermodynamic stability of g-C{sub 3}N{sub 4} monolayer sheets.

  8. Enhanced durability of a proton conducting oxide fuel cell with a purified yttrium-doped barium zirconate-cerate electrolyte

    NASA Astrophysics Data System (ADS)

    Hakim, Muhammad; Yoo, Chung-Yul; Joo, Jong Hoon; Yu, Ji Haeng

    2015-03-01

    The aim of this study is to investigate the effect of yttrium-doped barium zirconate-cerate (BaZr0.3Ce0.5Y0.2O3-δ, BZCY) refinement on cell stability under operational fuel cell conditions. For this purpose, anode-supported cells, comprised of a nickel oxide (NiO)-BZCY anode, a BZCY electrolyte, and a BZCY-La0.6Sr0.4Co0.2Fe0.8O3-δ composite cathode are successfully prepared with refined or as-calcined BZCY powder. The long-term fuel cell performance is evaluated under a potentiostatic measurement at 600 °C. The cell with the refined BZCY electrolyte shows a modest power density of 47 mW cm-2 at a 600 °C operating temperature over 480 h without any significant performance loss, whereas the cell with the as-calcined BZCY electrolyte displays a rapid degradation of cell performance over 110 h. A post-testing analysis of the cell with the refined BZCY does not reveal any evidence of delamination resulting from electrolyte surface decomposition. These results demonstrate that the refinement process significantly enhances the chemical stability of BZCY-based proton conducting fuel cells, which produce a high content of water vapor on the cathode side.

  9. Characteristics of solid-state batteries with zinc/cadmium halide-doped silver phosphate glasses as electrolytes

    NASA Astrophysics Data System (ADS)

    Das, S. S.; Baranwal, B. P.; Gupta, C. P.; Singh, Punita

    Several samples of ion-conducting silver phosphate glasses doped with zinc/cadmium halides are prepared and subjected to X-ray diffraction analysis, transference number measurement, and electrical conductivity studies. The percentage transference numbers of these glasses are found to lie between 98.3 and 99.3, which suggests that the glasses are essentially ionic conductors. The conductivity values range from 1.66×10 -2 to 8.66×10 -2 S cm -1 at 300 °C. Solid-state batteries using these glassy systems as electrolytes with the cell configurations Ag||Ag 2OP 2O 5(20%)Zn/CdX 2||(C+I 2) and Ag||Ag 2OP 2O 5(20%)Zn/CdX 2||(C+I 2+electrolyte) (where X is Cl, Br or I) have been fabricated and their discharge characteristics studied. Cells with undoped silver phosphate glasses as electrolytes have also been prepared and studied. The addition of Zn/CdX 2 to silver phosphate glass results in a substantial increase in the open-circuit voltage in the order MI 2>MBr 2>MCl 2 (where M is the dopant cation). Cells with Ag||Ag 2OP 2O 5(20%)Zn/CdI 2||(C+I 2+electrolyte) deliver the best performance.

  10. Lithium stoichiometry of solid electrolytes based on tetragonal Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}

    SciTech Connect

    Il’ina, E.A.; Raskovalov, A.A.; Shevelin, P.Y.; Voronin, V.I.; Berger, I.F.; Zhyravlev, N.A.

    2014-05-01

    Graphical abstract: - Highlights: • We prepared Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x} (x = 6, 7, 8, 9, 10) by the citrate–nitrate method. • We studied phase composition and conductivity of Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x}. • We proposed a simple method to determine the carbonate impurity content in the solid electrolytes. • The synthesized solid electrolytes Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x} (x = 7–9) have 1.32–3.49 wt.% Li{sub 2}CO{sub 3}. • The composition with x = 9 has high total conductivity, 7.5 × 10{sup −6} S cm{sup −1}, at room temperature. - Abstract: Samples of Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x} (x = 6, 7, 8, 9, 10) were synthesized with the citrate–nitrate method. Neutron diffraction studies have shown the presence of lithium carbonate impurities in the synthesized compounds. We propose a simple and effective method to determine the carbonate impurity content in the solid electrolytes. The technique is based on the measurement of the carbon dioxide volume produced from the interaction of the investigated material with acid. Determined in this way, the content of Li{sub 2}CO{sub 3} in the synthesized electrolytes Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}, Li{sub 8}La{sub 3}Zr{sub 2}O{sub 12.5} and Li{sub 9}La{sub 3}Zr{sub 2}O{sub 13} are 1.32 ± 0.04, 1.95 ± 0.06 and 3.49 ± 0.10 wt.%, respectively. From the obtained data, the actual lithium content per formula unit of complex oxide was calculated for the synthesized compounds. The composition with x = 9 had the highest total conductivity, σ = 7.5 × 10{sup −6} S cm{sup −1}, at room temperature. All the investigated electrolytes have an activation energy of approximately 50 kJ mol{sup −1}.

  11. Passivation of Aluminum in Lithium-ion Battery Electrolytes withLiBOB

    SciTech Connect

    Zhang, Xueyuan; Devine, Thomas M.

    2006-09-09

    A combination of cyclic polarization tests, electrochemical impedance spectroscopy, and electrochemical quartz crystal microbalance (EQCM) measurements indicate a film is formed when aluminum is polarized above 4.5V in 1:1 EC+DMC with 1M LiBOB. The quantity of film that is formed increases with increasing applied potential. Results of EQCM tests suggest the film is AlBO{sub 3}. The film is very protective against corrosion and inhibits pitting corrosion of aluminum in normally corrosive 1M LiTFSI.

  12. Electrochemical reactions and cathode properties of Fe-doped Li2O for the hermetically sealed lithium peroxide battery

    NASA Astrophysics Data System (ADS)

    Harada, Kosuke; Hibino, Mitsuhiro; Kobayashi, Hiroaki; Ogasawara, Yoshiyuki; Okuoka, Shin-ichi; Yonehara, Koji; Ono, Hironobu; Sumida, Yasutaka; Yamaguchi, Kazuya; Kudo, Tetsuichi; Mizuno, Noritaka

    2016-08-01

    Fe-doped Li2O (FDL) is synthesized mechanochemically and is demonstrated as a new Co-free cathode material for use in sealed Li2O2 batteries, which have been proposed as high energy density batteries. Fe3+ ions are substitutionally doped into the Li sites in an antifluorite-type Li2O structure to create FDL. The FDL consists of (Li0.82Fe0.06)2O (d-FDL) and high-temperature form of Li5FeO4 (o-FDL), in which Fe3+ ions disorderly and orderly arranged, respectively. According to the Mössbauer spectra and quantitative peroxide species analysis, the FDL cathode operates principally based on the redox reaction between O22- and O2-. X-ray diffraction study reveals that the reversible formation of O22- proceeds mainly in the d-FDL. An irreversible side reaction involving the evolution of oxygen gas occurs when the cathode is charged to more than 250 mAh g-1. The FDL (Fe/(Li + Fe) = 10 at%) cathode exhibits a reversible capacity of 200 mAh g-1 over 200 cycles at a current density of 22.5 mA g-1.

  13. Activated carbon and single-walled carbon nanotube based electrochemical capacitor in 1 M LiPF{sub 6} electrolyte

    SciTech Connect

    Azam, M.A.; Jantan, N.H.; Dorah, N.; Seman, R.N.A.R.; Manaf, N.S.A.; Kudin, T.I.T.; Yahya, M.Z.A.

    2015-09-15

    Highlights: • Activated carbon and single-walled CNT based electrochemical capacitor. • Electrochemical analysis by means of CV, charge/discharge and impedance. • 1 M LiPF{sub 6} non-aqueous solution as an electrolyte. • AC/SWCNT electrode exhibits a maximum capacitance of 60.97 F g{sup −1}. - Abstract: Carbon nanotubes have been extensively studied because of their wide range of potential application such as in nanoscale electric circuits, textiles, transportation, health, and the environment. Carbon nanotubes feature extraordinary properties, such as electrical conductivities higher than those of copper, hardness and thermal conductivity higher than those of diamond, and strength surpassing that of steel, among others. This research focuses on the fabrication of an energy storage device, namely, an electrochemical capacitor, by using carbon materials, i.e., activated carbon and single-walled carbon nanotubes, of a specific weight ratio as electrode materials. The electrolyte functioning as an ion carrier is 1 M lithium hexafluorophosphate. Variations in the electrochemical performance of the device, including its capacitance, charge/discharge characteristics, and impedance, are reported in this paper. The electrode proposed in this work exhibits a maximum capacitance of 60.97 F g{sup −1} at a scan rate of 1 mV s{sup −1}.

  14. Effect of water on solid electrolyte interphase formation in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Saito, M.; Fujita, M.; Aoki, Y.; Yoshikawa, M.; Yasuda, K.; Ishigami, R.; Nakata, Y.

    2016-03-01

    Time-of-flight-elastic recoil detection analysis (TOF-ERDA) with 20 MeV Cu ions has been applied to measure the depth profiles of solid electrolyte interphase (SEI) layers on the negative electrode of lithium ion batteries (LIB). In order to obtain quantitative depth profiles, the detector efficiency was first assessed, and the test highlighted a strong mass and energy dependence of the recoiled particles, especially H and He. Subsequently, we prepared LIB cells with different water contents in the electrolyte, and subjected them to different charge-discharge cycle tests. TOF-ERDA, X-ray photoelectron spectrometry (XPS), gas chromatography (GC), ion chromatography (IC), and 1H nuclear magnetic resonance (1H NMR) were applied to characterize the SEI region of the negative electrode. The results showed that the SEI layer is formed after 300 cycle tests, and a 500 ppm water concentration in the electrolyte does not appear to cause significant differences in the elemental and organic content of the SEI.

  15. Green synthesis of boron doped graphene and its application as high performance anode material in Li ion battery

    SciTech Connect

    Sahoo, Madhumita; Sreena, K.P.; Vinayan, B.P.; Ramaprabhu, S.

    2015-01-15

    Graphical abstract: Boron doped graphene (B-G), synthesized by simple hydrogen induced reduction technique using boric acid as boron precursor, have more uneven surface as a result of smaller bonding distance of boron compared to carbon, showed high capacity and high rate capability compared to pristine graphene as an anode material for Li ion battery application. - Abstract: The present work demonstrates a facile route for the large-scale, catalyst free, and green synthesis approach of boron doped graphene (B-G) and its use as high performance anode material for Li ion battery (LIB) application. Boron atoms were doped into graphene framework with an atomic percentage of 5.93% via hydrogen induced thermal reduction technique using graphite oxide and boric acid as precursors. Various characterization techniques were used to confirm the boron doping in graphene sheets. B-G as anode material shows a discharge capacity of 548 mAh g{sup −1} at 100 mA g{sup −1} after 30th cycles. At high current density value of 1 A g{sup −1}, B-G as anode material enhances the specific capacity by about 1.7 times compared to pristine graphene. The present study shows a simplistic way of boron doping in graphene leading to an enhanced Li ion adsorption due to the change in electronic states.

  16. Improving rate capability and decelerating voltage decay of Li-rich layered oxide cathodes via selenium doping to stabilize oxygen

    NASA Astrophysics Data System (ADS)

    Ma, Quanxin; Li, Ruhong; Zheng, Rujuan; Liu, Yuanlong; Huo, Hua; Dai, Changsong

    2016-11-01

    To improve the rate performance and decelerate the voltage decay of Li-rich layered oxide cathode materials, a series of cathode materials Li1.2[Mn0.7Ni0.2Co0.1]0.8-xSexO2 (x = 0, 0.07, 0.14 and 0.21) was synthesized via co-precipitation. Based on the characterization results, it can be concluded that uniform Se6+ doping can improve the degree of crystallinity of Li2MnO3, resulting in a better ordering of atoms in the transition metal layer of this type of cathode materials. In the electrochemical experiments, compared to un-doped samples, one of the Se doped samples (LLMO-Se0.14) exhibited a longer sloping region and shorter potential plateau in the initial charge curves, a larger first coulombic efficiency (ca. 77%), better rate capability (178 mAhm g-1 at 10 C) and higher mid-point voltage (MPV) retention (ca. 95%) after 100 cycles. These results prove that Se doping can effectively improve the rate capability and decelerate the voltage decay process of these cathode materials during cycling via suppressing the oxidation process of O2- to O2 and curbing a layered-to-spinel phase transformation. The above-mentioned functions of Se doping are probably due to the higher bonding energy of Sesbnd O than that of Mnsbnd O.

  17. In situ AFM imaging of Li-O2 electrochemical reaction on highly oriented pyrolytic graphite with ether-based electrolyte.

    PubMed

    Wen, Rui; Hong, Misun; Byon, Hye Ryung

    2013-07-24

    Understanding the lithium-oxygen (Li-O2) electrochemical reaction is of importance to improve reaction kinetics, efficiency, and mitigate parasitic reactions, which links to the strategy of enhanced Li-O2 battery performance. Many in situ and ex situ analyses have been reported to address chemical species of reduction intermediate and products, whereas details of the dynamic Li-O2 reaction have not as yet been fully unraveled. For this purpose, visual imaging can provide straightforward evidence, formation and decomposition of products, during the Li-O2 electrochemical reaction. Here, we present real-time and in situ views of the Li-O2 reaction using electrochemical atomic force microscopy (EC-AFM). Details of the reaction process can be observed at nano-/micrometer scale on a highly oriented pyrolytic graphite (HOPG) electrode with lithium ion-containing tetraglyme, representative of the carbon cathode and ether-based electrolyte extensively employed in the Li-O2 battery. Upon oxygen reduction reaction (ORR), rapid growth of nanoplates, having axial diameter of hundreds of nanometers, length of micrometers, and ~5 nm thickness, at a step edge of HOPG can be observed, which eventually forms a lithium peroxide (Li2O2) film. This Li2O2 film is decomposed during the oxygen evolution reaction (OER), for which the decomposition potential is related to a thickness. There is no evidence of byproduct analyzed by X-ray photoelectron spectroscopy (XPS) after first reduction and oxidation reaction. However, further cycles provide unintended products such as lithium carbonate (Li2CO3), lithium acetate, and fluorine-related species with irregular morphology due to the degradation of HOPG electrode, tetraglyme, and lithium salt. These observations provide the first visualization of Li-O2 reaction process and morphological information of Li2O2, which can allow one to build strategies to prepare the optimum conditions for the Li-O2 battery.

  18. In situ AFM imaging of Li-O2 electrochemical reaction on highly oriented pyrolytic graphite with ether-based electrolyte.

    PubMed

    Wen, Rui; Hong, Misun; Byon, Hye Ryung

    2013-07-24

    Understanding the lithium-oxygen (Li-O2) electrochemical reaction is of importance to improve reaction kinetics, efficiency, and mitigate parasitic reactions, which links to the strategy of enhanced Li-O2 battery performance. Many in situ and ex situ analyses have been reported to address chemical species of reduction intermediate and products, whereas details of the dynamic Li-O2 reaction have not as yet been fully unraveled. For this purpose, visual imaging can provide straightforward evidence, formation and decomposition of products, during the Li-O2 electrochemical reaction. Here, we present real-time and in situ views of the Li-O2 reaction using electrochemical atomic force microscopy (EC-AFM). Details of the reaction process can be observed at nano-/micrometer scale on a highly oriented pyrolytic graphite (HOPG) electrode with lithium ion-containing tetraglyme, representative of the carbon cathode and ether-based electrolyte extensively employed in the Li-O2 battery. Upon oxygen reduction reaction (ORR), rapid growth of nanoplates, having axial diameter of hundreds of nanometers, length of micrometers, and ~5 nm thickness, at a step edge of HOPG can be observed, which eventually forms a lithium peroxide (Li2O2) film. This Li2O2 film is decomposed during the oxygen evolution reaction (OER), for which the decomposition potential is related to a thickness. There is no evidence of byproduct analyzed by X-ray photoelectron spectroscopy (XPS) after first reduction and oxidation reaction. However, further cycles provide unintended products such as lithium carbonate (Li2CO3), lithium acetate, and fluorine-related species with irregular morphology due to the degradation of HOPG electrode, tetraglyme, and lithium salt. These observations provide the first visualization of Li-O2 reaction process and morphological information of Li2O2, which can allow one to build strategies to prepare the optimum conditions for the Li-O2 battery. PMID:23808397

  19. Zr4+ doping in Li4Ti5O12 anode for lithium-ion batteries: open Li+ diffusion paths through structural imperfection.

    PubMed

    Kim, Jae-Geun; Park, Min-Sik; Hwang, Soo Min; Heo, Yoon-Uk; Liao, Ting; Sun, Ziqi; Park, Jong Hwan; Kim, Ki Jae; Jeong, Goojin; Kim, Young-Jun; Kim, Jung Ho; Dou, Shi Xue

    2014-05-01

    One-dimensional nanomaterials have short Li(+) diffusion paths and promising structural stability, which results in a long cycle life during Li(+) insertion and extraction processes in lithium rechargeable batteries. In this study, we fabricated one-dimensional spinel Li4Ti5O12 (LTO) nanofibers using an electrospinning technique and studied the Zr(4+) doping effect on the lattice, electronic structure, and resultant electrochemical properties of Li-ion batteries (LIBs). Accommodating a small fraction of Zr(4+) ions in the Ti(4+) sites of the LTO structure gave rise to enhanced LIB performance, which was due to structural distortion through an increase in the average lattice constant and thereby enlarged Li(+) diffusion paths rather than changes to the electronic structure. Insulating ZrO2 nanoparticles present between the LTO grains due to the low Zr(4+) solubility had a negative effect on the Li(+) extraction capacity, however. These results could provide key design elements for LTO anodes based on atomic level insights that can pave the way to an optimal protocol to achieve particular functionalities.

  20. Atomic disorder of Li0.5Ni0.5O thin films caused by Li doping: estimation from X-ray Debye–Waller factors

    PubMed Central

    Yang, Anli; Sakata, Osami; Yamauchi, Ryosuke; Kumara, L. S. R.; Song, Chulho; Katsuya, Yoshio; Matsuda, Akifumi; Yoshimoto, Mamoru

    2015-01-01

    Cubic type room-temperature (RT) epitaxial Li0.5Ni0.5O and NiO thin films with [111] orientation grown on ultra-smooth sapphire (0001) substrates were examined using synchrotron-based thin-film X-ray diffraction. The 11 and 22 rocking curves including six respective equivalent reflections of the Li0.5Ni0.5O and NiO thin films were recorded. The RT B 1 factor, which appears in the Debye–Waller factor, of a cubic Li0.5Ni0.5O thin film was estimated to be 1.8 (4) Å2 from its 11 and 22 reflections, even though the Debye model was originally derived on the basis of one cubic element. The corresponding Debye temperature is 281 (39) K. Furthermore, the B 2 factor in the pseudo-Debye–Waller factor is proposed. This parameter, which is evaluated using one reflection, was also determined for the Li0.5Ni0.5O thin film by treating Li0.5Ni0.5O and NiO as ideal NaCl crystal structures. A structural parameter for the atomic disorder is introduced and evaluated. This parameter includes the combined effects of thermal vibration, interstitial atoms and defects caused by Li doping using the two Debye–Waller factors. PMID:26664345

  1. Enabling LiTFSI-based electrolytes for safer lithium-ion batteries by using linear fluorinated carbonates as (Co)solvent.

    PubMed

    Kalhoff, Julian; Bresser, Dominic; Bolloli, Marco; Alloin, Fannie; Sanchez, Jean-Yves; Passerini, Stefano

    2014-10-01

    In this Full Paper we show that the use of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as conducting salt in commercial lithium-ion batteries is made possible by introducing fluorinated linear carbonates as electrolyte (co)solvents. Electrolyte compositions based on LiTFSI and fluorinated carbonates were characterized regarding their ionic conductivity and electrochemical stability towards oxidation and with respect to their ability to form a protective film of aluminum fluoride on the aluminum surface. Moreover, the investigation of the electrochemical performance of standard lithium-ion anodes (graphite) and cathodes (Li[Ni1/3 Mn1/3 Co1/3 ]O2 , NMC) in half-cell configuration showed stable cycle life and good rate capability. Finally, an NMC/graphite full-cell confirmed the suitability of such electrolyte compositions for practical lithium-ion cells, thus enabling the complete replacement of LiPF6 and allowing the realization of substantially safer lithium-ion batteries.

  2. Study of a Li-air battery having an electrolyte solution formed by a mixture of an ether-based aprotic solvent and an ionic liquid

    NASA Astrophysics Data System (ADS)

    Cecchetto, Laura; Salomon, Mark; Scrosati, Bruno; Croce, Fausto

    2012-09-01

    Recent studies have clearly demonstrated that cyclic and linear carbonates are unstable when used in rechargeable Li-air batteries employing aprotic solvents mostly due to the cathodic formation of superoxide during the oxygen reduction reaction. In particular, it has been ascertained that nucleophilic attack by superoxide anion radical, O2-rad , at O-alkyl carbon is a common mechanism of decomposition of organic carbonates. Moreover, theoretical calculations showed that ether chemical functionalities are stable against nucleophilic substitution induced by superoxide. Aim of this study is to report on a new electrolyte solution for Li-air battery formed by a mixture of an ether-based aprotic solvent with an ionic liquid (IL). The IL-based electrolyte was obtained by mixing the pure ionic liquid N-methyl-(n-butyl) pyrrolidinium bis(trifluoromethane sulfonyl) imide (here denoted as PYR14TFSI) to a 0.91 M solution of lithium triflate (LiCF3SO3) in tetra ethylene glycol dimethyl etcher (TEGDME). We observed that the presence of IL beneficially affects the kinetics and the reversibility of the oxygen reactions involved at the cathode. The most significant result being a lower overvoltage for the charge reaction, compared to a Li/air cell containing the same electrolyte solution without IL.

  3. X-ray absorption spectroscopy of LiBF 4 in propylene carbonate. A model lithium ion battery electrolyte

    SciTech Connect

    Smith, Jacob W.; Lam, Royce K.; Sheardy, Alex T.; Shih, Orion; Rizzuto, Anthony M.; Borodin, Oleg; Harris, Stephen J.; Prendergast, David; Saykally, Richard J.

    2014-08-20

    Since their introduction into the commercial marketplace in 1991, lithium ion batteries have become increasingly ubiquitous in portable technology. Nevertheless, improvements to existing battery technology are necessary to expand their utility for larger-scale applications, such as electric vehicles. Advances may be realized from improvements to the liquid electrolyte; however, current understanding of the liquid structure and properties remains incomplete. X-ray absorption spectroscopy of solutions of LiBF4 in propylene carbonate (PC), interpreted using first-principles electronic structure calculations within the eXcited electron and Core Hole (XCH) approximation, yields new insight into the solvation structure of the Li+ ion in this model electrolyte. By generating linear combinations of the computed spectra of Li+-associating and free PC molecules and comparing to the experimental spectrum, we find a Li+–solvent interaction number of 4.5. This result suggests that computational models of lithium ion battery electrolytes should move beyond tetrahedral coordination structures.

  4. Fabrication of ultrathin solid electrolyte membranes of β-Li3PS4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

    DOE PAGESBeta

    Wang, Hui; Hood, Zachary D.; Xia, Younan; Liang, Chengdu

    2016-04-25

    All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li3PS4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreased to achievemore » ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li3PS4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.« less

  5. The Effect of Electrolyte Additives upon the Lithium Kinetics of Li-Ion Cells Containing MCMB and LiNi(x)Co(1-x)O2 Electrodes and Exposed to High Temperatures

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Gozdz, A. S.; Mani, S.

    2009-01-01

    With the intent of improving the performance of lithium-ion cells at high temperatures, we have investigated the use of a number of electrolyte additives in experimental MCMB- Li(x)Ni(y)Co(1-y)O2 cells, which were exposed to temperatures as high as 80 C. In the present work, we have evaluated the use of a number of additives, namely vinylene carbonate (VC), dimethyl acetamide (DMAc), and mono-fluoroethylene carbonate (FEC), in an electrolyte solution anticipated to perform well at warm temperature (i.e., 1.0M LiPF6 in EC+EMC (50:50 v/v %). In addition, we have explored the use of novel electrolyte additives, namely lithium oxalate and lithium tetraborate. In addition to determining the capacity and power losses at various temperatures sustained as a result of high temperature cycling (cycling performed at 60 and 80 C), the three-electrode MCMB-Li(x)Ni(y)Co(1-y)O2 cells (lithium reference) enabled us to study the impact of high temperature storage upon the solid electrolyte interphase (SEI) film characteristics on carbon anodes (MCMB-based materials), metal oxide cathodes, and the subsequent impact upon electrode kinetics.

  6. Properties of Li-Doped NiO Thin Films Prepared by RF-Magnetron Sputtering.

    PubMed

    Kwon, Ho-Beom; Han, Joo-Hwan; Lee, Hee Young; Lee, Jai-Yeoul

    2016-02-01

    Li-doped NiO thin films were deposited on glass and c-axis (0001) sapphire single crystal substrates by radio frequency (RF)-niagnetron sputtering. The effects of the type of substrate, substrate temperature and atmosphere on the structural, electrical and optical properties of the NiO thin films were examined. The electrical conductivity of the NiO thin films depends on the type of substrate, substrate temperature and oxygen atmosphere. The electrical conductivity of the thin films on the glass and sapphire substrates was improved by the introduction of oxygen and decreased with increasing substrate temperature. The optical transmittance decreased with the introduction of oxygen and increased with increasing substrate temperature.

  7. Anisotropy of ionic conduction in single-crystal Li x La(1- x )/3NbO3 solid electrolyte grown by directional solidification

    NASA Astrophysics Data System (ADS)

    Fujiwara, Yasuyuki; Taishi, Toshinori; Hoshikawa, Keigo; Kohama, Keiichi; Iba, Hideki

    2016-09-01

    The anisotropy of ionic conduction in a solid electrolyte (Li x La(1- x )/3NbO3) was experimentally confirmed for the first time. Ionic conduction measurements were carried out on the (100), (010), (001), (110), (111), and (112) planes of single-crystal ingots of Li x La(1- x )/3NbO3 grown by directional solidification. We found that the ionic conductivity in Li x La(1- x )/3NbO3 with x = 0.08 was 3.6 × 10-4 S cm-1 in the [100] and [010] directions, approximately 10 times higher than that in the [001] direction. Such anisotropy of the ionic conduction is discussed with respect to the characteristic layered structure of Li x La(1- x )/3NbO3.

  8. Anisotropy of ionic conduction in single-crystal Li x La(1‑ x )/3NbO3 solid electrolyte grown by directional solidification

    NASA Astrophysics Data System (ADS)

    Fujiwara, Yasuyuki; Taishi, Toshinori; Hoshikawa, Keigo; Kohama, Keiichi; Iba, Hideki

    2016-09-01

    The anisotropy of ionic conduction in a solid electrolyte (Li x La(1‑ x )/3NbO3) was experimentally confirmed for the first time. Ionic conduction measurements were carried out on the (100), (010), (001), (110), (111), and (112) planes of single-crystal ingots of Li x La(1‑ x )/3NbO3 grown by directional solidification. We found that the ionic conductivity in Li x La(1‑ x )/3NbO3 with x = 0.08 was 3.6 × 10‑4 S cm‑1 in the [100] and [010] directions, approximately 10 times higher than that in the [001] direction. Such anisotropy of the ionic conduction is discussed with respect to the characteristic layered structure of Li x La(1‑ x )/3NbO3.

  9. Insights into stability, electronic properties, defect properties and Li ions migration of Na, Mg and Al-doped LiVPO4F for cathode materials of lithium ion batteries: A first-principles investigation

    NASA Astrophysics Data System (ADS)

    Lv, Xiaojun; Xu, Zhenming; Li, Jie; Chen, Jiangan; Liu, Qingsheng

    2016-07-01

    The effects of Na, Mg and Al doping on the structure, electronic property, defect property and Li ions migration of LiVPO4F were investigated by the first-principles method. Calculations show that the processes of forming Li0.875Na0.125VPO4F, α- and β-LiMg0.375V0.75PO4F, α- and β-LiAl0.125V0.875PO4F are all feasible. Na, Mg and Al doping significantly improve the electrical conductivity of LiVPO4F and simultaneously maintain their structural stability attributing to the reduction of band gaps through variations of V-3d spin up orbitals. Li vacancy defects of LiVPO4F are not ignorable, and vacancy defects with a lower activation energy for Li atom are far more likely to occur than Frenkel defects for Li and vacancy defects for other atoms. For pristine LiVPO4F, path D along [0.012 0 . 17 ̅ 0.572] direction is found to have the lowest activation energy of 0.418 eV, suggesting that anisotropic nature of Li ion conduction and LiVPO4F is a one-dimensional (1D)-ion conductor. The corresponding diffusion coefficient was estimated to be 2.82×10-9 cm2/s, which is in good agreement with those experimental values.

  10. Nb doped TiO2 as a Cathode Catalyst Support Material for Polymer Electrolyte Membrane Fuel Cells

    NASA Astrophysics Data System (ADS)

    O'Toole, Alexander W.

    In order to reduce the emissions of greenhouse gases and reduce dependence on the use of fossil fuels, it is necessary to pursue alternative sources of energy. Transportation is a major contributor to the emission of greenhouse gases due to the use of fossil fuels in the internal combustion engine. To reduce emission of these pollutants into the atmosphere, research is needed to produce alternative solutions for vehicle transportation. Low temperature polymer electrolyte membrane fuel cells are energy conversion devices that provide an alternative to the internal combustion engine, however, they still have obstacles to overcome to achieve large scale implementation. T he following work presents original research with regards to the development of Nb doped TiO2 as a cathode catalyst support material for low temperature polymer electrolyte membrane fuel cells. The development of a new process to synthesize nanoparticles of Nb doped TiO2 with controlled compositions is presented as well as methods to scale up the process and optimize the synthesis for the aforementioned application. In addition to this, comparison of both electrochemical activity and durability with current state of the art Pt on high surface area carbon black (Vulcan XC-72) is investigated. Effects of the strong metal-support interaction on the electrochemical behavior of these materials is also observed and discussed.

  11. Thin-Film Solid Oxide Fuel Cell Based on Doped LaGaO3 Electrolyte

    NASA Astrophysics Data System (ADS)

    Wan, Jen-Hau; Goodenough, John B.

    2003-03-01

    Losses in a solid oxide fuel cell (SOFC) arise from the resistance to O2--ion conduction across the electrolyte and from the rate of reactant dissociative chemisorption and migration across the electrode/electrolyte interfaces. Efforts made to reduce the electrolyte thickness have increased the power density that can be withdrawn from the fuel cell. Whereas a SOFC based on a thin layer of yittria-stablized zirconia (YSZ) as the electrolyte has been under development for several years, a similar thin-electrolyte SOFC with La0.8Sr0.2Ga0.83Mg0.17O2.815 (LSGM) has received little attention. A SOFC with a thin layer of LSGM deposited on a porous YSZ substrate that was subsequently impregnated with Ni has been reported to give a power density of 850 mW/cm2 at 800¢XC with H2 as fuel. In our group, different methods have been used to fabricate a thin LSGM membrane on a composite anode, these methods include screen-printing, colloidal deposition, impregnation, and dry-pressing methods. Because of the reaction between LSGM and a Ni anode during fabrication, a layer of La0.4Ce0.6O1.8 (LDC) must be put between the LSGM electrolyte and a NiO+LDC composite anode. The thin-film SOFC made by screen-printing technique produced an anode-supported fuel cell with a 50 mm thick electrolyte+LDC layer. However because the screen-printing method did not produce an air-tight dense electrolyte membrane, the open-circuit voltage dropped to 0.7V instead of the theoretical 1.1V when running on humid hydrogen as fuel. The power density of this cell reaches 700 mW/cm2 at 850¢XC and 520mW/cm2 at 800¢XC. The dry-pressing method allows co-sintering of anode/electrolyte, which lowers the interfacial overpotentials and guarantees an air-tight, dense electrolyte layer. A SOFC power density of 1400 mW/cm2 at 800¢XC with a 200 mm thick LSGM electrolyte will be compared with the result for a thin-film electrolyte.

  12. CO oxidation over gold supported on Cs, Li and Ti-doped cryptomelane materials.

    PubMed

    Carabineiro, Sónia A C; Santos, Vera P; Pereira, M Fernando R; Órfão, José J M; Figueiredo, José L

    2016-10-15

    Cryptomelane-type manganese oxides were synthesized by redox reaction under acid and reflux conditions. Different metals (cesium, lithium and titanium) were incorporated into the tunnel structure by the ion-exchange technique. Gold was loaded onto these materials (1wt%) by a double impregnation method. The obtained catalysts were characterized by high-resolution transmission electron microscopy, energy-dispersive X-ray spectrometry, scanning electron microscopy, X-ray diffraction and temperature-programmed reduction. The catalytic activity of these materials was evaluated in the oxidation of carbon monoxide. The incorporation of Cs, Li or Ti into cryptomelane was detrimental in terms of catalytic activity. Further addition of gold to cryptomelane doped materials significantly improved the catalytic performance, especially for Cs-K-OMS-2 and Li-K-OMS-2 (to a smaller extent). Addition of gold to the Ti containing material did not show a significant improvement. The observed trends are related to the effect of gold on samples reducibility and to the gold particle size. The lattice oxygen can also be considered accountable for the activity of the materials, since the most active cryptomelane catalysts are those with higher lattice oxygen donating ability for the oxidation of the CO molecule.

  13. CO oxidation over gold supported on Cs, Li and Ti-doped cryptomelane materials.

    PubMed

    Carabineiro, Sónia A C; Santos, Vera P; Pereira, M Fernando R; Órfão, José J M; Figueiredo, José L

    2016-10-15

    Cryptomelane-type manganese oxides were synthesized by redox reaction under acid and reflux conditions. Different metals (cesium, lithium and titanium) were incorporated into the tunnel structure by the ion-exchange technique. Gold was loaded onto these materials (1wt%) by a double impregnation method. The obtained catalysts were characterized by high-resolution transmission electron microscopy, energy-dispersive X-ray spectrometry, scanning electron microscopy, X-ray diffraction and temperature-programmed reduction. The catalytic activity of these materials was evaluated in the oxidation of carbon monoxide. The incorporation of Cs, Li or Ti into cryptomelane was detrimental in terms of catalytic activity. Further addition of gold to cryptomelane doped materials significantly improved the catalytic performance, especially for Cs-K-OMS-2 and Li-K-OMS-2 (to a smaller extent). Addition of gold to the Ti containing material did not show a significant improvement. The observed trends are related to the effect of gold on samples reducibility and to the gold particle size. The lattice oxygen can also be considered accountable for the activity of the materials, since the most active cryptomelane catalysts are those with higher lattice oxygen donating ability for the oxidation of the CO molecule. PMID:27399615

  14. Performance Testing of Yardney MCMB-LiNiCoAlO2 Lithium-ion Cells Possessing Electrolytes with Improved Safety Characteristics

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Whitcanack, Larry D.; Krause, Frederick C.; Hwang, Constanza; Bugga, Ratnakumar V.; Santee, Stuart; Puglia, Frank J.; Gitzendanner, Rob

    2012-01-01

    Many future NASA missions aimed at exploring the Moon and Mars require high specific energy rechargeable batteries that possess enhanced safety characteristics. There is also a strong desire to develop Li-ion batteries with improved safety characteristics for terrestrial applications, most notably for HEV and PHEV automotive applications. In previous work focused upon evaluating various potential flame retardant additives1, triphenyl phosphate (TPP)2 was observed to have the most desirable attributes, including good life characteristics and resilience to high voltage operation. We have employed a number of approaches in the design of promising TPP-based electrolytes with improved safety, including: (a) varying the flame retardant additive (FRA) content (from 5 to 15%), (b) the use of fluorinated co-solvents, (c) the use of additives to improve compatibility, and (c) the use of ester co-solvents to decrease the viscosity and increase the conductivity. In recent work, we have demonstrated a number of these electrolyte formulations to be compatible with a number of chemistries, including: MCMB carbon-LiNi0.8Co0.2O2, graphite-LiNi0.8Co0.15Al0.05O2, Li-Li(Li0.17Ni 0.25 Mn 0.58 )O2, Li-LiNiCoMnO2 and graphite- LiNiCoMnO2.3,4 In the current study, we have demonstrated the performance of a number of TPP-containing electrolytes in 7 Ah prototype MCMB-LiNiCoO2 cells. We will describe the results of a number of performance tests, including: a) 100% DOD cycle life testing at various temperatures, b) discharge rate characterization as a function of temperature, c) charge rate characterization as a function of temperature, and d) impedance as a function of temperature. In addition to displaying good life characteristics, being comparable to baseline chemistries, a number of cells were observed to provide good performance over a wide temperature range.

  15. Purification of used eutectic (LiCl-KCl) salt electrolyte from pyroprocessing

    NASA Astrophysics Data System (ADS)

    Cho, Yung-Zun; Lee, Tae-Kyo; Eun, Hee-Chul; Choi, Jung-Hoon; Kim, In-Tae; Park, Geun-Il

    2013-06-01

    The separation characteristics of surrogate rare-earth fission products in a eutectic (LiCl-KCl) molten salt were investigated. This system is based on the eutectic salt used for the pyroprocessing treatment of used nuclear fuel (UNF). The investigation was performed using an integrated rare-earth separation apparatus comprising a precipitation reactor, a solid detachment device, and a layer separation device. To separate rare-earth fission products, a phosphate precipitation method using both Li3PO4 and K3PO4 as a precipitant was performed. The use of an equivalent phosphate precipitant composed of 0.408 molar ratio-K3PO4 and 0.592 molar ratio-Li3PO4 can preserve the original eutectic ratio, LiCl-0.592 molar ratio (or 45.2 wt%), as well as provide a high separation efficiency of over 99.5% under conditions of 550 °C and Ar sparging when using La, Nd, Ce, and Pr chlorides. The mixture of La, Nd, Ce, and Pr phosphate had a typical monoclinic (or monazite) structure, which has been proposed as a reliable host matrix for the permanent disposal of a high-level waste form. To maximize the reusability of purified eutectic waste salt after rare-earth separation, the successive rare-earth separation process, which uses both phosphate precipitation and an oxygen sparging method, were introduced and tested with eight rare-earth (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) chlorides. In the successive rare-earth separation process, the phosphate reaction was terminated within 1 h at 550 °C, and a 4-8 h oxygen sparging time were required to obtain over a 99% separation efficiency at 700-750 °C. The mixture of rare-earth precipitates separated by the successive rare-earth separation process was found to be phosphate, oxychloride, and oxide. Through the successive rare-earth separation process, the eutectic ratio of purified salt maintained its original value, and impurity content including the residual precipitant of purified salt can be minimized.

  16. White light emission from Dy3+-doped LiLuF4 single crystal grown by Bridgman method

    NASA Astrophysics Data System (ADS)

    Dong, Yan-ming; Xia, Hai-ping; Fu, Li; Li, Shan-shan; Gu, Xue-mei; Zhang, Jian-li; Wang, Dong-jie; Zhang, Yue-pin; Jiang, Hao-chuan; Chen, Bao-jiu

    2014-07-01

    Lithium lutetium fluoride (LiLuF4) single crystals doped with different Dy3+ ion concentrations were grown by Bridgman method. The Judd-Ofelt (J-O) strength parameters ( Ω 2, Ω 4, Ω 6) of Dy3+ in LiLuF4 crystal are calculated according to the measured absorption spectra and the J-O theory, by which the asymmetry of the Dy3+:LiLuF4 single crystal and the possibility of attaining stimulated emission from 4F9/2 level are analyzed. The capability of the Dy3+:LiLuF4 crystal in generating white light by simultaneous blue and yellow emissions under excitation with ultraviolet light is produced. The effects of excitation wavelength and doping concentration on chromaticity coordinates and photoluminescence intensity are also investigated. Favorable CIE coordinates, x=0.319 3 and y=0.349 3, can be obtained for Dy3+ ion in 2.701% molar doping concentration under excitation of 350 nm.

  17. Optimizing Hydrogen Storage by Doping the LiBH4 +MgH2 Reaction with Various Niobium Based Oxides

    NASA Astrophysics Data System (ADS)

    Hornung, Paul; Walko, Robert; Wenzel, Andrew; Wright, Richard; Dobbins, Tabbetha

    In this study, the effects of doping the dehydrogenation reaction of MgH2 + 2LiBH4 was combined with 5 mole% of three different Niobium based oxides (Nb2O5, NbO2, and LiNbO3). The compounds were mixed using high energy ball milling, and then heated using an air tight heating stage. We looked for changes in the Raman spectra as temperature increased (up to 350C) as an indication of hydrogen desorption reaction. We found that milled LiBH4 undergoes significant changes in Raman spectra during heating to 130C. MgH2 undergoes significant changes when comparing before and after milling--but in each case, the spectral peaks remain unchanged during heating to 350C. The sample with LiNbO3 exhibited a concrete change in Raman spectrum at 300 C while the sample doped with Nb2O5 underwent a change in spectra at 170C. The sample doped with NbO2 showed little change in spectra when the samples were heated up to 350C. Further studies are underway to examine the nature of the changes in the Raman spectra using X-ray diffraction and residual gas analysis.

  18. Green up-converted luminescence in (Er3+-Yb3+) co-doped LiNbO3 crystals

    NASA Astrophysics Data System (ADS)

    Stoffel, M.; Rinnert, H.; Kokanyan, E.; Demirkhanyan, G.; Demirkhanyan, H.; Aillerie, M.

    2016-07-01

    Er3+ doped and (Er3+-Yb3+) co-doped LiNbO3 (LN) crystals grown by the Czochralski method are investigated by photoluminescence spectroscopy. Green up-converted luminescence is observed in Er3+ doped LN crystals under 980 nm excitation. This is explained by an energy transfer between two neighboring Er3+ ions. In (Er3+, Yb3+) co-doped LN crystals, the intensity of the green up-converted luminescence can be further enhanced suggesting that Yb3+ ions also contribute to the up-conversion process. Time resolved photoluminescence measurements clearly demonstrate that an efficient energy transfer occurs between Yb3+ and Er3+ ions. A theoretical model taking into account the contribution of both Er3+-Er3+ pairs and Yb3+-Er3+ pairs is able to describe correctly the decay of the up-converted luminescence.

  19. Fano resonance of Li-doped KTa1−xNbxO3 single crystals studied by Raman scattering

    PubMed Central

    Rahaman, M. M.; Imai, T.; Sakamoto, T.; Tsukada, S.; Kojima, S.

    2016-01-01

    The enhancement of functionality of perovskite ferroelectrics by local structure is one of current interests. By the Li-doping to KTa1−xNbxO3 (KTN), the large piezoelectric and electro-optic effects were reported. In order to give new insights into the mechanism of doping, the microscopic origin of the Fano resonance induced by the local structure was investigated in 5%Li-doped KTN single crystals by Raman scattering. The coupling between the continuum states and the transverse optical phonon near 196 cm−1 (Slater mode) caused a Fano resonance. In the vicinity of the cubic-tetragonal phase transition temperature, TC-T = 31 °C, the almost disappearance of the Fano resonance and the remarkable change of the central peak (CP) intensity were observed upon heating. The local symmetry of the polar nanoregions (PNRs), which was responsible for the symmetry breaking in the cubic phase, was determined to E(x, y) symmetry by the angular dependence of Raman scattering. The electric field induced the significant change in the intensity of both CP and Fano resonance. From these experimental results, it is concluded that the origin of the Fano resonance in Li-doped KTN crystals is the coupling between polarization fluctuations of PNRs and the Slater mode, both belong to the E(x, y) symmetry. PMID:27049847

  20. Doping Li and K into Na2ZrO3 Sorbent to Improve Its CO2 Capture Capability

    NASA Astrophysics Data System (ADS)

    Duan, Yuhua

    Carbon dioxide is one of the major combustion products which once released into the air can contribute to global climate change. Solid sorbents have been reported in several previous studies to be promising candidates for CO2 sorbent applications due to their high CO2 absorption capacities at moderate working temperatures. However, at a given CO2 pressure, the turnover temperature (Tt) of an individual solid capture CO2 reaction is fixed and may be outside the operating temperature range (ΔTo) for a particularly capture technology. In order to shift such Tt for a solid into the range of ΔTo, its corresponding thermodynamic property must be changed by changing its structure by reacting (mixing) with other materials or doping with other elements. As an example, by combining thermodynamic database searching with ab initio thermodynamics calculations, in this work, we explored the Li- and K-doping effects on the Tt shifts of Na2ZrO3 at different doping levels. The obtained results showed that compared to pure Na2ZrO3, the Li- and K-doped mixtures Na2-αMαZrO3 (M =Li, K) have lower Tt and higher CO2 capture capacities.

  1. Fano resonance of Li-doped KTa(1-x)NbxO3 single crystals studied by Raman scattering.

    PubMed

    Rahaman, M M; Imai, T; Sakamoto, T; Tsukada, S; Kojima, S

    2016-01-01

    The enhancement of functionality of perovskite ferroelectrics by local structure is one of current interests. By the Li-doping to KTa(1-x)NbxO3 (KTN), the large piezoelectric and electro-optic effects were reported. In order to give new insights into the mechanism of doping, the microscopic origin of the Fano resonance induced by the local structure was investigated in 5%Li-doped KTN single crystals by Raman scattering. The coupling between the continuum states and the transverse optical phonon near 196 cm(-1) (Slater mode) caused a Fano resonance. In the vicinity of the cubic-tetragonal phase transition temperature, TC-T = 31 °C, the almost disappearance of the Fano resonance and the remarkable change of the central peak (CP) intensity were observed upon heating. The local symmetry of the polar nanoregions (PNRs), which was responsible for the symmetry breaking in the cubic phase, was determined to E(x, y) symmetry by the angular dependence of Raman scattering. The electric field induced the significant change in the intensity of both CP and Fano resonance. From these experimental results, it is concluded that the origin of the Fano resonance in Li-doped KTN crystals is the coupling between polarization fluctuations of PNRs and the Slater mode, both belong to the E(x, y) symmetry. PMID:27049847

  2. Interface Properties between Lithium Metal and a Composite Polymer Electrolyte of PEO18Li(CF3SO2)2N-Tetraethylene Glycol Dimethyl Ether

    PubMed Central

    Wang, Hui; Matsui, Masaki; Takeda, Yasuo; Yamamoto, Osamu; Im, Dongmin; Lee, Dongjoon; Imanishi, Nobuyuki

    2013-01-01

    The electrochemical properties of a composite solid polymer electrolyte, consisting of poly(ethylene oxide) (PEO)-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and tetraethylene glycol dimethyl ether (TEGDME) was examined as a protective layer between lithium metal and a water-stable lithium ion-conducting glass ceramic of Li1+x+y(Ti,Ge)2−xAlxP3−ySiyO12 (LTAP). The lithium ion conductivity and salt diffusion coefficient of PEO18LiTFSI were dramatically enhanced by the addition of TEGDME. The water-stable lithium electrode with PEO18LiTFSI-2TEGDME, as the protective layer, exhibited a low and stable electrode resistance of 85 Ω·cm2 at 60 °C, after 28 days, and low overpotentials of 0.3 V for lithium plating and 0.4 V for lithium stripping at 4.0 mA·cm−2 and 60 °C. A Li/PEO18LiTFSI-2TEGDME/LTAP/saturated LiCl aqueous solution/Pt, air cell showed excellent cyclability up to 100 cycles at 2.0 mAh·cm−2. PMID:24957059

  3. Physico-chemical investigations on the electronic partial conductivity of molten electrolytes, especially of the eutectic mixture LiCl-KCl

    NASA Astrophysics Data System (ADS)

    Rickert, H.; Meyer, M.

    1984-09-01

    The self-discharge of lithium-sulfur batteries caused by the electronic partial conductivity of the electrolyte was estimated. Stationary polarization measurements were used to determine the electronic conductivity in the eutectic melt LiCl-KCl at temperatures from 400 to 500 C. From investigations on the solubility of lithium in the melt, the diffusion coefficient of the conducting particles was obtained using a coulometric titration method.

  4. Resolving the grain boundary and lattice impedance of hot-pressed Li7La3Zr2O12 garnet electrolytes

    DOE PAGESBeta

    Tenhaeff, Wyatt E.; Wang, Yangyang; Sokolov, Alexei P.; Wolfenstine, Jeff; Sakamoto, Jeffrey; Dudney, Nancy J.; Rangasamy, Ezhiyl

    2013-07-24

    Here, the cubic-stabilized garnet solid electrolyte with a nominal composition of Li6.28Al0.24La3Zr2O12 is thoroughly characterized by impedance spectroscopy. By varying the frequency of the applied AC signal over 11 orders of magnitude for characterizations from –100 to +60 °C, the relative contributions of grain and grain boundary conduction are unambiguously resolved.

  5. Li doping effect on the photoluminescence behaviors of KSrPO{sub 4}:Dy{sup 3+} phosphors for WLED light

    SciTech Connect

    Gou, Jing; Wang, Jing; Yu, Binxun; Duan, Dongyu; Ye, Shufen; Liu, Shengzhong

    2015-04-15

    Highlights: • The luminescence intensity of KSrPO{sub 4}:Dy{sup 3+} can be increased with Li{sup +} ions co-doping. • The mechanisms for the emitting enhancement with Li{sup +} ions co-doping were investigated. • The thermal stability demonstrated that KSrPO{sub 4}:0.01Dy{sup 3+}, 0.06Li{sup +} is suitable for WLEDs. • The chromaticity coordinates of KSrPO{sub 4}:Dy{sup 3+}, Li{sup +} can be tuned with Li{sup +} ions increasing. - Abstract: A novel warm-white phosphor KSrPO{sub 4} co-doped with Dy{sup 3+} and Li{sup +} ions was prepared by solid state reaction. A strategy of Li{sup +} doping was used with the aim of enhancing the luminescence of 475 nm and 570 nm emission bands under NUV excitation. Compared to lithium-free KSrPO{sub 4}:Dy{sup 3+}, the intensities of the 570 nm emission peaks were increased by 4.32 times and 2.84 times excited by 351 nm and 388 nm with 6 mol% Li{sup +} ions co-doping, respectively. The mechanism of the enhancement was discussed, that is due to the improvement of the phosphors’ crystallinity and charge compensation when the Li{sup +} ions were introduced. Furthermore, the thermal stability of KSrPO{sub 4}:0.01Dy{sup 3+}, 0.06Li{sup +} was measured and discussed, demonstrating it can be applied for high-powered LED. And the chromaticity coordinates of KSrPO{sub 4}:0.01Dy{sup 3+}, xLi{sup +} can be tuned efficiently from the cold-white region to warm-white region with Li{sup +} ions increasing, presenting its potential applied value as a new warm-white LED phosphor.

  6. Lithium ionic mobility study in xLi{sub 2}CO{sub 3}-yLiI (x = 95-70, y = 5-30 wt.%) solid electrolyte by impedance spectroscopy technique

    SciTech Connect

    Omar, Mohd Khari; Ahmad, Azizah Hanom

    2015-08-28

    A detailed systematic study on the effects of different amount (wt.%) of LiI addition on the electrical conductivity and dielectric behavior of the xLi{sub 2}CO{sub 3}-xLiI (x = 95-70, y = 5-30 wt.%) electrolyte system was carried out. The samples with different compositions were prepared and ground by mechanical milling method. The electrical and dielectric properties of the samples over a range of frequency (50Hz – 1MHz) were investigated by deploying electrical impedance spectroscopy (EIS) technique in a series of temperature set (298–373K). Normally, Li{sub 2}CO{sub 3} itself shows a very low electrical conductivity (10{sup −5} Scm{sup −1}). However, the electrical conductivity of the system was found to be increased (10{sup −3} Scm{sup −1}) as the lithium salt (LiI) were introduced to the system. The dielectric analysis displayed that the activation energy was inversely proportional to the increment of LiI (wt.%). As the electrical conductivity reached their maximum value (4.63 × 10{sup −3} Scm{sup −1}) at the 20 wt.% of LiI, the activation energy was dropped to the minimum (0.1 eV). The electrical conductivity increases with the temperature (298 – 373K) indicate that the system obeys Arrhenius law.

  7. Electrolytically exfoliated graphene-loaded flame-made Ni-doped SnO2 composite film for acetone sensing.

    PubMed

    Singkammo, Suparat; Wisitsoraat, Anurat; Sriprachuabwong, Chakrit; Tuantranont, Adisorn; Phanichphant, Sukon; Liewhiran, Chaikarn

    2015-02-11

    In this work, flame-spray-made SnO2 nanoparticles are systematically studied by doping with 0.1-2 wt % nickel (Ni) and loading with 0.1-5 wt % electrolytically exfoliated graphene for acetone-sensing applications. The sensing films (∼12-18 μm in thickness) were prepared by a spin-coating technique on Au/Al2O3 substrates and evaluated for acetone-sensing performances at operating temperatures ranging from 150 to 350 °C in dry air. Characterizations by X-ray diffraction, transmission/scanning electron microscopy, Brunauer-Emmett-Teller analysis, X-ray photoelectron spectroscopy and Raman spectroscopy demonstrated that Ni-doped SnO2 nanostructures had a spheriodal morphology with a polycrystalline tetragonal SnO2 phase, and Ni was confirmed to form a solid solution with SnO2 lattice while graphene in the sensing film after annealing and testing still retained its high-quality nonoxidized form. Gas-sensing results showed that SnO2 sensing film with 0.1 wt % Ni-doping concentration exhibited an optimal response of 54.2 and a short response time of ∼13 s toward 200 ppm acetone at an optimal operating temperature of 350 °C. The additional loading of graphene at 5 wt % into 0.1 wt % Ni-doped SnO2 led to a drastic response enhancement to 169.7 with a very short response time of ∼5.4 s at 200 ppm acetone and 350 °C. The superior gas sensing performances of Ni-doped SnO2 nanoparticles loaded with graphene may be attributed to the large specific surface area of the composite structure, specifically the high interaction rate between acetone vapor and graphene-Ni-doped SnO2 nanoparticles interfaces and high electronic conductivity of graphene. Therefore, the 5 wt % graphene loaded 0.1 wt % Ni-doped SnO2 sensor is a promising candidate for fast, sensitive and selective detection of acetone. PMID:25602118

  8. Synthesis of LiNiO2 cathode materials with homogeneous Al doping at the atomic level

    SciTech Connect

    Liu, Zengcai; Zhen, Honghe; Kim, Yoongu; Liang, Chengdu

    2011-01-01

    Aluminum doped LiNiO2 cathode materials are synthesized by using Raney nickel as the starting material. The structure and composition are characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) coupled with elemental mapping. The lithium deficiency is analyzed by Rieveld refinement. The initial capacity and retention of capacity are correlated to the lithium deficiency of the resulting cathode material. Using strong oxidant of Li2O2 in the synthesis results in materials with improved electrochemical cyclability. The improvement is related to the diminishing of lithium deficiency in strong oxidizing synthesis conditions.

  9. Interfacial characteristics of a PEGylated imidazolium bistriflamide ionic liquid electrolyte at a lithium ion battery cathode of LiMn2O4.

    PubMed

    Rock, Simon E; Wu, Lin; Crain, Daniel J; Krishnan, Sitaraman; Roy, Dipankar

    2013-03-01

    Nonvolatile and nonflammable ionic liquids (ILs) have distinct thermal advantages over the traditional organic solvent electrolytes of lithium ion batteries. However, this beneficial feature of ILs is often counterbalanced by their high viscosity (a limiting factor for ionic conductivity) and, sometimes, by their unsuitable electrochemistry for generating protective layers on electrode surfaces. In an effort to alleviate these limiting aspects of ILs, we have synthesized a PEGylated imidazolium bis(trifluoromethylsulfonyl)amide (bistriflamide) IL that exhibited better thermal and electrochemical stability than a conventional electrolyte based on a blend of ethylene carbonate and diethyl carbonate. The electrochemical performance of this IL has been demonstrated using a cathode consisting of ball-milled LiMn2O4 particles. A direct comparison of the ionic liquid electrolyte with the nonionic low-viscosity conventional solvent blend is presented.

  10. The surface film formed on a lithium metal electrode in a new imide electrolyte, lithium bis(perfluoroethylsulfonylimide) [LiN(C{sub 2}F{sub 5}SO{sub 2}){sub 2}

    SciTech Connect

    Naoi, Katsuhiko; Mori, Mitsuhiro; Naruoka, Yoshinori; Lamanna, W.M.; Atanasoski, R.

    1999-02-01

    A newly developed imide electrolyte salt, LiN(C{sub 2}F{sub 5}SO{sub 2}){sub 2} (LiBETI) was found to give very uniform, thin, and stable surface films on a lithium metal electrode in the propylene carbonate (PC) solution. LiBETI/PC was studied and compared to determine its ability to form such a stable surface film, with conventional electrolyte systems such as LiCF{sub 3}SO{sub 3}/PC, LiPF{sub 6}/PC, and LiN(CF{sub 3}So{sub 2}){sub 2}/PC (LiTFSI/PC). The surface film formed in LiBETI/PC system was a hemispherical, and the composition of the film consisted mainly of LiF, which is similar to that in a LiPF{sub 6}/PC system. Quartz crystal microbalance (QCM) and cyclic voltammetry (after the tenth cycle) indicated that the surface film formed in LiBETI/PC (ca. 50 nm) was thinner than those in LiPF{sub 6}/PC (ca. 90 nm), LiTFSI/PC (ca. 140 nm), or LiCF{sub 3}SO{sub 3}/PC (ca. 255 nm). The variation of the resonance resistance ({Delta}R) obtained from in situ CV/QCM measurement, which has been demonstrated to be a good measure of the surface roughness, also suggested that LiBETI/PC system gave a compact and smooth surface topology during lithium deposition-dissolution cycles. Impedance spectroscopy together with preliminary cycling tests showed that the LiBETI/PC system provides the highest cycling efficiency and improved cycleability among existing electrolyte salt systems in rechargeable battery systems employing lithium metal anodes.

  11. Colossal thermoelectric power in charge-ordered Li-doped La0.75Li0.25MnO3 manganite system

    NASA Astrophysics Data System (ADS)

    Taran, Subhrangsu; Sun, C. P.; Yang, H. D.; Chatterjee, S.

    2016-05-01

    A detail study of transport and magnetic properties of La1-xLixMnO3+δ (0.05 ≤ x ≤ 0.3) system synthesized by wet-chemical mixing route has been done. The room temperature x-ray powder diffraction (XRD) data show single phase behavior of all samples except x = 0.3. Rietveld refinement of XRD data shows structural transition from rhombohedral (R3-C) to orthorhombic (Pnma) symmetry occurs at the Li-doping level x > 0.2 with both the lattice parameter and unit-cell volume decrease with increase of `x'. All the samples show ferromagnetic (FM) behavior while metallic behavior are shown by the samples up to Li-concentration x = 0.2. With further Li doping i.e. for x = 0.25, the sample shows insulating behavior accompanied by charge-order transition around T ~ 225K. Metallic part of the resistivity data of the samples is best fitted with an expression ρ(T) = ρ0 + ρ4.5T4.5 + C/ sinh2(hvs/2kBT) containing small-polaron contribution (last term). Most interesting finding in the present study is the observation of large anomalous decrease in thermoelectric power (S) below 100K shown by the sample with x = 0.25. Probable mechanisms responsible for the observed colossal thermoelectric power have been discussed.

  12. Self-discharge suppression of 4.9 V LiNi0.5Mn1.5O4 cathode by using tris(trimethylsilyl)borate as an electrolyte additive

    NASA Astrophysics Data System (ADS)

    Liao, Xiaolin; Huang, Qiming; Mai, Shaowei; Wang, Xianshu; Xu, Mengqing; Xing, Lidan; Liao, Youhao; Li, Weishan

    2014-12-01

    In this paper, tris(trimethylsilyl)borate (TMSB) is evaluated as an electrolyte additive for the self-discharge suppression of 4.9 V LiNi0.5Mn1.5O4 cathode for lithium ion battery. The effect of TMSB on the surface properties of LiNi0.5Mn1.5O4 is investigated via linear sweep voltammetry (LSV), cyclic voltammetry (CV), chronoamperometry (CA), charge-discharge test, electrochemical impedance spectra (EIS), scanning electron microscopy (SEM), X-ray diffraction (XRD), inductively coupled plasma atomic emission spectrometer (ICP-AES) and Fourier transform infrared spectroscopy (FTIR). It is found that the LiNi0.5Mn1.5O4 cathode charged to 4.9 V (vs. Li/Li+) suffers a serious self-discharge in 1 mol L-1 LiPF6-EC/DMC (1:2, in weight), which can be suppressed effectively by adding 1 wt.% TMSB into the electrolyte. After storage for 20 days, the voltage of the charged cathode decreases from 4.7 to 0.5 V (vs. Li/Li+) in the additive-free electrolyte, while that remains almost unchanged in the TMSB-containing electrolyte. The self-discharge suppression of the charged LiNi0.5Mn1.5O4 cathode results from the preferential oxidation of TMSB and the subsequent formation of a protective solid electrolyte interphase film, which prevents electrolyte decomposition and protects LiNi0.5Mn1.5O4 from destruction.

  13. Lithium Ion Polymer Electrolyte Based on Pva-Pan

    NASA Astrophysics Data System (ADS)

    Genova, F. Kingslin Mary; Selvasekarapandian, S.; Rajeswari, N.; Devi, S. Siva; Karthikeyan, S.; Raja, C. Sanjeevi

    2013-07-01

    The polymer blend electrolytes based on polyvinylalcohol(PVA) and polyacrylonitrile (PAN) doped with lithium per chlorate (LiClO4) have been prepared by solution casting technique using DMF as solvent. The complex formation between blend polymer and the salt has been confirmed by Fourier transform infrared spectroscopy. The amorphous nature of the blend polymer electrolyte has been confirmed by X-ray diffraction analysis. The ionic conductivity of the prepared blend polymer electrolyte has been found by ac impedence spectroscopic analysis. The highest ionic conductivity has been found to be 5.0 X10-4 S cm -1 at room temperature for 92.5 PVA: 7.5PAN: 20 molecular wt. % of LiClO4. The effect of salt concentration on the conductivity of the blend polymer electrolyte has been discussed.

  14. Influences of neodymium doping on magnetic and electrochemical properties of Li3V2(PO4)3/C synthesized via a sol-gel method

    NASA Astrophysics Data System (ADS)

    Liu, Liying; Qiu, Yongbin; Mai, Yongzhi; Wu, Qibai; Zhang, Haiyan

    2015-11-01

    A series of neodymium doped Li3V2-xNdx(PO4)3/C cathode materials have been successfully synthesized by a citric acid assisted sol-gel method. Nd doped samples (x ≤ 0.10) have well developed monoclinic structure of Li3V2(PO4)3 with enlarged unit cell volume. All samples present typical characteristics of paramagnetism in 4 < T ≤ 300 K, but the magnetic susceptibilities of Nd doped samples increase with Nd content (except for x = 0.15). Nd doped composites show better electrochemical property than that of the undoped one. Among them, the Li3V1.95Nd0.05(PO4)3/C displays the highest capacity and best cycle stability. The Li3V1.95Nd0.05(PO4)3/C presents the first discharge capacity of 129.2 mAh g-1 at 1 C rate in the voltage range of 3.0-4.3 V, 21.7% higher than that of Li3V2(PO4)3/C. And no capacity loss occurs after 100 cycles. The high structural stability, low charge-transfer resistance and rapid Li+ diffusion due to the presence of Nd3+ are mainly responsible for the superior electrochemical performance of Nd doped Li3V2(PO4)3/C cathode materials.

  15. Numerical predictions and experimental verification of Li-O2 battery capacity limits for cathodes with spherical conductors and solid electrolytes

    NASA Astrophysics Data System (ADS)

    Lee, Heung Chan; Roev, Victor; Kim, Tae Young; Park, Min Sik; Lee, Dong Joon; Im, Dongmin; Doo, Seok-Gwang

    2016-11-01

    The capacity limits, local formation of Li2O2, passivation of active surfaces, and depletion of oxygen by mass transport characteristics in a composite cathode are modeled, numerically simulated, and experimentally evaluated for non-aqueous Li-O2 batteries employing composites of a solid polymer electrolyte and carbon particles as the cathode, Li metal as the anode, and an ion conductive oxide membrane as the separator. Although the theoretical maximum specific energy of the Li-O2 battery is known to be 3458 Wh kg-1cathode, our simulation predicts a maximum specific energy of 1840 Wh kg-1cathode with an optimized weight ratio of all essential components as well as cathode thickness. A specific energy of 1713 Wh kg-1cathode is experimentally demonstrated in a cell with a composite cathode of poly(ethylene oxide) electrolyte and Printex carbon nanoparticles with 48% carbon volume and 30 μm thickness. The model also predicts that the incorporation of voids in the cathode can significantly improve the specific energy.

  16. Transition metal redox and Mn disproportional reaction in LiMn0.5Fe0.5PO4 electrodes cycled with aqueous electrolyte

    NASA Astrophysics Data System (ADS)

    Zhuo, Zengqing; Hu, Jiangtao; Duan, Yandong; Yang, Wanli; Pan, Feng

    2016-07-01

    We performed soft x-ray absorption spectroscopy (sXAS) and a quantitative analysis of the transition metal redox in the LiMn0.5Fe0.5PO4 electrodes upon electrochemical cycling. In order to circumvent the complication of the surface reactions with organic electrolyte at high potential, the LiMn0.5Fe0.5PO4 electrodes are cycled with aqueous electrolyte. The analysis of the transitional metal L-edge spectra allows a quantitative determination of the redox evolution of Mn and Fe during the electrochemical cycling. The sXAS analysis reveals the evolving Mn oxidation states in LiMn0.5Fe0.5PO4. We found that electrochemically inactive Mn2+ is formed on the electrode surface during cycling. Additionally, the signal indicates about 20% concentration of Mn4+ at the charged state, providing a strong experimental evidence of the disproportional reaction of Mn3+ to Mn2+ and Mn4+ on the surface of the charged LiMn0.5Fe0.5PO4 electrodes.

  17. Doping Cu{sub 2}O in Electrolyte Solution: Dopant Incorporation, Atomic Structures and Electrical Properties

    SciTech Connect

    Tao, Meng; Zhang, Qiming

    2013-11-24

    We have pursued a number of research activities between April 2010 and April 2011: A detailed study on n-type doping in Cu2O by Br; An analysis of natural resource limitations to terawatt-scale solar cells; Attempt to achieve a 1.4-eV direct band gap in Ni sulfides (NiSx); First-principles studies of doping in Cu2O and electronic structures of NiSx.

  18. Electrochemical properties of graphene flakes as an air cathode material for Li-O2 batteries in an ether-based electrolyte.

    PubMed

    Kim, Se Young; Lee, Ho-Taek; Kim, Kwang-Bum

    2013-12-14

    We employed graphene flakes as an air-cathode material for Li-O2 batteries and investigated their electrochemical properties in the dimethyl ether electrolyte. Graphene flakes were prepared by microwave-assisted reduction of graphene oxide, and their electrochemical properties were compared with those of Ketjen Black and carbon nanotubes. The catalytic effect of the prepared graphene flake-air cathode was demonstrated using cyclic voltammetry and discharge-charge testing performed under a limited discharge capacity. The catalytic effect of graphene flakes was also supported by morphological and spectroscopic analysis of the discharge-charge products formed on the graphene surface. Scanning electron microscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy revealed that Li2O2, Li2O, and Li2CO3 were the main discharge products on all carbon-air cathode surfaces. Raman spectroscopy revealed that LiRCO3 was additionally formed on Ketjen Black and carbon nanotubes during the first discharge; however, its formation was not observed on the graphene flakes. The catalytic effect of the graphene flakes and the absence of LiRCO3 in the discharge product could explain the higher Coulombic efficiency in the discharge-charge tests.

  19. Electrochemical properties of graphene flakes as an air cathode material for Li-O2 batteries in an ether-based electrolyte.

    PubMed

    Kim, Se Young; Lee, Ho-Taek; Kim, Kwang-Bum

    2013-12-14

    We employed graphene flakes as an air-cathode material for Li-O2 batteries and investigated their electrochemical properties in the dimethyl ether electrolyte. Graphene flakes were prepared by microwave-assisted reduction of graphene oxide, and their electrochemical properties were compared with those of Ketjen Black and carbon nanotubes. The catalytic effect of the prepared graphene flake-air cathode was demonstrated using cyclic voltammetry and discharge-charge testing performed under a limited discharge capacity. The catalytic effect of graphene flakes was also supported by morphological and spectroscopic analysis of the discharge-charge products formed on the graphene surface. Scanning electron microscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy revealed that Li2O2, Li2O, and Li2CO3 were the main discharge products on all carbon-air cathode surfaces. Raman spectroscopy revealed that LiRCO3 was additionally formed on Ketjen Black and carbon nanotubes during the first discharge; however, its formation was not observed on the graphene flakes. The catalytic effect of the graphene flakes and the absence of LiRCO3 in the discharge product could explain the higher Coulombic efficiency in the discharge-charge tests. PMID:24166701

  20. Diphenyloctyl phosphate and tris(2,2,2-trifluoroethyl) phosphite as flame-retardant additives for Li-ion cell electrolytes at elevated temperature

    NASA Astrophysics Data System (ADS)

    Nam, Tae-Heum; Shim, Eun-Gi; Kim, Jung-Gu; Kim, Hyun-Soo; Moon, Seong-In

    The effect of diphenyloctyl phosphate (DPOF) and tris(2,2,2-trifluoroethyl) phosphite (TTFP) as flame-retardant (FR) additives in the liquid electrolyte of Li-ion cells is evaluated at both elevated temperature (40 °C) and room temperature (RT, 25 °C). The tested cells use mesocarbon microbeads (MCMB) and LiCoO 2 as the anode and cathode materials, respectively. Cell characteristics are investigated by means of electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The results of the cycle performance tests demonstrate the superior discharge capacity and capacity retention of the DPOF-containing cell compared will TTFP after cycling at both RT and 40 °C. Therefore, these results confirm the promising potential of DPOF as an FR additive for improving the electrochemical performance of Li-ion batteries.

  1. The effects of silicon doping on the performance of PMAN carbon anodes in Li-ion cells

    SciTech Connect

    Guidotti, R.A.; Johnson, B.J.; Even, W. Jr.

    1996-05-01

    Carbons derived from polymethylacrylonitrile (PMAN) have been studied for use as intercalation anodes in Li-ion cells. The effect of Si doping upon the electrochemical performance of PMAN carbons was studied using tetravinylsilane (TVS) and tetramethysilane (TMS) as sources of Si during the formation of the PMAN precursors. The carbons were characterized by galvanostatic cycling, cyclic voltammetry, and complex impedance. The presence of 9 to 11 w/o Si in the PMAN lattice greatly increased the irreversible capacity of these materials.

  2. Mechanical degradation under hydrogen of yttrium doped barium zirconate electrolyte material prepared with NiO additive

    NASA Astrophysics Data System (ADS)

    Ciria, D.; Ben Hassine, M.; Jiménez-Melendo, M.; Iakovleva, A.; Haghi-Ashtiani, P.; Aubin, V.; Dezanneau, G.

    2016-07-01

    Recently, a novel process was presented to fabricate dense yttrium-doped barium zirconate electrolytes with high proton conductivity. This process was based on the use of a NiO additive during reactive sintering. We show here that materials made from this process present a fast degradation of mechanical properties when put in hydrogen-rich conditions, while material made from conventional sintering without NiO aid remains intact in the same conditions. The fast degradation of samples made from reactive sintering, leading to sample failure under highly compressive conditions, is due to the reduction of NiO nanoparticles at grain boundaries as shown from structural and chemical analyses using Transmission Electron Microscopy. By the present study, we alert about the potential risk of cell failure due to this mechanical degradation.

  3. Novel Proton Conducting Solid Bio-polymer Electrolytes Based on Carboxymethyl Cellulose Doped with Oleic Acid and Plasticized with Glycerol

    NASA Astrophysics Data System (ADS)

    Chai, M. N.; Isa, M. I. N.

    2016-06-01

    The plasticized solid bio-polymer electrolytes (SBEs) system has been formed by introducing glycerol (Gly) as the plasticizer into the carboxymethyl cellulose (CMC) doped with oleic acid (OA) via solution casting techniques. The ionic conductivity of the plasticized SBEs has been studied using Electrical Impedance Spectroscopy. The highest conductivity achieved is 1.64 × 10‑4 S cm‑1 for system containing 40 wt. % of glycerol. FTIR deconvolution technique had shown that the conductivity of CMC-OA-Gly SBEs is primarily influenced by the number density of mobile ions. Transference number measurement has shown that the cation diffusion coefficient and ionic mobility is higher than anion which proved the plasticized polymer system is a proton conductor.

  4. Novel Proton Conducting Solid Bio-polymer Electrolytes Based on Carboxymethyl Cellulose Doped with Oleic Acid and Plasticized with Glycerol.

    PubMed

    Chai, M N; Isa, M I N

    2016-01-01

    The plasticized solid bio-polymer electrolytes (SBEs) system has been formed by introducing glycerol (Gly) as the plasticizer into the carboxymethyl cellulose (CMC) doped with oleic acid (OA) via solution casting techniques. The ionic conductivity of the plasticized SBEs has been studied using Electrical Impedance Spectroscopy. The highest conductivity achieved is 1.64 × 10(-4) S cm(-1) for system containing 40 wt. % of glycerol. FTIR deconvolution technique had shown that the conductivity of CMC-OA-Gly SBEs is primarily influenced by the number density of mobile ions. Transference number measurement has shown that the cation diffusion coefficient and ionic mobility is higher than anion which proved the plasticized polymer system is a proton conductor. PMID:27265642

  5. Novel Proton Conducting Solid Bio-polymer Electrolytes Based on Carboxymethyl Cellulose Doped with Oleic Acid and Plasticized with Glycerol

    PubMed Central

    Chai, M. N.; Isa, M. I. N.

    2016-01-01

    The plasticized solid bio-polymer electrolytes (SBEs) system has been formed by introducing glycerol (Gly) as the plasticizer into the carboxymethyl cellulose (CMC) doped with oleic acid (OA) via solution casting techniques. The ionic conductivity of the plasticized SBEs has been studied using Electrical Impedance Spectroscopy. The highest conductivity achieved is 1.64 × 10−4 S cm−1 for system containing 40 wt. % of glycerol. FTIR deconvolution technique had shown that the conductivity of CMC-OA-Gly SBEs is primarily influenced by the number density of mobile ions. Transference number measurement has shown that the cation diffusion coefficient and ionic mobility is higher than anion which proved the plasticized polymer system is a proton conductor. PMID:27265642

  6. Room temperature p-type conductivity and coexistence of ferroelectric order in ferromagnetic Li doped ZnO nanoparticles

    SciTech Connect

    Awan, Saif Ullah E-mail: ullahphy@gmail.com; Hasanain, S. K.; Anjum, D. H.; Awan, M. S.; Shah, Saqlain A.

    2014-10-28

    Memory and switching devices acquired new materials which exhibit ferroelectric and ferromagnetic order simultaneously. We reported multiferroic behavior in Zn{sub 1−y}Li{sub y}O(0.00≤y≤0.10) nanoparticles. The analysis of transmission electron micrographs confirmed the hexagonal morphology and wurtzite crystalline structure. We investigated p-type conductivity in doped samples and measured hole carriers in range 2.4 × 10{sup 17}/cc to 7.3 × 10{sup 17}/cc for different Li contents. We found that hole carriers are responsible for long range order ferromagnetic coupling in Li doped samples. Room temperature ferroelectric hysteresis loops were observed in 8% and 10% Li doped samples. We demonstrated ferroelectric coercivity (remnant polarization) 2.5 kV/cm (0.11 μC/cm{sup 2}) and 2.8 kV/cm (0.15 μC/cm{sup 2}) for y = 0.08 and y = 0.10 samples. We propose that the mechanism of Li induced ferroelectricity in ZnO is due to indirect dipole interaction via hole carriers. We investigated that if the sample has hole carriers ≥5.3 × 10{sup 17}/cc, they can mediate the ferroelectricity. Ferroelectric and ferromagnetic measurements showed that higher electric polarization and larger magnetic moment is attained when the hole concentration is larger and vice versa. Our results confirmed the hole dependent coexistence of ferromagnetic and ferroelectric behavior at room temperature, which provide potential applications for switchable and memory devices.

  7. Rare earth doped LiYbF{sub 4} phosphors with controlled morphologies: Hydrothermal synthesis and luminescent properties

    SciTech Connect

    Huang, Wenjuan; Lu, Chunhua; Jiang, Chenfei; Jin, Junyang; Ding, Mingye; Ni, Yaru; Xu, Zhongzi

    2012-06-15

    Highlights: ► LiYbF{sub 4} microparticles as an excellent upconverting materials. ► High temperature and long time can favor high crystalline LiYbF{sub 4} microparticles. ► The shape of LiYbF{sub 4} microparticles can be tuned by the molar ratio of EDTA to Yb{sup 3+}. ► Bright green emission can be obtained by changing the doping concentration of Er{sup 3+}. -- Abstract: High quality monodisperse LiYbF{sub 4} microparticles with shape of octahedron had been prepared via a facile hydrothermal route. The crystalline phase, size, morphology and luminescence properties were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectra and Commission Internationale de L’Eclairage (CIE 1931) chromaticity coordinates, respectively. The influences of reaction temperature, reaction time and the molar ratio of EDTA to Yb{sup 3+} on the crystal phases and shapes of as-prepared products had been investigated in detail. The upconversion (UC) luminescence properties of LiYb{sub 1−x}F{sub 4}:xEr{sup 3+} (x =0.1, 0.2, 0.5, 1, 2, 5 and 10 mol%) particles with octahedral microstructures were studied under 976 nm excitation. The results showed that the luminescence colors of the corresponding products could be tuned to bright green by changing the doping concentration of Er{sup 3+} ion. The luminescence mechanisms for the doped Er{sup 3+} ion were thoroughly analyzed, showing great potential in applications such as biolabels, displays and other optical technologies.

  8. Interrelationships among Grain Size, Surface Composition, Air Stability, and Interfacial Resistance of Al-Substituted Li7La3Zr2O12 Solid Electrolytes.

    PubMed

    Cheng, Lei; Wu, Cheng Hao; Jarry, Angelique; Chen, Wei; Ye, Yifan; Zhu, Junfa; Kostecki, Robert; Persson, Kristin; Guo, Jinghua; Salmeron, Miquel; Chen, Guoying; Doeff, Marca

    2015-08-19

    The interfacial resistances of symmetrical lithium cells containing Al-substituted Li7La3Zr2O12 (LLZO) solid electrolytes are sensitive to their microstructures and histories of exposure to air. Air exposure of LLZO samples with large grain sizes (∼150 μm) results in dramatically increased interfacial impedances in cells containing them, compared to those with pristine large-grained samples. In contrast, a much smaller difference is seen between cells with small-grained (∼20 μm) pristine and air-exposed LLZO samples. A combination of soft X-ray absorption (sXAS) and Raman spectroscopy, with probing depths ranging from nanometer to micrometer scales, revealed that the small-grained LLZO pellets are more air-stable than large-grained ones, forming far less surface Li2CO3 under both short- and long-term exposure conditions. Surface sensitive X-ray photoelectron spectroscopy (XPS) indicates that the better chemical stability of the small-grained LLZO is related to differences in the distribution of Al and Li at sample surfaces. Density functional theory calculations show that LLZO can react via two different pathways to form Li2CO3. The first, more rapid, pathway involves a reaction with moisture in air to form LiOH, which subsequently absorbs CO2 to form Li2CO3. The second, slower, pathway involves direct reaction with CO2 and is favored when surface lithium contents are lower, as with the small-grained samples. These observations have important implications for the operation of solid-state lithium batteries containing LLZO because the results suggest that the interfacial impedances of these devices is critically dependent upon specific characteristics of the solid electrolyte and how it is prepared.

  9. Thermochemical compatibility between selected (La,Sr)(Co,Fe,Ni)O 3 cathodes and rare earth doped ceria electrolytes

    NASA Astrophysics Data System (ADS)

    Zając, Wojciech; Świerczek, Konrad; Molenda, Janina

    In this paper the results of thermal expansion coefficient measurements of different singly and doubly doped ceria electrolytes, together with results for selected cathode materials from (La,Sr)(Co,Fe,Ni)O 3 system are given. A high temperature chemical stability of the cathode-electrolyte interface was measured on 1:1 wt. mixtures of previously characterized ceria and perovskite powders. The samples were heated at 800, 1000 or at 1200 °C in air for 6 or 100 h. Chemical reactivity investigations were conducted using XRD with Rietveld analysis. For all heated samples the crystal structure of both components were preserved. However, their lattice parameters evolved to a different extent, suggesting the existence of cation exchange. A formation of the solid state solution between Ce 1- xRE xO 2- x/2 and La(Co,Fe,Ni)O 3- δ was found, with mobile La cation. On the basis of the obtained results a qualitative mechanism of the observed reaction was proposed.

  10. Direct Observation of Lattice Aluminum Environments in Li Ion Cathodes LiNi1-y-zCoyAlzO2 and Al-Doped LiNixMnyCozO2 via (27)Al MAS NMR Spectroscopy.

    PubMed

    Dogan, Fulya; Vaughey, John T; Iddir, Hakim; Key, Baris

    2016-07-01

    Direct observations of local lattice aluminum environments have been a major challenge for aluminum-bearing Li ion battery materials, such as LiNi1-y-zCoyAlzO2 (NCA) and aluminum-doped LiNixMnyCozO2 (NMC). (27)Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is the only structural probe currently available that can qualitatively and quantitatively characterize lattice and nonlattice (i.e., surface, coatings, segregation, secondary phase etc.) aluminum coordination and provide information that helps discern its effect in the lattice. In the present study, we use NMR to gain new insights into transition metal (TM)-O-Al coordination and evolution of lattice aluminum sites upon cycling. With the aid of first-principles DFT calculations, we show direct evidence of lattice Al sites, nonpreferential Ni/Co-O-Al ordering in NCA, and the lack of bulk lattice aluminum in aluminum-"doped" NMC. Aluminum coordination of the paramagnetic (lattice) and diamagnetic (nonlattice) nature is investigated for Al-doped NMC and NCA. For the latter, the evolution of the lattice site(s) upon cycling is also studied. A clear reordering of lattice aluminum environments due to nickel migration is observed in NCA upon extended cycling.

  11. Characterization of CH3SO3H-doped PMMA/PVP blend-based proton-conducting polymer electrolytes and its application in primary battery

    NASA Astrophysics Data System (ADS)

    Ambika, C.; Hirankumar, G.

    2016-02-01

    Various compositions of solid blend polymer electrolytes based on poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP) complexed with methanesulfonic acid (MSA) as proton donor were prepared by solution casting technique. The complex nature of polymer blend with MSA was confirmed by Fourier transform infrared spectroscopy. Good thermal stability of PMMA/PVP blend polymer electrolyte was identified by thermogravimetric analysis. The surface morphology of the prepared electrolytes was studied through optical microscopy. Ion transport number was determined in the range of 0.93-0.97 for proton-conducting blend polymer electrolytes. The maximum conductivity value was calculated as 2.51 × 10-5 S/cm at 303 K for 14.04 mol% MSA-doped polymer electrolytes. Dielectric studies were also carried out. The electrochemical stability window of blend polymer electrolyte was found to be 1.82 V. Primary proton battery was fabricated with Zn + ZnSO4·7H2O/solid polymer electrolytes/MnO2. The discharge characteristics were studied at constant current drain of 5, 20 and 50 μA. The energy and power density were calculated as 0.27 W h kg-1 and 269.23 mW kg-1 for 20 μA of discharge, respectively.

  12. Near room temperature magnetodielectric consequence in (Li, Ti) doped NiO ceramic

    NASA Astrophysics Data System (ADS)

    Mukherjee, S.; Chatterjee, S.; Rayaprol, S.; Kaushik, S. D.; Bhattacharya, S.; Jana, P. K.

    2016-04-01

    In the quest for high-k dielectrics with decent magnetodielectric (MD) response, ball-milled processed (Li, Ti) doped NiO ceramics have been evaluated by various experimental techniques. Magnetic properties in these ceramics manifest with a pronounced anomaly appearing at ˜260 K, suggesting ferrimagnetic phase (related to cluster magnetism) and co-existence with a glassy-like antiferromagnetic phase at ˜7 K. Room temperature neutron diffraction pattern shows the existence of short-range magnetic correlations. In the magnetically ordered state below 250 K, the magnetic structure is found to be phase coexistence of G-type antiferromagnet and ferrimagnet. Impedance spectroscopy measurements over a wide temperature range can be perfectly described with appropriate microstructural model (internal barrier layer capacitor), based on domain and domain boundary relaxations, justifying the enhancement of the dielectric response. The low-temperature (T < 100 K) dielectric relaxation is polaronic in nature, associated with the charge ordering of a mixed valence states of Ti ions (co-existence of Ti3+ and Ti4+). Finally, our investigations in external magnetic fields up to 15 T reveal the occurrence of negative MD effect near room temperature. This intriguing intrinsic feature has been understood by the mechanism of charge-hopping-mediated MD effects.

  13. Effects of magnesium doping on electronic conductivity and electrochemical properties of LiFePO 4 prepared via hydrothermal route

    NASA Astrophysics Data System (ADS)

    Ou, Xiuqin; Liang, Guangchuan; Wang, Li; Xu, Shengzhao; Zhao, Xia

    Carbon free composites Li 1- xMg xFePO 4 (x = 0.00, 0.02) were synthesized from LiOH, H 3PO 4, FeSO 4 and MgSO 4 through hydrothermal route at 180 °C for 6h followed by being fired at 750 °C for 6 h. The samples were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), flame atomic absorption spectroscopy and electronic conductivity measurement. To investigate their electrochemical properties, the samples were mixed with glucose as carbon precursors, and fired at 750 °C for 6 h. The charge-discharge curves and cycle life test were carried out at 23 ± 2 °C. The Rietveid refinement results of lattice parameters of the samples indicate that the magnesium ion has been successfully doped into the M1 (Li) site of the phospho-olivine structure. With the same order of magnitude, there is no material difference in terms of the electronic conductivities between the doped and undoped composites. Conductivities of the doped and undoped samples are 10 -10 S cm -1 before being fired, 10 -9 S cm -1 after being fired at 750 °C, and 10 -1 S cm -1 after coated with carbon, respectively. Both the doped and undoped composites coated with carbon exhibit comparable specific capacities of 146 mAh g -1 vs. 144 mAh g -1 at 0.2 C, 140 mAh g -1 vs. 138 mAh g -1 at 1 C, and 124 mAh g -1 vs. 123 mAh g -1 at 5 C, respectively. The capacity retention rates of both doped and undoped samples over 50 cycles at 5 C are close to 100% (vs. the first-cycle corresponding C-rate capacity). Magnesium doping has little effects on electronic conductivity and electrochemical properties of LiFePO 4 composites prepared via hydrothermal route.

  14. The electrical and optical studies of the KC1 doped PVA polymer electrolyte materials

    NASA Astrophysics Data System (ADS)

    Kamani, K. K.; Madhu, B. J.; Nethravathi, M.; Ashwini, S. T.

    2013-06-01

    In the recent years the greatest attention has been paid to determine the conductivity of different concentration solutions conducting polymers exhibit a wide range of novel electrochemical and chemical properties that has led to their use in a diverse array of applications including sensors PVA is fully degradable and dissolves quickly. PVA biodegradation is believed to be due to a random chain cleavage process. PVA molecular matrix and KC1 solutions were prepared with distilled water as solvent. The saturated solutions electric conductivity, pH values reveals the increase of ionic concentrations with increase of dopant weight fractions. Dielectric properties and UV visible studies of PVA and KC1 polymer complex experimental observations suggest the variations in the ionic nature electrolyte. Material. We are reporting the conducting properties of the PVA and KC1 polymer matrix and electrical nature of the PVA complex structure as electrolyte.

  15. A systematic study on the reactivity of different grades of charged Li[NixMnyCoz]O2 with electrolyte at elevated temperatures using accelerating rate calorimetry

    NASA Astrophysics Data System (ADS)

    Ma, Lin; Nie, Mengyun; Xia, Jian; Dahn, J. R.

    2016-09-01

    The reactivity between charged Li[NixMnyCoz]O2 (NMC, with x + y + z = 1, x:y:z = 1:1:1 (NMC111), 4:4:2 (NMC442), 5:3:2 (NMC532), 6:2:2 (NMC622) and 8:1:1 (NMC811)) and traditional carbonate-based electrolytes at elevated temperatures was systematically studied using accelerating rate calorimetry (ARC). The ARC results showed that the upper cut-off potential and NMC composition strongly affect the thermal stability of the various NMC grades when traditional carbonate-based electrolyte was used. Although higher cut-off potential and higher Ni content can help increase the energy density of lithium ion cells, these factors generally increase the reactivity between charged NMC and electrolyte at elevated temperatures. It is hoped that this report can be used to help guide the wise selection of NMC grade and upper cut-off potential to achieve high energy density Li-ion cells without seriously compromising cell safety.

  16. Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) components.

    SciTech Connect

    Leung, Kevin; Lin, Yu -Xiao; Liu, Zhe; Chen, Long -Qing; Lu, Peng; Qi, Yue

    2016-01-01

    The formation and continuous growth of a solid electrolyte interphase (SEI) layer are responsible for the irreversible capacity loss of batteries in the initial and subsequent cycles, respectively. In this article, the electron tunneling barriers from Li metal through three insulating SEI components, namely Li2CO3, LiF and Li3PO4, are computed by density function theory (DFT) approaches. Based on electron tunneling theory, it is estimated that sufficient to block electron tunneling. It is also found that the band gap decreases under tension while the work function remains the same, and thus the tunneling barrier decreases under tension and increases under compression. A new parameter, η, characterizing the average distances between anions, is proposed to unify the variation of band gap with strain under different loading conditions into a single linear function of η. An analytical model based on the tunneling results is developed to connect the irreversible capacity loss, due to the Li ions consumed in forming these SEI component layers on the surface of negative electrodes. As a result, the agreement between the model predictions and experimental results suggests that only the initial irreversible capacity loss is due to the self-limiting electron tunneling property of the SEI.

  17. Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) components.

    DOE PAGESBeta

    Leung, Kevin; Lin, Yu -Xiao; Liu, Zhe; Chen, Long -Qing; Lu, Peng; Qi, Yue

    2016-01-01

    The formation and continuous growth of a solid electrolyte interphase (SEI) layer are responsible for the irreversible capacity loss of batteries in the initial and subsequent cycles, respectively. In this article, the electron tunneling barriers from Li metal through three insulating SEI components, namely Li2CO3, LiF and Li3PO4, are computed by density function theory (DFT) approaches. Based on electron tunneling theory, it is estimated that sufficient to block electron tunneling. It is also found that the band gap decreases under tension while the work function remains the same, and thus the tunneling barrier decreases under tension and increases under compression.more » A new parameter, η, characterizing the average distances between anions, is proposed to unify the variation of band gap with strain under different loading conditions into a single linear function of η. An analytical model based on the tunneling results is developed to connect the irreversible capacity loss, due to the Li ions consumed in forming these SEI component layers on the surface of negative electrodes. As a result, the agreement between the model predictions and experimental results suggests that only the initial irreversible capacity loss is due to the self-limiting electron tunneling property of the SEI.« less

  18. Preparation of thick-film electrode-solid electrolyte composites on Li7La3Zr2O12 and their electrochemical properties

    NASA Astrophysics Data System (ADS)

    Kato, Takeshia; Iwasaki, Shinya; Ishii, Yosuke; Motoyama, Munekazu; West, William C.; Yamamoto, Yuta; Iriyama, Yasutoshi

    2016-01-01

    We prepared up to 20 μm-thick LiNi1/3Co1/3Mn1/3O2 (NMC)-Li+ conductive glass-ceramic solid electrolyte (LATP: σLi+ ˜ 10-3 S cm-2 at 298 K) composite cathode films on Li7La3Zr2O12 (LLZ) substrates by aerosol deposition (AD) and investigated their electrochemical properties as all-solid-state batteries. The resultant NMC/LATP interface in the composite film had a thin mutual diffusion layer (˜5 nm) and a film had a porosity of ca. 0.15% in volume. The composite films were well adhered to the LLZ substrates even though the films were prepared at room temperature. All-solid-state batteries, consisting of Li/LLZ/NMC-LATP composite film (20 μm), repeated charge-discharge reactions for 90 cycles at 100 °C at a 1/10 C rate (capacity retention: 99.97%/cycle). Rate capability of this battery was improved by modifying both the LATP and electron conductive source amount in the composite film, and a battery with 16 μm-thick composite electrode delivered 60 mAh g-1 at 1 mA cm-2.

  19. First-principle calculation of core level binding energies of Li{sub x}PO{sub y}N{sub z} solid electrolyte

    SciTech Connect

    Guille, Émilie; Vallverdu, Germain Baraille, Isabelle

    2014-12-28

    We present first-principle calculations of core-level binding energies for the study of insulating, bulk phase, compounds, based on the Slater-Janak transition state model. Those calculations were performed in order to find a reliable model of the amorphous Li{sub x}PO{sub y}N{sub z} solid electrolyte which is able to reproduce its electronic properties gathered from X-ray photoemission spectroscopy (XPS) experiments. As a starting point, Li{sub 2}PO{sub 2}N models were investigated. These models, proposed by Du et al. on the basis of thermodynamics and vibrational properties, were the first structural models of Li{sub x}PO{sub y}N{sub z}. Thanks to chemical and structural modifications applied to Li{sub 2}PO{sub 2}N structures, which allow to demonstrate the relevance of our computational approach, we raise an issue concerning the possibility of encountering a non-bridging kind of nitrogen atoms (=N{sup −}) in Li{sub x}PO{sub y}N{sub z} compounds.

  20. Temperature effects on Li4Ti5O12 electrode/electrolyte interfaces at the first cycle: A X-ray Photoelectron Spectroscopy and Scanning Auger Microscopy study

    NASA Astrophysics Data System (ADS)

    Gieu, J.-B.; Courrèges, C.; El Ouatani, L.; Tessier, C.; Martinez, H.

    2016-06-01

    Li4Ti5O12-based negative electrodes for Lithium-ion batteries are of interest because of the high reversibility of Li+ insertion/extraction. In this study, the surface of cycled electrodes is analysed by X-ray Photoelectron Spectroscopy (XPS) and Scanning Auger Microscopy (SAM) to investigate the effects of cycling temperature (room temperature, 60 °C and 85 °C) upon the solid electrolyte interphase (SEI) formation, which plays a major role in batteries electrochemical performances. Half-cells, with a vinylene carbonate containing electrolyte, are galvanostatically cycled at different steps of the first cycle: the mid-plateau during the first discharge, the end of the first discharge at 1.2 V and the end of the first charge at 2.0 V. XPS analysis evidences that higher temperatures promote the formation of a thicker SEI, which can explain the increase of the irreversible capacity with temperature. SAM mappings (allowing high spatial resolution ∼10-100 nm) evidence that this SEI homogeneously covers the electrode surface, regardless of the cycling temperature. During charge, the SEI is partially dissolved at room temperature, more slightly at 60 °C whereas at 85 °C, no clear evidence of layer thinning is observed. The SEI chemical composition is also investigated and reveals a majority of organic species and an increasing proportion of LiF with the temperature.

  1. Nano-granulization of gadolinia-doped ceria electrolyte surface by aerosol-assisted chemical vapor deposition for low-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kim, Jun Woo; Jang, Dong Young; Kim, Manjin; Choi, Hyung Jong; Shim, Joon Hyung

    2016-01-01

    We have fabricated nano-scale gadolinia-doped ceria (GDC) at the electrode-electrolyte boundary by aerosol-assisted chemical vapor deposition (AACVD) for high-performance solid oxide fuel cells (SOFCs) working at low temperatures below 500 °C. In AACVD, temperature is the key factor affecting the grain size. We have confirmed that by nano-granulizing the electrolyte surface using optimized AACVD, the power output of the SOFC is 50% higher than that of the bare GDC SOFC. From the impedance analysis, significant enhancement of the cathodic oxygen reduction reaction is identified from the AACVD-GDC nano-grain surface treatment.

  2. Li and Ag Co-Doped ZnO Photocatalyst for Degradation of RO 4 Dye Under Solar Light Irradiation.

    PubMed

    Dhatshanamurthi, P; Shanthi, M

    2016-06-01

    The synthesis of Li doped Ag-ZnO (Li-Ag-ZnO) has been successfully achieved by a sonochemically assisted precipitation-decomposition method. The synthesized catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), diffuse reflectance spectra (DRS), photoluminescence spectra (PL), X-ray photoelectron spectra (XPS) and BET surface area measurements. The photocatalytic activity of Li-Ag-ZnO was investigated for the degradation of Reactive orange 4 (RO 4) dye in aqueous solution under solar light irradiation. Co-dopants shift the absorbance of ZnO to the visible region. Li-Ag-ZnO is found to be more efficient than Ag-ZnO, Li-ZnO, commercial ZnO and prepared ZnO at pH 7 for the mineralization of RO 4 dye under solar light irradiation. The influences of operational parameters such as the amount of photocatalyst, dye concentration, initial pH on photo-mineralization of RO 4 have been analyzed. The mineralization of RO 4 dye has been confirmed by COD measurements. A degradation mechanism is proposed for the degradation of RO 4 under solar light. The catalyst was found to be more stable and reusable. PMID:27427652

  3. Enhanced rate performance of molybdenum-doped spinel LiNi0.5Mn1.5O4 cathode materials for lithium ion battery

    NASA Astrophysics Data System (ADS)

    Yi, Ting-Feng; Chen, Bin; Zhu, Yan-Rong; Li, Xiao-Ya; Zhu, Rong-Sun

    2014-02-01

    The Mo-doped LiNi0.5Mn1.5O4 cathodes are successfully synthesized by citric acid-assisted sol-gel method. The result demonstrates that the Mo-doped LiMn1.4Ni0.55Mo0.05O4 cathodes present the improved electrochemical performance over pristine LiNi0.5Mn1.5O4. At the 2 C rate after 80 cycles, the discharge capacities are 68.5 mAh g-1 for the pristine LiNi0.5Mn1.5O4 material (53.9% of the capacity at 0.1 C), 107.4 mAh g-1 for the LiMn1.425Ni0.5Mo0.05O4 material (82.1% at 0.1 C), and 122.7 mAh g-1 for the LiMn1.4Ni0.55Mo0.05O4 material (90.5% at 0.1 C). Mo-doping is favorable for reducing the electrode polarization, suggesting that Mo-doped LiNi0.5Mn1.5O4 electrodes have faster lithium insertion/extraction kinetics during cycling. Mo-doped LiNi0.5Mn1.5O4 electrodes show lower charge-transfer resistance and higher lithium diffusion coefficients. In addition, LiMn1.4Ni0.55Mo0.05O4 cathode exhibits the smallest particle size, the lowest charge-transfer resistance and the highest lithium diffusion coefficient among all samples, indicating that it has a high reversibility and good rate capability.

  4. Synthesis and characterization of lithium aluminum-doped spinel (LiAl xMn 2- xO 4) for lithium secondary battery

    NASA Astrophysics Data System (ADS)

    Lee, Yun-Sung; Kumada, Naoki; Yoshio, Masaki

    LiAl xMn 2- xO 4 has been synthesized using various aluminum starting materials, such as Al(NO 3) 3, Al(OH) 3, AlF 3 and Al 2O 3 at 600-800°C for 20 h in air or oxygen atmosphere. A melt-impregnation method was used to synthesize Al-doped spinel with good battery performance in this research. The Al-doped content and the intensity ratio of (3 1 1)/(4 0 0) peaks can be important parameters in synthesizing Al-doped spinel which satisfies the requirements of high discharge capacity and good cycleability at the same time. The decrease in Mn 3+ ion by Al substitution induces a high average oxidation state of Mn ion in the LiAl xMn 2- xO 4 material. The electrochemical behavior of all samples was studied in Li/LiPF 6-EC/DMC (1:2 by volume)/LiAl xMn 2- xO 4 cells. Especially, the initial and last discharge capacity of LiAl 0.09Mn 1.97O 4 using LiOH, Mn 3O 4 and Al(OH) 3 complex were 128.7 and 115.5 mAh/g after 100 cycles. The Al substitution in LiMn 2O 4 was an excellent method of enhancing the cycleability of stoichiometric spinel during electrochemical cycling.

  5. The synthesis and mechanism exploration of europium-doped LiYF4 micro-octahedron phosphors with multilevel interiors.

    PubMed

    Zhang, Xiangyu; Wang, Minqiang; Ding, Jijun; Deng, Jianping; Ran, Chenxin; Yang, Zhi

    2014-04-14

    Multi-layered hollow LiYF4:Eu(3+) micro-octahedrons, with about 400 nm of single-layer thickness and 300 nm of interlayer space, have been synthesized via a facile hydrothermal route in the presence of surfactant ethylenediamine tetraacetic acid (EDTA). The mechanisms of the morphology evolution of the LiYF4:Eu micro-octahedrons are investigated in detail. Time-dependent experiments indicate that the growth of the micro-octahedrons undergoes four different stages including the aggregation growth of the primary YF3 particle, the transformation of the substance from the orthorhombic-phase YF3 to the tetragonal-phase LiYF4 by the Kirkendall effect with the inward diffusion of quasi-steady state LiF species, adsorption and in situ crystallization, and local Ostwald ripening. The Ostwald ripening process is terminated by the organic adsorption of interlaminar leading to a hollow structure with multilevel interiors. The LiYF4:Eu micro-octahedrons are annealed under the designed temperatures, which leads to the collapse of octahedral structures indicating the role of EDTA on building the octahedron. The spectral measurements show that the calcination approach has a stronger effect on the luminescence tuning of the LiYF4:Eu micro-octahedrons due to the modification of the crystal phase, structure and size. The present study is of great importance in the preparation of rare-earth ion doped LiYF4 hollow materials as well as in applications as building blocks for functional devices. PMID:24522524

  6. The synthesis and mechanism exploration of europium-doped LiYF4 micro-octahedron phosphors with multilevel interiors.

    PubMed

    Zhang, Xiangyu; Wang, Minqiang; Ding, Jijun; Deng, Jianping; Ran, Chenxin; Yang, Zhi

    2014-04-14

    Multi-layered hollow LiYF4:Eu(3+) micro-octahedrons, with about 400 nm of single-layer thickness and 300 nm of interlayer space, have been synthesized via a facile hydrothermal route in the presence of surfactant ethylenediamine tetraacetic acid (EDTA). The mechanisms of the morphology evolution of the LiYF4:Eu micro-octahedrons are investigated in detail. Time-dependent experiments indicate that the growth of the micro-octahedrons undergoes four different stages including the aggregation growth of the primary YF3 particle, the transformation of the substance from the orthorhombic-phase YF3 to the tetragonal-phase LiYF4 by the Kirkendall effect with the inward diffusion of quasi-steady state LiF species, adsorption and in situ crystallization, and local Ostwald ripening. The Ostwald ripening process is terminated by the organic adsorption of interlaminar leading to a hollow structure with multilevel interiors. The LiYF4:Eu micro-octahedrons are annealed under the designed temperatures, which leads to the collapse of octahedral structures indicating the role of EDTA on building the octahedron. The spectral measurements show that the calcination approach has a stronger effect on the luminescence tuning of the LiYF4:Eu micro-octahedrons due to the modification of the crystal phase, structure and size. The present study is of great importance in the preparation of rare-earth ion doped LiYF4 hollow materials as well as in applications as building blocks for functional devices.

  7. Studies of defects in combustion synthesized europium-doped LiAl{sub 5}O{sub 8} red phosphor

    SciTech Connect

    Singh, Vijay Gundu Rao, T.K.

    2008-06-15

    Europium-doped LiAl{sub 5}O{sub 8} red phosphor was prepared using a self-propagating (combustion) synthesis. The formation of crystalline LiAl{sub 5}O{sub 8} was confirmed by X-ray diffraction. The morphological aspect of the resulting powders was examined by scanning electron microscopy. Electron spin resonance studies have been carried out in order to study the characteristics of the defect centres and the thermoluminescence (TL) peaks observed in this phosphor. Two types of centres (centre I and centre II) have been identified in LiAl{sub 5}O{sub 8}:Eu. Centre I is characteristic of a species exhibiting an isotropic g-value 2.0089 with a line width of 70 G and is assigned to a V-centre. Centre II is also characterized by an isotropic g-value 2.0059 with a line width of about 10 G. Centre II is ascribed to a F{sup +}-centre. A room temperature photoluminescence study shows a strong emission line at 613 nm corresponding to the {sup 5}D{sub 0}{yields}{sup 7}F{sub 2} transition of Eu{sup 3+} ions. - Graphical abstract: LiAl{sub 5}O{sub 8}:Eu{sup 3+} phosphors have been synthesized in a very short time (lt;5 min) by combustion process and are well characterized by XRD and SEM. TL glow peak was observed in gamma-irradiated Eu ion-doped LiAl{sub 5}O{sub 8} at around 180 deg. C. Electron spin resonance studies have been carried out in order to study the characteristics of the defect centres. Photoluminescence studies showed red emission located at about 613 nm and is ascribed to {sup 5}D{sub 0}-{sup 7}F{sub 2} transition of Eu{sup 3+} ions.

  8. Solid polymer electrolytes

    DOEpatents

    Abraham, K.M.; Alamgir, M.; Choe, H.S.

    1995-12-12

    This invention relates to Li ion (Li{sup +}) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF{sub 3}SO{sub 2}){sub 2}, LiAsF{sub 6}, and LiClO{sub 4}. 2 figs.

  9. Solid polymer electrolytes

    DOEpatents

    Abraham, Kuzhikalail M.; Alamgir, Mohamed; Choe, Hyoun S.

    1995-01-01

    This invention relates to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF.sub.3 SO.sub.2).sub.2, LiAsF.sub.6, and LiClO.sub.4.

  10. Solid polymer electrolyte lithium batteries

    DOEpatents

    Alamgir, Mohamed; Abraham, Kuzhikalail M.

    1993-01-01

    This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

  11. Solid polymer electrolyte lithium batteries

    DOEpatents

    Alamgir, M.; Abraham, K.M.

    1993-10-12

    This invention pertains to Lithium batteries using Li ion (Li[sup +]) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride). 3 figures.

  12. Near-stoichiometric Ti-diffused LiNbO(3) strip waveguide doped with Zr(4+).

    PubMed

    Zhang, De-Long; Yang, Xiao-Fei; Zhang, Qun; Wong, Wing-Han; Yu, Dao-Yin; Pun, Edwin Yue-Bun

    2015-11-15

    We report a near-stoichiometric Ti:Zr:LiNbO(3) strip waveguide fabricated from a congruent substrate with a technological process in the following sequence: Zr4+-diffusion-doping, diffusion of 8-μm-wide, 100-nm-thick Ti strips, and post-Li-rich vapor transport equilibration. We show that Zr(4+)-doping has little effect on the LiNbO(3) refractive index, and the waveguide is in a near-stoichiometric environment. The waveguide well supports both the TE and TM modes, shows weak polarization dependence, is in single mode at the 1.5 μm wavelength, and has a loss of ≤0.6/0.8 dB/cm for the TE/TM modes. A secondary ion mass spectrometry analysis shows that the Zr(4+)-profile part with a concentration above the threshold of photorefractive damage entirely covers the waveguide, implying that the waveguide would be optical-damage resistant.

  13. Current-voltage characteristics and grain growth of Li{sub 2}CO{sub 3}-doped tungsten trioxide ceramics

    SciTech Connect

    Wang, Y.; Yang, X.S.; Li, Z.Q.; Yao, K.L.; Liu, Z.L

    2004-08-03

    Ceramics samples of tungsten trioxide doped with lithium carbonate from 0.5 to 5 mol% were prepared by conventional electroceramic technique. The current-voltage characteristics of these ceramics were measured under various ambient temperatures. All of the I-V curves showed non-ohmic electrical properties with obvious negative-resistance characteristic at room temperature. It is found that there exists a direct correlation between the negative-resistance phenomenon in the I-V curves and the electrical history of these samples. The suitability of some models regarding the negative-resistance characteristics is discussed. X-ray diffraction (XRD) revealed coexistence of two phases of tungsten trioxide, which depends on the amount of lithium. Scanning electron microscope (SEM) showed great differences for both grain shape and size between the Li-doped and undoped WO{sub 3} ceramics, and this indicates that Li{sub 2}CO{sub 3} doped into WO{sub 3} influences strongly the growing of WO{sub 3} during sintering process.

  14. FTIR and Raman Study of the LixTiyMn1-yO2 (y = 0, 0.11) Cathodes in Methylpropyl Pyrrolidinium Bis(fluoro-sulfonyl)imide, LiTFSI Electrolyte

    SciTech Connect

    Hardwick, L.J.; Lucas, I.T.; Doeff, M.M.; Kostecki, R.; Saint, J.A.

    2009-02-02

    This work demonstrates the protective effect of partial titanium substitution in Li{sub x}Ti{sub 0.11}Mn{sub 0.89}O{sub 2} against surface decomposition in room-temperature ionic liquid (RTILs) cells. Raman microscopy and reflectance Fourier transform IR (FTIR) spectroscopy were used to analyze electrodes recovered from cycled Li/Li{sub x}Ti{sub y}Mn{sub 1-y}O{sub 2} (y=0, 0.11) cells containing the 0.5 mol/kg LiTFSI in P{sub 13}FSI RTIL electrolyte. [TFSI=bis(trifluoromethanesulfonyl)imide.] Raman and FTIR spectra of cycled Li{sub x}MnO{sub 2} cathodes showed many distinct bands that can be attributed to both the electrolyte and electrode decomposition products. The thickness of the amorphous porous layer on the Li{sub x}MnO{sub 2} cathode increased during cycling. The surface degradation of Li{sub x}MnO{sub 2} and precipitation of electrolyte decomposition products contributed to the film growth. Improved cycling behavior was observed in cells containing Li{sub x}Ti{sub 0.11}Mn{sub 0.89}O{sub 2}, yet Raman spectroscopy also showed possible surface degradation. The FTIR spectra of cycled Li{sub x}MnO{sub 2} and Li{sub x}Ti{sub 0.11}Mn{sub 0.89}O{sub 2} cathodes displayed bands characteristic for LiSO{sub 3}CF{sub 3} and Li{sub 2}NSO{sub 2}CF{sub 3}, which originate from the reaction of the TFSI anion with traces of water present in the cell.

  15. The effect of electrolyte additives on both LaPO4-coated Li(Ni0.4Mn0.4Co0.2)O2 and uncoated Li(Ni0.4Mn0.4Co0.2)O2 in Li-ion pouch cells

    NASA Astrophysics Data System (ADS)

    Xia, Jian; Lu, Z.; Camardese, J.; Dahn, J. R.

    2016-02-01

    The effectiveness of some selected electrolyte additive blends were systematically studied in Li[Ni0.4Mn0.4Co0.2]O2/graphite and 3 wt% LaPO4-coated Li[Ni0.4Mn0.4Co0.2]O2/graphite pouch cells using ex-situ gas measurements, ultra high precision coulometry, automated storage experiments, long-term cycling and electrochemical impedance spectroscopy. For cells tested to an upper cutoff potential of 4.4 V the LaPO4-coating provided no benefit when state-of-the-art electrolyte additives were used. For cells tested to 4.5 V, the LaPO4 coating appeared to limit electrolyte oxidation slightly and resulted in better capacity retention compared to uncoated cells for cells with state-of-the-art electrolyte additives. However, even for cells tested to 4.5 V, the benefits of the additives far outweighed the benefits of the coating. This suggests literature papers that compare the impact of coatings on positive electrode materials in cells that contain electrolytes without electrolyte additives have limited value.

  16. NMR T{sub 1} relaxation time measurements and calculations with translational and rotational components for liquid electrolytes containing LiBF{sub 4} and propylene carbonate

    SciTech Connect

    Richardson, P. M. Voice, A. M. Ward, I. M.

    2013-12-07

    Longitudinal relaxation (T{sub 1}) measurements of {sup 19}F, {sup 7}Li, and {sup 1}H in propylene carbonate/LiBF{sub 4} liquid electrolytes are reported. Comparison of T{sub 1} values with those for the transverse relaxation time (T{sub 2}) confirm that the measurements are in the high temperature (low correlation time) limit of the T{sub 1} minimum. Using data from pulsed field gradient measurements of self-diffusion coefficients and measurements of solution viscosity measured elsewhere, it is concluded that although in general there are contributions to T{sub 1} from both translational and rotational motions. For the lithium ions, this is mainly translational, and for the fluorine ions mainly rotational.

  17. 3, 3‧-sulfonyldipropionitrile: A novel electrolyte additive that can augment the high-voltage performance of LiNi1/3Co1/3Mn1/3O2/graphite batteries

    NASA Astrophysics Data System (ADS)

    Zheng, Xiangzhen; Huang, Tao; Pan, Ying; Wang, Wenguo; Fang, Guihuang; Ding, Kaining; Wu, Maoxiang

    2016-07-01

    Our study shows that 3, 3‧-sulfonyldipropionitrile (SDPN), as an electrolyte additive, can dramatically enhance the performance of LiNi1/3Co1/3Mn1/3O2/graphite lithium-ion batteries (LIBs) at high voltages (3.0-4.6 V vs. Li/Li+). After adding 0.2 wt% SDPN to the electrolytes; i.-e., 1.0 M LiPF6-EC/DMC/EMC, the capacity for the LiNi1/3Co1/3Mn1/3O2/graphite cell to retain power was significantly increased from 59.5% to 77.3% after only 100 cycles, which shows the promising application of SDPN at higher voltages. Density functional theory calculation results indicate that SDPN had reduced oxidative constancy compared to ethylene carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC). The effects of SDPN on cell performance are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). The testing results indicate that the improvement in cycling activity could be ascribed to the thinner cathode electrolyte interface film originated from SDPN on the LIB using LiNi1/3Co1/3Mn1/3O2, which reduced the interfacial resistance at a high voltage, but also protected the decomposition of electrolytes and suppressed transition metal dissolution.

  18. Polar clusters in impurity-doped quantum paraelectric K{sub 1-x}Li{sub x}TaO{sub 3}

    SciTech Connect

    Geneste, Gregory; Kiat, Jean-Michel; Yokota, Hiroko; Uesu, Yoshiaki; Porcher, Florence

    2010-04-01

    From density-functional calculations, we show that large off-center motions (approx =1.0 A) of Li impurities in the KTaO{sub 3} matrix (studied at 3.7% concentration) create very anisotropic polar clusters oriented along the Li off-center dipole. The polarization induced by Li in the matrix decreases very sharply in the lateral directions so that polar clusters are only approx = two lattice constants thick (one-dimensional or needlelike clusters). The polarization in such polar regions is mainly constituted by the displacements in the (highly polarizable) matrix rather than by the impurity itself. These results suggest that Li-doped potassium tantalate (3.7% concentration) is not ferroelectric at low temperature and rather behaves as a relaxor. These small polar zones around Li correlate at T{sub B} to form larger polar nanoregions, in which the matrix remains however nonpolar. This is confirmed by a low temperature neutron-diffraction analysis showing that the KTaO{sub 3} matrix remains paraelectric. Li-doped KTaO{sub 3} is an order-disorder system with a very deep local potential felt by the Li impurities (approx =-200 meV). The energy barrier for Li hopping is estimated at 80-90 meV. An analytic expression for this local potential is provided, as well as a simple model describing the energetics of K{sub 1-x}Li{sub x}TaO{sub 3}.

  19. Achieving high capacity in bulk-type solid-state lithium ion battery based on Li6.75La3Zr1.75Ta0.25O12 electrolyte: Interfacial resistance

    NASA Astrophysics Data System (ADS)

    Liu, Ting; Ren, Yaoyu; Shen, Yang; Zhao, Shi-Xi; Lin, Yuanhua; Nan, Ce-Wen

    2016-08-01

    A bulk-type all-solid-state lithium ion battery based on Ta-doped Li6.75La3Zr1.75Ta0.25O12 (LLZ-Ta) is prepared by a simple solid state process with high capacity of 279.0 μAh cm-2 at 80 °C. However, severe polarization is discovered during charging/discharging cycles at room temperature (RT) for battery with a higher active cathode loading. Large interfacial resistance due to the poor contact at the interfaces between cathode and LLZ-Ta solid electrolyte and at the interfaces within the composite cathode layer is proven to be the main reason for the poor electrochemical performance of the battery at RT. The polarization could be suppressed at elevated temperature, which is attributed to the decreased interfacial resistance as indicated by the results of impedance measurements and gives rise to much enhanced performance of the all-solid-state battery.

  20. Achieving high capacity in bulk-type solid-state lithium ion battery based on Li6.75La3Zr1.75Ta0.25O12 electrolyte: Interfacial resistance

    NASA Astrophysics Data System (ADS)

    Liu, Ting; Ren, Yaoyu; Shen, Yang; Zhao, Shi-Xi; Lin, Yuanhua; Nan, Ce-Wen

    2016-08-01

    A bulk-type all-solid-state lithium ion battery based on Ta-doped Li6.75La3Zr1.75Ta0.25O12 (LLZ-Ta) is prepared by a simple solid state process with high capacity of 279.0 μAh cm-2 at 80 °C. However, severe polarization is discovered during charging/discharging cycles at room temperature (RT) for battery with a higher active cathode loading. Large interfacial resistance due to the poor contact at the interfaces between cathode and LLZ-Ta solid electrolyte and at the interfaces within the composite cathode layer is proven to be the main reason for the poor electrochemical performance of the battery at RT. The polarization could be suppressed at elevated temperature, which is attributed to the decreased interfacial resistance as indicated by the results of impedance measurements and gives rise to much enhanced performance of the all-solid-state battery.