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Sample records for olivines limnpo4 lifepo4

  1. Formation and diffusion of vacancy-polaron complex in olivine-type LiMnPO4 and LiFePO4

    NASA Astrophysics Data System (ADS)

    Asari, Yusuke; Suwa, Yuji; Hamada, Tomoyuki

    2011-10-01

    Formation and diffusion of a vacancy-polaron complex in olivine-type cathode-active materials, namely, LiMPO4 (M = Fe, Mn), were theoretically investigated by using the first-principles density functional theory within a framework of GGA + U method. It is shown that a lithium vacancy and a corresponding hole-polaron form the complex at the fully lithiated limit owing to lattice distortion and Coulomb interaction between them. It is also shown that the formation energy of the complex in LiMnPO4 is 0.19 eV higher than that in LiFePO4, since a hole polaron in LiMnPO4 is not sufficiently relaxed. As a result, the nucleation rate of MnPO4 phase in LiMnPO4 is 10-3 times slower than that in LiFePO4 and represents the main difference between the kinetics in the initial stage of charging of the two olivine materials. It was also found that the activation energy of the complex diffusion is limited by vacancy hopping in LiMnPO4, while it is determined by both vacancy hopping and polaron hopping in LiFePO4. The activation energy in LiMnPO4, 0.38 eV, is comparable with that in LiFePO4, 0.42 eV. The calculated potential energy profile, showed that the minimum energy path of the diffusing lithium in LiMnPO4 has the same winding shape as that in LiFePO4.

  2. Dynamic solubility limits in nanosized olivine LiFePO4.

    PubMed

    Wagemaker, Marnix; Singh, Deepak P; Borghols, Wouter J H; Lafont, Ugo; Haverkate, Lucas; Peterson, Vanessa K; Mulder, Fokko M

    2011-07-01

    Because of its stability, nanosized olivine LiFePO(4) opens the door toward high-power Li-ion battery technology for large-scale applications as required for plug-in hybrid vehicles. Here, we reveal that the thermodynamics of first-order phase transitions in nanoinsertion materials is distinctly different from bulk materials as demonstrated by the decreasing miscibility gap that appears to be strongly dependent on the overall composition in LiFePO(4). In contrast to our common thermodynamic knowledge, that dictates solubility limits to be independent of the overall composition, combined neutron and X-ray diffraction reveals strongly varying solubility limits below particle sizes of 35 nm. A rationale is found based on modeling of the diffuse interface. Size confinement of the lithium concentration gradient, which exists at the phase boundary, competes with the in bulk energetically favorable compositions. Consequently, temperature and size diagrams of nanomaterials require complete reconsideration, being strongly dependent on the overall composition. This is vital knowledge for the future nanoarchitecturing of superior energy storage devices as the performance will heavily depend on the disclosed nanoionic properties. PMID:21598941

  3. Advanced carbon materials/olivine LiFePO4 composites cathode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Gong, Chunli; Xue, Zhigang; Wen, Sheng; Ye, Yunsheng; Xie, Xiaolin

    2016-06-01

    In the past two decades, LiFePO4 has undoubtly become a competitive candidate for the cathode material of the next-generation LIBs due to its abundant resources, low toxicity and excellent thermal stability, etc. However, the poor electronic conductivity as well as low lithium ion diffusion rate are the two major drawbacks for the commercial applications of LiFePO4 especially in the power energy field. The introduction of highly graphitized advanced carbon materials, which also possess high electronic conductivity, superior specific surface area and excellent structural stability, into LiFePO4 offers a better way to resolve the issue of limited rate performance caused by the two obstacles when compared with traditional carbon materials. In this review, we focus on advanced carbon materials such as one-dimensional (1D) carbon (carbon nanotubes and carbon fibers), two-dimensional (2D) carbon (graphene, graphene oxide and reduced graphene oxide) and three-dimensional (3D) carbon (carbon nanotubes array and 3D graphene skeleton), modified LiFePO4 for high power lithium ion batteries. The preparation strategies, structure, and electrochemical performance of advanced carbon/LiFePO4 composite are summarized and discussed in detail. The problems encountered in its application and the future development of this composite are also discussed.

  4. Coupling of Li motion and structural distortions in olivine LiMnPO4 from 7Li and 31P NMR

    NASA Astrophysics Data System (ADS)

    Rudisch, Christian; Grafe, Hans-Joachim; Geck, Jochen; Partzsch, Sven; Zimmermann, M. v.; Wizent, Nadja; Klingeler, Rüdiger; Büchner, Bernd

    2013-08-01

    We present a detailed 7Li- and 31P-NMR study on single crystalline LiMnPO4 in the paramagnetic and antiferromagnetic phase (AFM, TN˜34 K). This allows us to determine the spin directions in the field-induced spin-flop phase. In addition, the anisotropic dipolar hyperfine coupling tensor of the 7Li and 31P nuclei is also fully determined by orientation and temperature-dependent NMR experiments and compared to the calculated values from crystal structure data. Deviations of the experimental values from the theoretical ones are discussed in terms of Mn disorder which is induced by Li disorder. In fact, the disorder in the Mn sublattice is directly revealed by diffuse x-ray scattering data. The present results provide experimental evidence for the Li diffusion strongly coupling to structural distortions within the MnPO4 host, which is expected to significantly affect the Li mobility as well as the performance of batteries based on this material.

  5. What Happens to LiMnPO4 upon Chemical Delithiation?

    PubMed

    Huang, Yiqing; Chernova, Natasha A; Yin, Qiyue; Wang, Qi; Quackenbush, Nicholas F; Leskes, Michal; Fang, Jin; Omenya, Fredrick; Zhang, Ruibo; Wahila, Matthew J; Piper, Louis F J; Zhou, Guangwen; Grey, Clare P; Whittingham, M Stanley

    2016-05-01

    Olivine MnPO4 is the delithiated phase of the lithium-ion-battery cathode (positive electrode) material LiMnPO4, which is formed at the end of charge. This phase is metastable under ambient conditions and can only be produced by delithiation of LiMnPO4. We have revealed the manganese dissolution phenomenon during chemical delithiation of LiMnPO4, which causes amorphization of olivine MnPO4. The properties of crystalline MnPO4 obtained from carbon-coated LiMnPO4 and of the amorphous product resulting from delithiation of pure LiMnPO4 were studied and compared. The phosphorus-rich amorphous phases in the latter are considered to be MnHP2O7 and MnH2P2O7 from NMR, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy analysis. The thermal stability of MnPO4 is significantly higher under high vacuum than at ambient condition, which is shown to be related to surface water removal. PMID:27065434

  6. Enhanced thermal safety and high power performance of carbon-coated LiFePO4 olivine cathode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zaghib, K.; Dubé, J.; Dallaire, A.; Galoustov, K.; Guerfi, A.; Ramanathan, M.; Benmayza, A.; Prakash, J.; Mauger, A.; Julien, C. M.

    2012-12-01

    The carbon-coated LiFePO4 Li-ion oxide cathode was studied for its electrochemical, thermal, and safety performance. This electrode exhibited a reversible capacity corresponding to more than 89% of the theoretical capacity when cycled between 2.5 and 4.0 V. Cylindrical 18,650 cells with carbon-coated LiFePO4 also showed good capacity retention at higher discharge rates up to 5C rate with 99.3% coulombic efficiency, implying that the carbon coating improves the electronic conductivity. Hybrid Pulse Power Characterization (HPPC) test performed on LiFePO4 18,650 cell indicated the suitability of this carbon-coated LiFePO4 for high power HEV applications. The heat generation during charge and discharge at 0.5C rate, studied using an Isothermal Microcalorimeter (IMC), indicated cell temperature is maintained in near ambient conditions in the absence of external cooling. Thermal studies were also investigated by Differential Scanning Calorimeter (DSC) and Accelerating Rate Calorimeter (ARC), which showed that LiFePO4 is safer, upon thermal and electrochemical abuse, than the commonly used lithium metal oxide cathodes with layered and spinel structures. Safety tests, such as nail penetration and crush test, were performed on LiFePO4 and LiCoO2 cathode based cells, to investigate on the safety hazards of the cells upon severe physical abuse and damage.

  7. Cycling stability and degradation mechanism of LiMnPO4 based electrodes

    NASA Astrophysics Data System (ADS)

    Moskon, J.; Pivko, M.; Jerman, I.; Tchernychova, E.; Logar, N. Zabukovec; Zorko, M.; Selih, V. S.; Dominko, R.; Gaberscek, M.

    2016-01-01

    Long term stability of LiMnPO4 particles with a crystallite size between ˜20 and 50 nm covered with a dense native carbon coating (14 wt.%) is demonstrated. More than 500 cycles at a rate of C/20, in the potential window of 2.7-4.5 V and a temperature of 55 °C were achieved. During most of the cycling the average capacity decay was less than 0.06% per cycle. After about 500 cycles a sudden capacity drop was observed. Degradation processes in various stages of cycling were thoroughly examined using a range of techniques. Severe surface film formation, manganese dissolution and degradation of LixMnPO4 accompanied by formation of Li4P2O7 were clearly identified. The good long term stability seems to be due to dense, protective carbon coating. Decomposition is most likely initiated at local defects in the microstructure of pyrolytic carbon coating around LiMnPO4 particles. In addition to known degradation mechanisms of LiMnPO4 we observed pronounced gradual amorphization of the olivine crystallites during long-term cycling at 55 °C. Finally, changes in morphology of the carbon black additive after prolonged cycling are reported and commented.

  8. Structural and Electrochemical Characterization of Pure LiFePO 4 and Nanocomposite C- LiFePO 4 Cathodes for Lithium Ion Rechargeable Batteries

    DOE PAGESBeta

    Kumar, Arun; Thomas, R.; Karan, N. K.; Saavedra-Arias, J. J.; Singh, M. K.; Majumder, S. B.; Tomar, M. S.; Katiyar, R. S.

    2009-01-01

    Pure limore » thium iron phosphate ( LiFePO 4 ) and carbon-coated LiFePO 4 (C- LiFePO 4 ) cathode materials were synthesized for Li-ion batteries. Structural and electrochemical properties of these materials were compared. X-ray diffraction revealed orthorhombic olivine structure. Micro-Raman scattering analysis indicates amorphous carbon, and TEM micrographs show carbon coating on LiFePO 4 particles. Ex situ Raman spectrum of C- LiFePO 4 at various stages of charging and discharging showed reversibility upon electrochemical cycling. The cyclic voltammograms of LiFePO 4 and C- LiFePO 4 showed only a pair of peaks corresponding to the anodic and cathodic reactions. The first discharge capacities were 63, 43, and 13 mAh/g for C/5, C/3, and C/2, respectively for LiFePO 4 where as in case of C- LiFePO 4 that were 163, 144, 118, and 70 mAh/g for C/5, C/3, C/2, and 1C, respectively. The capacity retention of pure LiFePO 4 was 69% after 25 cycles where as that of C- LiFePO 4 was around 97% after 50 cycles. These results indicate that the capacity and the rate capability improved significantly upon carbon coating.« less

  9. Ultralong Lifespan and Ultrafast Li Storage: Single-Crystal LiFePO4 Nanomeshes.

    PubMed

    Zhang, Yan; Zhang, Hui Juan; Feng, Yang Yang; Fang, Ling; Wang, Yu

    2016-01-27

    A novel LiFePO4 material, in the shape of a nanomesh, has been rationally designed and synthesized based on the low crystal-mismatch strategy. The LiFePO4 nanomesh possesses several advantages in morphology and crystal structure, including a mesoporous structure, its crystal orientation that is along the [010] direction, and a shortened Li-ion diffusion path. These properties are favorable for their application as cathode in Li-ion batteries, as these will accelerate the Li-ion diffusion rate, improve the Li-ion exchange between the LiFePO4 nanomesh and the electrolyte, and reduce the Li-ion capacitive behavior during Li intercalation. So the LiFePO4 nanomesh exhibits a high specific capacity, enhanced rate capability, and strengthened cyclability. The method developed here can also be extended to other similar systems, for instance, LiMnPO4 , LiCoPO4 , and LiNiPO4 , and may find more applications in the designed synthesis of functional materials. PMID:26643716

  10. Cathode performance of LiMnPO 4/C nanocomposites prepared by a combination of spray pyrolysis and wet ball-milling followed by heat treatment

    NASA Astrophysics Data System (ADS)

    Doan, The Nam Long; Taniguchi, Izumi

    LiMnPO 4/C nanocomposites could be prepared by a combination of spray pyrolysis and wet ball-milling followed by heat treatment in the range of spray pyrolysis temperature from 200 to 500 °C. The ordered LiMnPO 4 olivine structure without any impurity phase could be identified by X-ray diffraction analysis for all samples. It could be also confirmed from scanning electron microscopy and transmission electron microscopy observations that the final samples were the LiMnPO 4/C nanocomposites with approximately 100 nm in primary particles size. The LiMnPO 4/C nanocomposite samples were used as cathode active materials for lithium batteries, and the electrochemical tests were carried out for the cell Li|1 M LiPF 6 in EC:DMC = 1:1|LiMnPO 4/C at various charge/discharge rates in three charge modes. As a result, the final sample which was synthesized at 300 °C by spray pyrolysis showed the best electrochemical performance due to the largest specific surface area, the smallest primary particle size and a well distribution of carbon. At galvanostatic charge/discharge rates of 0.05 C, the cell delivered first discharge capacities of 123 and 165 mAh g -1 in correspondence to charge cutoff voltages of 4.4 and 5.0 V, respectively. Furthermore, in a constant current-constant voltage charge mode at 4.4 V, the cells also exhibited initial discharge capacities of 147 mAh g -1 at 0.05 C, 145 mAh g -1 at 0.1 C, 123 mAh g -1 at 1 C and 65 mAh g -1 at 10 C. Moreover, the cells showed fair good cycleability over 100 cycles.

  11. Synthesis and Electrochemical Properties of LiFePO4/C for Lithium Ion Batteries.

    PubMed

    Gao, Hong; Wang, Jiazhao; Yin, Shengyu; Zheng, Hao; Wang, Shengfu; Feng, Chuanqi; Wang, Shiquan

    2015-03-01

    LiFePO4/C was prepared through a facile rheological phase reaction method by using Fe3(PO4)2, Li3PO4 · 8H2O, and glucose as reactants. The LiFePO4/C samples were characterized by X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. The electrochemical properties of the samples were investigated. The results show that the LiFePO4/C samples have single-phase olivine-type structure, and their particles feature a spherical shape. The carbon coating on the particles of LiFePO4 is about 1.8% of the LiFePO4/C by weight. The particle size was distributed from 0.2 to 1 µm. The initial discharge capacity of LiFePO4/C reached 154 mA h/g at 0.1 C. The retained discharge capacity of LiFePO4/C was 152.9 mA h g(-1) after 50 cycles. The LiFePO4/C also showed better cycling performance than that of the bare LiPeO4 at a higher charge/discharge rate (1 C). The LIFePO4/C prepared in this way could be a promising cathode material for lithium ion battery application. PMID:26413648

  12. Optical Properties and Electrochemical Performance of LiFePO4 Thin Films Deposited on Transparent Current Collectors.

    PubMed

    Lee, HyunSeok; Yim, Haena; Kim, Kwang-Bum; Choi, Ji-Won

    2015-11-01

    LiFePO4 thin film cathodes are deposited on various transparent conducting oxide thin films on glass, which are used as cathode current collectors. The XRD patterns show that the thin films have the phase of LiFePO4 with an ordered olivine structure indexed to the orthorhombic Pmna space group. LiFePO4 thin film deposited on various TCO glass substrates exhibits transmittance of about 53%. The initial specific discharge capacities of LiFePO4 thin films are 25.0 μAh/cm2 x μm on FTO, 33.0 μAh/cm2 x μm on ITO, and 13.0 μAh/cm2 x μm on AZO coated glass substrates. Interestingly, the retention capacities of LiFePO4 thin films are 76.0% on FTO, 31.2% on ITO, and 37.7% on AZO coated glass substrates at 20th cycle. The initial specific discharge capacity of the LiFePO4/FTO electrode is slightly lower, but the discharge capacities of the LiFePO4/FTO electrode relatively decrease less than those of the others such as LiFePO4/ITO and LiFePO4/AZO with cycling. The results reported here provide the high transparency of LiFePO4 thin films cathode materials and the good candidate as FTO current collector of the LiFePO4 thin film cathode of transparent thin film rechargeable batteries due to its high transparency and cyclic retention. PMID:26726564

  13. First-Principles Investigation of Li Intercalation Kinetics in Phospho-Olivines

    NASA Astrophysics Data System (ADS)

    Malik, Rahul

    This thesis focuses broadly on characterizing and understanding the Li intercalation mechanism in phospho-olivines, namely LiFePO 4 and Li(Fe,Mn)PO4, using first-principles calculations. Currently Li-ion battery technology is critically relied upon for the operation of electrified vehicles, but further improvements mainly in cathode performance are required to ensure widespread adoption, which in itself requires learning from existing commercial cathode chemistries. LiFePO4 is presently used in commercial Li-ion batteries, known for its rapid charge and discharge capability but with underwhelming energy density. This motivates the three central research efforts presented herein. First, we investigate the modified phase diagram and electrochemical properties of mixed olivines, such as Li(Fe,Mn)PO4, which offer improved theoretical energy density over LiFePO4 (due to the higher redox voltage associated with Mn2+/Mn3+). The Lix(Fe1-yMny)PO4 phase diagram is constructed by Monte Carlo simulation on a cluster expansion Hamiltonian parametrized by first-principles determined energies. Deviations from the equilibrium phase behavior and voltages of pure LiFePO4 and LiMnPO 4 are analyzed and discussed to good agreement with experimental observations. Second, we address why LiFePO4 exhibits superior rate performance strictly when the active particle size is brought down to the nano-scale. By considering the presence of immobile point defects residing in the 1D Li diffusion path, specifically by calculating from first principles both defect formation energies and Li migration barriers in the vicinity of likely defects, the Li diffusivity is recalculated and is found to strongly vary with particle size. At small particle sizes, the contribution from defects is small, and fast 1D Li diffusion is accessible. However, at larger particle sizes (microm scale and above) the contribution from defects is much larger. Not only is Li transport impeded, but it is also less anisotropic in

  14. Microwave synthesis of molybdenum doped LiFePO4/C and its electrochemical studies.

    PubMed

    Naik, Amol; P, Sajan C

    2016-05-10

    A Mo-doped LiFePO4 composite was prepared successfully from an iron carbonyl complex by adopting a facile and rapid microwave assisted solid state method. The evolution of gases from the iron precursor produces a highly porous product. The formation and substitution of Mo in LiFePO4 were confirmed by X-ray diffraction; surface analysis was carried out by scanning electron microscopy, field emission scanning electron microscopy, and transmission electron microscopy. The electrochemical properties of the substituted LiFePO4 were examined by cyclic voltammetry, electrochemical impedance spectroscopy and by recording charge-discharge cycles. It was observed that the as prepared composites consisted of a single phase orthorhombic olivine-type structure, where Mo(6+) was successfully introduced into the M2(Fe) sites. Incorporation of supervalent Mo(6+) introduced Li(+) ion vacancies in LiFePO4. The synthesized material facilitated lithium ion diffusion during charging/discharging due to the charge compensation effect and porosity. The battery performance studies showed that LiMo0.05Fe0.095PO4 exhibited a maximum capacity of 169.7 mA h g(-1) at 0.1 C current density, with admirable stability retention. Even at higher current densities, the retention of the specific capacity was exceptional. PMID:27071463

  15. Diffusion and possible freezing phases of Li-ions in LiFePO4

    NASA Astrophysics Data System (ADS)

    Yiu, Yuen; Toft-Petersen, Rasmus; Ehlers, Georg; Vaknin, David

    Elastic and inelastic neutron scattering studies of LiFePO4 single crystal reveal new Li-ion diffusion properties relevant to its function as Li-battery materials. In the past decade there has been broad interest in LiFePO4 and its related compounds, largely due to the applications of these materials as cathodes in Li- batteries. This is owing to these materials' high charge-discharge ability and conductivity, both of which are by virtue of the Li-ions' high mobility. In this talk, we present our findings on the temperature and directional dependence of Li-ions' diffusion in LiFePO4. LiFePO4 adopts the olivine structure at room temperature (Space group: Pnma), which contains channels along principal crystalline directions that allow Li-ion motion. Elastic neutron scattering reveals lowering of symmetry from the Pnma structure below room temperature, which can be interpreted as the freezing of Li-ions, and can be subsequently linked to the reported decrease in Li-ion conductivity. Inelastic neutron scattering, in the 35K to 720K temperature range, shows temperature dependence, as well as anisotropy (i.e. along 0K0 versus 00L) of Li-ion diffusion. Ames Laboratory is supported by U.S. DOE, BES, DMSE, under Contract #DE-AC02-07CH11358. Spallation Neutron Source of Oak Ridge National Laboratory is sponsored by U.S. DOE, BES, SUFD.

  16. Synthesis of a LiFePO4/C cathode material by using a high-energy nano mill

    NASA Astrophysics Data System (ADS)

    Islam, Mobinul; Yoon, Man-Soon; Ur, Soon-Chul

    2015-07-01

    Olivine lithium iron phosphate (LiFePO4) is a promising cathode material for Li-ion battery. A temperature around 700 - 800 ℃ is generally required to prepare LiFePO4 powder with good crystallinity. The LiFePO4 materials are synthesized via a solid-state method by using a highenergy nano mill (HENM). The conventional ball-milling process is also conducted for the same material for a comparative study. The effect of the precursor's mixing processes on the synthesis temperature of LiFePO4 is investigated in this study. The required reaction temperature of LiFePO4 is 432 ℃ for the HENM process and 480 ℃ for the ball-mill process as found from the differential scanning calorimetry (DSC) results. The HENM process improves the reaction activity and the homogeneity of the materials used throughout process and lowers the reaction temperature as compared with the conventional ball-mill process. The milled powders are characterized by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The sample synthesized by using the HENM process exhibits a discharge capacity of 136 mAhg -1 at 0.1 C rate. The results in this study indicate that the HENM process is a substantial and promising process for LiFePO4 cathode preparation owing to its short fabrication time and ability to improve the reaction condition. A HENM can be used to promote formation of LiFePO4 at lower temperatures.

  17. Rapid Polyol-Assisted Microwave Synthesis of Nanocrystalline LiFePO4/C Cathode for Lithium-Ion Batteries.

    PubMed

    Paul, Baboo Joseph; Gim, Jihyeon; Baek, Sora; Kang, Jungwon; Song, Jinju; Kim, Sungjin; Kim, Jaekook

    2015-08-01

    Nanocrystalline LiFePO4/C has been synthesized under a very short period of time (90 sec) using a polyol-assisted microwave heating synthesis technique. The X-ray diffraction (XRD) data indicates that the rapidly synthesized materials correspond to phase pure olivine. Post-annealing of the as-prepared sample at 600 °C in argon atmosphere yields highly crystalline LiFePO4/C. The morphology of the samples studied using scanning electron microscopy (SEM) reveals the presence of secondary particles formed from aggregation of primary particles in the range of 30-50 nm. Transmission electron microscopy (TEM) images reveal a thin carbon layer coating on the surface of the primary particle. The charge/discharge studies indicate that the as-prepared and annealed LiFePO4/C samples delivered initial discharge capacities of 126 and 160 mA h g-1, respectively, with good capacity retentions at 0.05 mA cm-2 current densities. The post-annealing process indeed improves the crystallinity of the LiFePO4 nanocrystals, which enhances the electrode performance of LiFePO4/C. PMID:26369219

  18. 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.

  19. Effects of Ag-embedment on electronic and ionic conductivities of LiMnPO4 and its performance as a cathode for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lee, Kug-Seung; Lee, Kyung Jae; Kang, Yun Sik; Shin, Tae Joo; Sung, Yung-Eun; Ahn, Docheon

    2015-08-01

    An Ag-embedded LiMnPO4 (LMP) cathode was synthesized by solid-state reaction using a 1 wt% Ag precursor. Structure, morphology, and electrical conductivity studies of Ag-embedded LMP were performed by high resolution powder X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and four probe measurements. An Ag nanoparticle (~26 nm) surrounded by several olivine crystallites within a single particle dramatically improved the overall electrical conductivity of LMP by four orders of magnitude relative to that of pristine LMP, playing roles as conducting bridges among LMP crystallites as well as particles. Rietveld analysis confirmed structural variations related to the modification of atomic bond lengths of Mn-O, P-O, and Li-O coordination due to Ag-embedment and thereby leads to facile Li ion diffusion in LMP. Consequently, although a small amount of Ag was included, the Ag-embedded LMP cathode exhibited outstanding electrochemical performances (92 mA h g-1 at 10 C) versus lithium.An Ag-embedded LiMnPO4 (LMP) cathode was synthesized by solid-state reaction using a 1 wt% Ag precursor. Structure, morphology, and electrical conductivity studies of Ag-embedded LMP were performed by high resolution powder X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and four probe measurements. An Ag nanoparticle (~26 nm) surrounded by several olivine crystallites within a single particle dramatically improved the overall electrical conductivity of LMP by four orders of magnitude relative to that of pristine LMP, playing roles as conducting bridges among LMP crystallites as well as particles. Rietveld analysis confirmed structural variations related to the modification of atomic bond lengths of Mn-O, P-O, and Li-O coordination due to Ag-embedment and thereby leads to facile Li ion diffusion in LMP. Consequently, although a small amount of Ag was included, the Ag-embedded LMP

  20. Analysis of optimization processses for solid state fabrication of olivine cathode materials

    NASA Astrophysics Data System (ADS)

    Oladimeji, Charles

    Lithium ion battery discovered since the 1980s has become pivotal to our energy needs. With the need for a shift to renewable energy and increased use of portable devices, energy storage has become a very important aspect of modern day life and technology. In the thesis, optimization techniques for solid state calcination of lithium olivine batteries are characterized and analyzed. A brief introduction into lithium ion battery is discussed, the chemistry and physics of the materials is studied in details. Emphasis is placed on the olivine structure, industrially utilized synthesis method and the performance of olivine lithium ion batteries are also discussed in details. Olivine structure LiFePO4 (LFP) was synthesized via solid state processes, using Li2CO3, NH4H 2PO4 and FeC2O4˙H2O and C12H22O11 as precursor materials. The effects of calendaring in terms of charge/discharge capacity, cycle life performance, surface morphology, and ac impedance was analyzed. The resulting LFP electrode was divided in part, Part A was left as is and Part B was calendared. The calendared electrode exhibited lower impedance under electrochemical impedance test. The calendared electrode also exhibited a higher discharge capacity of about 130 mAh/g at 0.1C compared to the as-is electrode with discharge capacity of about 120mAh/g. Olivine structure LiMnPO4 (LMP) was also synthesized via solid state processes, using Li2CO3, NH4H 2PO4, MnCO3 and C12H22O 11 as precursor materials. Comparison of the carbon addition process was done by adding sucrose to the initial precursor mix and carbon black at the later stages of fabrication. The 3 step carbon addition exhibited the highest specific capacity of about 72mAh/g, 1 step carbon addition possessed the least capacity of about 45mAh/g, while the 2 step process had a capacity of about 65mA/g.

  1. LiMnPO4 Nanoplate Grown via Solid-State Reaction in Molten Hydrocarbon for Li-ion Battery Cathode

    SciTech Connect

    Choi, Daiwon; Wang, Donghai; Bae, In-Tae; Xiao, Jie; Nie, Zimin; Wang, Wei; Viswanathan, Vilayanur V.; Lee, Yun Jung; Zhang, Jiguang; Graff, Gordon L.; Yang, Zhenguo; Liu, Jun

    2010-08-11

    Electrochemically active LiMnPO4 nanoplates have been synthesized via novel single step solid state reaction in molten hydrocarbon. The LiMnPO4 prepared show unique porous nanoplate shape ~50nm in thickness with highly preferred crystallographic orientation. The reversible cycling of carbon coated LiMnPO4 show flat potential at 4.1 V vs. Li with specific capacity reaching up to 168mAh/g and excellent cycling performance using only galvanostatic charging / discharging mode.

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

    PubMed

    Wu, Jiaxiong; Cai, Wei; Shang, Guangyi

    2016-12-01

    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. PMID:27117633

  3. A polyethylene glycol-assisted carbothermal reduction method to synthesize LiFePO4 using industrial raw materials

    NASA Astrophysics Data System (ADS)

    Fey, George Ting-Kuo; Huang, Kai-Pin; Kao, Hsien-Ming; Li, Wen-Hsien

    2011-03-01

    Olivine LiFePO4 is synthesized by a carbothermal reduction method (CTR) using industrial raw materials with polyethylene glycol (PEG) as a reductive agent and carbon source. A required amount of acetone is added to the starting materials for the ball milling process and the precursor is sintered at 973 K for 8 h to form crystalline phase LiFePO4. The structure and morphology of the LiFePO4/C composite samples have been characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, differential scanning calorimetry and magnetic susceptibility. Electrochemical measurements show that the LiFePO4/C composite cathode delivers an initial discharge capacity of 150 mAh g-1 at a 0.2C-rate between 4.0 and 2.8 V, and almost no capacity loss is observed for up to 50 cycles. Remarkably, the cell can sustain a 30C-rate between 4.6 and 2.0 V, and this rate capability is equivalent to charge or discharge in 2 min. The simple technique, low-cost starting materials, and excellent electrochemical performance make this process easier to commercialize than other synthesized methods.

  4. 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.

  5. Effects of Ag-embedment on electronic and ionic conductivities of LiMnPO4 and its performance as a cathode for lithium-ion batteries.

    PubMed

    Lee, Kug-Seung; Lee, Kyung Jae; Kang, Yun Sik; Shin, Tae Joo; Sung, Yung-Eun; Ahn, Docheon

    2015-09-01

    An Ag-embedded LiMnPO4 (LMP) cathode was synthesized by solid-state reaction using a 1 wt% Ag precursor. Structure, morphology, and electrical conductivity studies of Ag-embedded LMP were performed by high resolution powder X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and four probe measurements. An Ag nanoparticle (∼26 nm) surrounded by several olivine crystallites within a single particle dramatically improved the overall electrical conductivity of LMP by four orders of magnitude relative to that of pristine LMP, playing roles as conducting bridges among LMP crystallites as well as particles. Rietveld analysis confirmed structural variations related to the modification of atomic bond lengths of Mn-O, P-O, and Li-O coordination due to Ag-embedment and thereby leads to facile Li ion diffusion in LMP. Consequently, although a small amount of Ag was included, the Ag-embedded LMP cathode exhibited outstanding electrochemical performances (92 mA h g(-1) at 10 C) versus lithium. PMID:26186268

  6. Aqueous synthesis of LiFePO4 with Fractal Granularity

    NASA Astrophysics Data System (ADS)

    Cabán-Huertas, Zahilia; Ayyad, Omar; Dubal, Deepak P.; Gómez-Romero, Pedro

    2016-06-01

    Lithium iron phosphate (LiFePO4) electrodes with fractal granularity are reported. They were made from a starting material prepared in water by a low cost, easy and environmentally friendly hydrothermal method, thus avoiding the use of organic solvents. Our method leads to pure olivine phase, free of the impurities commonly found after other water-based syntheses. The fractal structures consisted of nanoparticles grown into larger micro-sized formations which in turn agglomerate leading to high tap density electrodes, which is beneficial for energy density. These intricate structures could be easily and effectively coated with a thin and uniform carbon layer for increased conductivity, as it is well established for simpler microstructures. Materials and electrodes were studied by means of XRD, SEM, TEM, SAED, XPS, Raman and TGA. Last but not least, lithium transport through fractal LiFePO4 electrodes was investigated based upon fractal theory. These water-made fractal electrodes lead to high-performance lithium cells (even at high rates) tested by CV and galvanostatic charge-discharge, their performance is comparable to state of the art (but less environmentally friendly) electrodes.

  7. Aqueous synthesis of LiFePO4 with Fractal Granularity.

    PubMed

    Cabán-Huertas, Zahilia; Ayyad, Omar; Dubal, Deepak P; Gómez-Romero, Pedro

    2016-01-01

    Lithium iron phosphate (LiFePO4) electrodes with fractal granularity are reported. They were made from a starting material prepared in water by a low cost, easy and environmentally friendly hydrothermal method, thus avoiding the use of organic solvents. Our method leads to pure olivine phase, free of the impurities commonly found after other water-based syntheses. The fractal structures consisted of nanoparticles grown into larger micro-sized formations which in turn agglomerate leading to high tap density electrodes, which is beneficial for energy density. These intricate structures could be easily and effectively coated with a thin and uniform carbon layer for increased conductivity, as it is well established for simpler microstructures. Materials and electrodes were studied by means of XRD, SEM, TEM, SAED, XPS, Raman and TGA. Last but not least, lithium transport through fractal LiFePO4 electrodes was investigated based upon fractal theory. These water-made fractal electrodes lead to high-performance lithium cells (even at high rates) tested by CV and galvanostatic charge-discharge, their performance is comparable to state of the art (but less environmentally friendly) electrodes. PMID:27256504

  8. Aqueous synthesis of LiFePO4 with Fractal Granularity

    PubMed Central

    Cabán-Huertas, Zahilia; Ayyad, Omar; Dubal, Deepak P.; Gómez-Romero, Pedro

    2016-01-01

    Lithium iron phosphate (LiFePO4) electrodes with fractal granularity are reported. They were made from a starting material prepared in water by a low cost, easy and environmentally friendly hydrothermal method, thus avoiding the use of organic solvents. Our method leads to pure olivine phase, free of the impurities commonly found after other water-based syntheses. The fractal structures consisted of nanoparticles grown into larger micro-sized formations which in turn agglomerate leading to high tap density electrodes, which is beneficial for energy density. These intricate structures could be easily and effectively coated with a thin and uniform carbon layer for increased conductivity, as it is well established for simpler microstructures. Materials and electrodes were studied by means of XRD, SEM, TEM, SAED, XPS, Raman and TGA. Last but not least, lithium transport through fractal LiFePO4 electrodes was investigated based upon fractal theory. These water-made fractal electrodes lead to high-performance lithium cells (even at high rates) tested by CV and galvanostatic charge-discharge, their performance is comparable to state of the art (but less environmentally friendly) electrodes. PMID:27256504

  9. Direct formation of LiFePO4/graphene composite via microwave-assisted polyol process

    NASA Astrophysics Data System (ADS)

    Lim, Jinsub; Gim, Jihyeon; Song, Jinju; Nguyen, Dang Thanh; Kim, Sungjin; Jo, Jeonggeun; Mathew, Vinod; Kim, Jaekook

    2016-02-01

    The present study reports on the direct synthesis of LiFePO4 nanoparticles and graphene nanosheets to form a composite cathode (LFP/GNs) in a one-step microwave-assisted polyol reaction. The polyol reaction induced by microwave irradiation for a few minutes produces nanocrystalline LFP and graphene nanosheets simultaneously from lithium, iron and phosphorus and carbon (5 wt% of graphite oxide) sources, respectively, used as starting precursors. Powder X-ray diffraction (XRD), electron microscopy, and atomic force microscopy (AFM) studies on microwave-reacted sample obtained using just graphite oxide confirms the formation of graphene nanosheets separately. Whereas, electron microscopy studies on the LFP/GNs composite reveals that olivine nanoparticles of average sizes ranging between 5 and 20 nm are well-dispersed on the graphene nanosheets. Electrochemical measurements reveal that the LiFePO4/GNs nanocomposite cathodes registered enhanced discharge capacities (79 and 108 mAh g-1 for the as-prepared and annealed composite cathodes, respectively) at 32 C rates with good capacity retention capabilities. The AC impedance measurements confirm that the enhanced cathode properties of the LFP/GNs nanocomposite are ascribed to the improved electronic conductivity of the graphene nanosheets and the nano-sized particles. The slightly better electrochemical properties of the annealed LFP/GNs are attributed to its higher crystallinity.

  10. Enhanced rate performance of LiFePO4/C by co-doping titanium and vanadium

    NASA Astrophysics Data System (ADS)

    Long, Yun-Fei; Su, Jing; Cui, Xiao-Ru; Lv, Xiao-Yan; Wen, Yan-Xuan

    2015-10-01

    V and Ti co-doped LiFePO4/C composites were synthesized by a wet milling assisted carbothermal reduction technology. The structure, morphology and electrochemical performance of the samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), magnetic susceptibility, positron annihilation lifetime spectra (PAS), scanning electron microscope (SEM), charge/discharge tests, electrochemical impedance spectroscopy (EIS) and cyclic voltammograms (CV). The results showed that the V and Ti co-doped samples kept the olivine structure of LiFePO4, but the synergistic effects between V3+ and Ti4+ in the lattice can increase the disorder degree of the lattice and create Li+ vacancies in LiFePO4/C, thus improve electronic conductivity and Li+ diffusion coefficient. LiV0.069Ti0.025Fe0.905PO4/C delivers an initial discharge capacity of 144.1 mAh g-1 with a capacity retention ratio of 99.4%, 96.3% and 93.6% after 100, 200 and 300 cycles at 10C, respectively. Remarkably, it still gives a high discharge capacity of 124.8 mAh g-1 even at a high rate of 20C.

  11. 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.

  12. Effect of synthesizing method on the properties of LiFePO4/C composite for rechargeable lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Yoon, Man-Soon; Islam, Mobinul; Park, Young Min; Ur, Soon-Chul

    2013-03-01

    Olivine-type LiFePO4/C cathode materials are fabricated with FePO4 powders that are pre-synthesized by two different processes from iron chloride solution. Process I is a modified precipitation method which is implemented by the pH control of a solution using NH4OH to form FePO4 precipitates at room temperature. Process II is a conventional precipitation method, of which H3PO4 (85%) solution is gradually added to a FeCl3 solution during the process to maintain a designated mole ratio. The solution is subsequently aged at 90°C in a water bath until FePO4 precipitates appear. In order to synthesize LiFePO4/C composites, each batch of FePO4 powders is then mixed with pre-milled lithium carbonate and glucose (8 wt. %) as a carbon source in a ball-mill. The structural characteristics of both LiFePO4/C composites fabricated using iron phospates from two different routes have been examined employing XRD and SEM. The modified precipitation process is considered to be a relatively simple and effective process for the preparation of LiFePO4/C composites owing to their excellent electrochemical properties and rate capabilities.

  13. Solid Solution Phases in the Olivine-Type LiMnPO4/MnPO4 System

    SciTech Connect

    Chen, Guoying; Richardson, Thomas J.

    2009-04-07

    Nonstoichiometry is reported in the LiMnPO{sub 4}/MnPO{sub 4} system for the first time. As lithium is removed from crystalline LiMnPO{sub 4} by chemical or electrochemical methods, the resulting two phase mixture consists of stoichiometric LiMnPO{sub 4} and a delithiated phase, Li{sub y}MnPO{sub 4}, whose lattice parameters depend upon the global extent of delithiation and on the crystalline domain size of the delithiated phase. This behavior is reproduced during electrochemical insertion of lithium. Again, no evidence for nonstoichiometry was found in the vicinity of LiMnPO{sub 4}. Attempts to create single phase solid solutions by heating mixtures of the two phases failed due to the thermal instability of Li{sub y}MnPO{sub 4}.

  14. Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes.

    PubMed

    Chen, Lin; Dilena, Enrico; Paolella, Andrea; Bertoni, Giovanni; Ansaldo, Alberto; Colombo, Massimo; Marras, Sergio; Scrosati, Bruno; Manna, Liberato; Monaco, Simone

    2016-02-17

    LiMnPO4 is an attractive cathode material for the next-generation high power Li-ion batteries, due to its high theoretical specific capacity (170 mA h g(-1)) and working voltage (4.1 V vs Li(+)/Li). However, two main drawbacks prevent the practical use of LiMnPO4: its low electronic conductivity and the limited lithium diffusion rate, which are responsible for the poor rate capability of the cathode. The electronic resistance is usually lowered by coating the particles with carbon, while the use of nanosize particles can alleviate the issues associated with poor ionic conductivity. It is therefore of primary importance to develop a synthetic route to LiMnPO4 nanocrystals (NCs) with controlled size and coated with a highly conductive carbon layer. We report here an effective surface etching process (using LiPF6) on colloidally synthesized LiMnPO4 NCs that makes the NCs dispersible in the aqueous glucose solution used as carbon source for the carbon coating step. Also, it is likely that the improved exposure of the NC surface to glucose facilitates the formation of a conductive carbon layer that is in intimate contact with the inorganic core, resulting in a high electronic conductivity of the electrode, as observed by us. The carbon coated etched LiMnPO4-based electrode exhibited a specific capacity of 118 mA h g(-1) at 1C, with a stable cycling performance and a capacity retention of 92% after 120 cycles at different C-rates. The delivered capacities were higher than those of electrodes based on not etched carbon coated NCs, which never exceeded 30 mA h g(-1). The rate capability here reported for the carbon coated etched LiMnPO4 nanocrystals represents an important result, taking into account that in the electrode formulation 80% wt is made of the active material and the adopted charge protocol is based on reasonable fast charge times. PMID:26799094

  15. Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes

    PubMed Central

    2016-01-01

    LiMnPO4 is an attractive cathode material for the next-generation high power Li-ion batteries, due to its high theoretical specific capacity (170 mA h g–1) and working voltage (4.1 V vs Li+/Li). However, two main drawbacks prevent the practical use of LiMnPO4: its low electronic conductivity and the limited lithium diffusion rate, which are responsible for the poor rate capability of the cathode. The electronic resistance is usually lowered by coating the particles with carbon, while the use of nanosize particles can alleviate the issues associated with poor ionic conductivity. It is therefore of primary importance to develop a synthetic route to LiMnPO4 nanocrystals (NCs) with controlled size and coated with a highly conductive carbon layer. We report here an effective surface etching process (using LiPF6) on colloidally synthesized LiMnPO4 NCs that makes the NCs dispersible in the aqueous glucose solution used as carbon source for the carbon coating step. Also, it is likely that the improved exposure of the NC surface to glucose facilitates the formation of a conductive carbon layer that is in intimate contact with the inorganic core, resulting in a high electronic conductivity of the electrode, as observed by us. The carbon coated etched LiMnPO4-based electrode exhibited a specific capacity of 118 mA h g–1 at 1C, with a stable cycling performance and a capacity retention of 92% after 120 cycles at different C-rates. The delivered capacities were higher than those of electrodes based on not etched carbon coated NCs, which never exceeded 30 mA h g–1. The rate capability here reported for the carbon coated etched LiMnPO4 nanocrystals represents an important result, taking into account that in the electrode formulation 80% wt is made of the active material and the adopted charge protocol is based on reasonable fast charge times. PMID:26799094

  16. Ultrathin carbon nanopainting of LiFePO4 by oxidative surface polymerization of dopamine

    NASA Astrophysics Data System (ADS)

    Ding, Bo; Tang, Wei Chin; Ji, Ge; Ma, Yue; Xiao, Pengfei; Lu, Li; Lee, Jim Yang

    2014-11-01

    The common strategy to address the low electronic conductivity of LiFePO4 is to downsize LiFePO4 and to coat the nanocrystal with conductive carbon film. The major issues with existing carbon coating techniques are thickness and quality control. This paper reports a facile carbon coating method which can provide ultrathin, uniform and fully encapsulating carbon coating on LiFePO4. This coating method capitalizes on the redox chemistry of surface Fe3+ on solvothermally synthesized LiFePO4 nanocrystal, to deposit uniform thin films of polydopamine films. The polymer film is easily carbonized into ultrathin carbon film. The carbon coated LiFePO4 exhibits very high rate performance (143 mAh g-1 at current density of 1700 mA g-1) with excellent capacity retention.

  17. Comparison of LiFePO4 from different sources

    SciTech Connect

    Striebel, Kathryn; Shim, Joongpyo; Srinivasan, Venkat; Newman, John

    2003-11-25

    The lithium iron phosphate chemistry is plagued by the poor conductivity and slow lithium diffusion in the solid phase. In order to alleviate these problems, various research groups have adopted different strategies including decreasing the particle sizes, increasing the carbon content, and adding dopants. In this study we obtained LiFePO4 electrodes from six different sources and used a combined model-experimental approach to compare the performance. Samples ranged from one with no carbon coating to one with 15 percent coating. In addition, particle sizes varied by as much as a order of magnitude between samples. The study detailed in this manuscript allows us to provide insight into the relative importance of the conductivity of the samples compared to the particle size, the impact of dopant on performance and ideas for making materials in order to maximize the power capability of this chemistry.

  18. Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Xu, Binghui; Liu, Tiefeng; Liu, Peng; Guo, Chenfeng; Wang, Shuo; Wang, Qiuming; Xiong, Zhigang; Wang, Dianlong; Zhao, X. S.

    2013-12-01

    In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg2+ doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg2+ doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li+ diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg2+ doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of ``cushion'' as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability.In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co

  19. Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries.

    PubMed

    Wang, Bo; Xu, Binghui; Liu, Tiefeng; Liu, Peng; Guo, Chenfeng; Wang, Shuo; Wang, Qiuming; Xiong, Zhigang; Wang, Dianlong; Zhao, X S

    2014-01-21

    In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg(2+) doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg(2+) doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li(+) diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg(2+) doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of "cushion" as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability. PMID:24287590

  20. Electrochemical performance of patterned LiFePO4 nano-electrode with a pristine amorphous layer

    NASA Astrophysics Data System (ADS)

    Wang, Mao; Zhang, Wei; Liu, Yihang; Yang, Yong; Wang, Chunsheng; Wang, Yuan

    2014-04-01

    A patterned LiFePO4 nanorod with a pristine amorphous LiFePO4 surface layer was fabricated by controlling the temperature gradient from the interior to the exterior layer in high-temperature annealing process through designing hierarchical multilayer electrode structure. The three dimensional patterned LiFePO4 nanorods were prepared using tobacco mosaic virus nanoforest arrays. The results indicate that the nano-electrodes nearly reached the theoretical capacity at a very low C rate even without conductive coatings. The amorphous LiFePO4 can fast transport the Li-ion to inside crystal LiFePO4, thus enhancing the rate capability.

  1. Rate-dependent, Li-ion insertion/deinsertion behavior of LiFePO4 cathodes in commercial 18650 LiFePO4 cells.

    PubMed

    Liu, Qi; He, Hao; Li, Zhe-Fei; Liu, Yadong; Ren, Yang; Lu, Wenquan; Lu, Jun; Stach, Eric A; Xie, Jian

    2014-03-12

    We have performed operando synchrotron high-energy X-ray diffraction (XRD) to obtain nonintrusive, real-time monitoring of the dynamic chemical and structural changes in commercial 18650 LiFePO4/C cells under realistic cycling conditions. The results indicate a nonequilibrium lithium insertion and extraction in the LiFePO4 cathode, with neither the LiFePO4 phase nor the FePO4 phase maintaining a static composition during lithium insertion/extraction. On the basis of our observations, we propose that the LiFePO4 cathode simultaneously experiences both a two-phase reaction mechanism and a dual-phase solid-solution reaction mechanism over the entire range of the flat voltage plateau, with this dual-phase solid-solution behavior being strongly dependent on charge/discharge rates. The proposed dual-phase solid-solution mechanism may explain the remarkable rate capability of LiFePO4 in commercial cells. PMID:24521163

  2. Structure and performance of LiFePO4 cathode materials: A review

    NASA Astrophysics Data System (ADS)

    Zhang, Wei-Jun

    2011-03-01

    LiFePO4 has been considered a promising battery material in electric vehicles. However, there are still a number of technical challenges to overcome before its wide-spread applications. In this article, the structure and electrochemical performance of LiFePO4 are reviewed in light of the major technical requirements for EV batteries. The rate capability, capacity density, cyclic life and low-temperature performance of various LiFePO4 materials are described. The major factors affecting these properties are discussed, which include particle size, doping, carbon coating, conductive carbon loading and synthesis techniques. Important future research for science and engineering is suggested.

  3. Effect of conductive additives in LiFePO4 cathode for lithium-ion batteries

    SciTech Connect

    Shim, J.; Guerfi, A.; Zaghib, K.; Striebel, K.A.

    2003-11-25

    The electrochemical properties of LiFePO4 cathodes with different carbon contents were studied to find out the role of carbon as conductive additive. LiFePO4 cathodes containing from 0 percent to 12 percent of conductive additive (carbon black or mixture of carbon black and graphite) were cycled at different C rates. The capacity of LiFePO4 cathode increased, as conductive additive content increased. Carbon increased the utilization of active material and the electrical conductivity of electrode, but decreased volumetric capacity of electrode.

  4. [100]-Oriented LiFePO4 Nanoflakes toward High Rate Li-Ion Battery Cathode.

    PubMed

    Li, Zhaojin; Peng, Zhenzhen; Zhang, Hui; Hu, Tao; Hu, Minmin; Zhu, Kongjun; Wang, Xiaohui

    2016-01-13

    [100] is believed to be a tough diffusion direction for Li(+) in LiFePO4, leading to the belief that the rate performance of [100]-oriented LiFePO4 is poor. Here we report the fabrication of 12 nm-thick [100]-oriented LiFePO4 nanoflakes by a simple one-pot solvothermal method. The nanoflakes exhibit unexpectedly excellent electrochemical performance, in stark contrast to what was previously believed. Such an exceptional result is attributed to a decreased thermodynamic transformation barrier height (Δμb) associated with increased active population. PMID:26694590

  5. Atomic structural and electrochemical impact of Fe substitution on nano porous LiMnPO4

    NASA Astrophysics Data System (ADS)

    Seo, Inseok; Senthilkumar, B.; Kim, Kwang-Ho; Kim, Jae-Kwang; Kim, Youngsik; Ahn, Jou-Hyeon

    2016-07-01

    The atomic structural and electrochemical properties of Fe substituted nano porous LiMn1-xFexPO4 (x = 0-0.8) composites are investigated and compared. X-ray scattering method is used for atomic structural investigation. Rietveld refinement shows that all Fe substituted composites have the same olivine structure (Pnma) with lithium occupying octahedral 4a sites, Fe2+ replacing Mn2+ at the octahedral 4c sites. The a, b, c parameters and cell volume decrease with the addition of Fe2+. When the nano porous LiMn1-xFexPO4 composites are evaluated as cathode materials in lithium cells at room temperature, x = 0.6, and 0.8 resulted in the best overall electrochemical performance, exhibiting stable cycling and high discharge capacities of 149 and 154 mA h g-1, respectively. The composites with above x = 0.4 show a fast lithium ions transfer with high electronic conductivity because Fe transition metal substitution reduce the partly occupation of Mn in the M1 (LiO6) sites and thereby Mn block the lithium ion diffusion pathway. We here firstly find the antisite defect in the high Mn content in porous LiMn1-xFexPO4 composites.

  6. Probing the failure mechanism of nanoscale LiFePO4 for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Gu, Meng; Shi, Wei; Zheng, Jianming; Yan, Pengfei; Zhang, Ji-guang; Wang, Chongmin

    2015-05-01

    LiFePO4 is a high power rate cathode material for lithium ion battery and shows remarkable capacity retention, featuring a 91% capacity retention after 3300 cycles. In this work, we use high-resolution transmission electron microscopy and electron energy loss spectroscopy to study the gradual capacity fading mechanism of LiFePO4 materials. We found that upon prolonged electrochemical cycling of the battery, the LiFePO4 cathode shows surface amorphization and loss of oxygen species, which directly contribute to the gradual capacity fading of the battery. The finding can guide the design and improvement of LiFePO4 cathode for high-energy and high-power rechargeable battery for electric transportation.

  7. Dispersion, agglomeration, and gelation of LiFePO4 in water-based slurry

    NASA Astrophysics Data System (ADS)

    Tsai, Feng-Yen; Jhang, Jia-Hao; Hsieh, Han-Wei; Li, Chia-Chen

    2016-04-01

    The gelation of commercially available lithium iron phosphate (LiFePO4) in water-based slurry and its corresponding mechanism are studied. Based on surface chemistry analyses using zeta potential measurements and Fourier transform infrared spectroscopy, it is found that the key factor that causes LiFePO4 gelation in the aqueous slurry is the quality of the surface carbon coating on powder. When the surface carbon exhibits functional derivatives, such as carboxyl, hydroxyl, and carbonyl polar functional groups, LiFePO4 tends to form a three-dimensional, gel-like structure via hydrogen bonding. Moreover, the presence of the derivatives reduces the amount of conduction-favorable sp2-bonded carbon to LiFePO4, resulting in an electric resistance increase of the as-prepared electrode and the deterioration of the specific capacity of the as-constructed cell.

  8. Unlocking the energy capabilities of micron-sized LiFePO4

    NASA Astrophysics Data System (ADS)

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C.; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G.; Peng, Zhangquan

    2015-08-01

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a `carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations.

  9. Unlocking the energy capabilities of micron-sized LiFePO4

    PubMed Central

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C.; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G.; Peng, Zhangquan

    2015-01-01

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a ‘carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations. PMID:26235395

  10. Optimization of LiFePO4 nanoparticle suspensions with polyethyleneimine for aqueous processing.

    PubMed

    Li, Jianlin; Armstrong, Beth L; Kiggans, Jim; Daniel, Claus; Wood, David L

    2012-02-28

    Addition of dispersants to aqueous based lithium-ion battery electrode formulations containing LiFePO(4) is critical to obtaining a stable suspension. The resulting colloidal suspensions enable dramatically improved coating deposition when processing electrodes. This research examines the colloidal chemistry modifications based on polyethyleneimine (PEI) addition and dispersion characterization required to produce high quality electrode formulations and coatings for LiFePO(4) active cathode material. The isoelectric point, a key parameter in characterizing colloidal dispersion stability, of LiFePO(4) and super P C45 were determined to be pH = 4.3 and 3.4, respectively. PEI, a cationic surfactant, was found to be an effective dispersant. It is demonstrated that 1.0 wt % and 0.5 wt % PEI were required to stabilize the LiFePO(4) and super P C45 suspension, respectively. LiFePO(4) cathode suspensions with 1.5 wt % PEI demonstrated the best dispersibility of all components, as evidenced by viscosity and agglomerate size of the suspensions and elemental distribution within dry cathodes. The addition of PEI significantly improved the LiFePO(4) performance. PMID:22292836

  11. Unlocking the energy capabilities of micron-sized LiFePO4.

    PubMed

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G; Peng, Zhangquan

    2015-01-01

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a 'carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations. PMID:26235395

  12. Enhanced rate performance of multiwalled carbon nanotube encrusted olivine type composite cathode material using polyol technique

    NASA Astrophysics Data System (ADS)

    Muruganantham, R.; Sivakumar, M.; Subadevi, R.

    2015-12-01

    Olivine type multi-walled carbon nanotube encrusted LiFePO4/C composites have been prepared using economic and energy efficient simple polyol technique without any subsequent heat treatment. The prepared material has an olivine type orthorhombic phase. Also, the iron oxidation state is 2+, which is identified by X-ray diffraction and X-ray photoelectron spectroscopy. It is possible to attain the discharge capacity almost close to theoretical capacity of LiFePO4 as in high temperature methods with ∼100% coulombic efficiency. The specific surface area has been increased upon encrusting multi walled carbon nano tube on LiFePO4/C, which results in enhanced reversible capacity upto 166 mAh g-1 at C/10. Also, it exhibits 89 mAh g-1 even at 30 C rate. This is due to the formation of conductive networks by carbon nanotube, and excellent attachment of LiFePO4/C composite particles on multi-walled carbon nanotube, which induced the kinetics during intercalation/deintercalation process. Multi-walled carbon nanotube acts as the electro-conductive filler on the LiFePO4 surface. The direct addition of MWCNT would result better performances than blending the MWCNT with LiFePO4/C.

  13. Synthesis, non-isothermal kinetic and thermodynamic studies of the formation of LiMnPO4 from NH4MnPO4·H2O precursor

    NASA Astrophysics Data System (ADS)

    Sronsri, Chuchai; Noisong, Pittayagorn; Danvirutai, Chanaiporn

    2014-06-01

    NH4MnPO4·H2O was successfully synthesized by precipitating method. The LiMnPO4 was successfully generated through solid state reaction between synthesized NH4MnPO4·H2O precursor and Li2CO3. The morphologies were observed to depend on the reaction temperatures. The thermal decomposition of NH4MnPO4·H2O and the formation process of LiMnPO4 were confirmed by TG/DTG/DTA, FTIR, AAS/AES, XRD and SEM methods. The average crystallite size of NH4MnPO4·H2O, Mn2P2O7 and LiMnPO4 were found to be around 51.2, 44.9 and 48.1 nm, respectively. The non-isothermal kinetic parameters (kinetic triplet: Eα, A, g(α)) of the formation process of LiMnPO4 were evaluated from TG data by using Ozawa-Flynn-Wall and Kissinger-Akahira-Sunose methods. The iterative methods of both equations were carried out to determine the exact values of Eα. The Coats-Redfern equation and kinetic compensation effects were successfully applied to confirm the activation energy and the most probable mechanism functions of the formation of LiMnPO4. The thermodynamic functions (ΔH≠, ΔS≠, ΔG≠) of the transition state complexes of the formation of LiMnPO4 were calculated from the kinetic parameters for the first time.

  14. Synthesis and characterization of LiFePO4 cathode preparation by low temperature method

    NASA Astrophysics Data System (ADS)

    Rajesh, Desapogu; Srinivas Naik, V.; Sunandana, C. S.

    2015-05-01

    We review in detail the physics and technology of the novel material LiFePO4, a potential cathode material for Li-ion batteries. In the present work, nano crystalline LiFePO4 film has been synthesized in both powder and thin film forms from a non-aqueous sol-gel synthesis route based on oxalates of Li and Fe (II). Ferrous oxalate has been synthesized indigenously using a ferrous sulphate based chemical reaction and characterized. Nano powders and thin films of LiFePO4 have been fabricated and coated on stainless steel substrates with the aim of device development in future. The material has been characterized extensively by XRD for crystal structure, FESEM for microstructure, EDS for elemental analysis and FTIR for the internal modes of phosphate ion. Fe3+ impurity characterization has been done by using ESR.

  15. Synthesis of LiFePO4/Pani/C composite as a cathode material for lithium ion battery

    NASA Astrophysics Data System (ADS)

    Rahayu, Iman; Hidayat, Sahrul; Aryadi, Lutfi

    2016-02-01

    In recent years, LiFePO4 studied intensively as a cathode material for Li-ion batteries because of high theoretical capacity, stability, and environmental friendly. However, its low intrinsic electronic conductivity. One way to improve its conductivity is addition of conductive material. Polyaniline (PANI) is one of the conductive polymer materials that widely studied because its unique physical and chemical properties which can be an insulator and conductor by doping-dedoping processes and has large potential application. The purpose of this research is to improve the conductivity of LiFePO4 with conductive polymer PANI. The method is performed by the addition of LiFePO4 during the polymerization process to form LiFePO4 polyaniline then added to the C-PANI with the addition of mass percent variation of 5%, 10%, 15%, 20% form-LiFePO4 composite PANI-C. In LiFePO4 added during polymerization PANI provide a smooth surface profile after composited with the carbon to LiFePO4-PANI-C compared to LiFePO4-C. LiFePO4-PANI-C composite provided higher conductivity is 18.45×10-4 S/cm compared to LiFePO4-C is 10.48×10-4 S/cm at 20% addition of carbon. This is due to PANI in LiFePO4 is added to the polyaniline polymerization process can act as a conductive adhesive to glue between carbon and LiFePO4.

  16. Dynamic study of sub-micro sized LiFePO4 cathodes by in-situ tender X-ray absorption near edge structure

    NASA Astrophysics Data System (ADS)

    Wang, Dongniu; Wang, Huixin; Yang, Jinli; Zhou, Jigang; Hu, Yongfeng; Xiao, Qunfeng; Fang, Haitao; Sham, Tsun-Kong

    2016-01-01

    Olivine-type phosphates (LiMPO4, M = Fe, Mn, Co) are promising cathode materials for lithium-ion batteries that are generally accepted to follow first order equilibrium phase transformations. Herein, the phase transformation dynamics of sub-micro sized LiFePO4 particles with limited rate capability at a low current density of 0.14 C was investigated. An in-situ X-ray Absorption Near Edge Structure (XANES) measurement was conducted at the Fe and P K-edge for the dynamic studies upon lithiation and delithiation. Fe K-edge XANES spectra demonstrate that not only lithium-rich intermediate phase LixFePO4 (x = 0.6-0.75), but also lithium-poor intermediate phase LiyFePO4 (y = 0.1-0.25) exist during the charge and discharge, respectively. Furthermore, during charge and discharge, a fluctuation of the FePO4 and LiFePO4 fractions obtained by liner combination fitting around the imaginary phase fractions followed Faraday's law and the equilibrium first-order two-phase transformation versus reaction time is present, respectively. The charging and discharging process has a reversible phase transformation dynamics with symmetric structural evolution routes. P K-edge XANES spectra reveal an enrichment of PF6-1 anions at the surface of the electrode during charging.

  17. Carbon Surface Layers on a High-Rate LiFePO4

    SciTech Connect

    Gabrisch, Heike; Wilcox, James D.; Doeff, Marca M.

    2005-09-06

    Transmission electron microscopy (TEM) was used to image particles of a high-rate LiFePO4 sample containing a small amount of in situ carbon. The particle morphology is highly irregular, with a wide size distribution. Nevertheless, coatings, varying from about 5-10 nm in thickness, could readily be detected on surfaces of particles as well as on edges of agglomerates. Elemental mapping using Energy Filtered TEM (EFTEM) indicates that these very thin surface layers are composed of carbon. These observations have important implications for the design of high-rate LiFePO4 materials in which, ideally, a minimal amount of carbon coating is used.

  18. TEM Studies of Carbon Coated LiFePO4 after Charge DischargeCycling

    SciTech Connect

    Gabrisch, H.; Wilcox, J.; Doeff, M.

    2006-11-30

    Carbon coating has proven to be a successful approach toimprove the rate capability of LiFePO4 used in rechargeable Li-ionbatteries. Investigations of the microstructure of carbon coated LiFePO4after charge discharge cycling shows that the carbon surface layerremains intact over 100 cycles. We find micro cracks in the cycledmaterial that extend parallel to low indexed lattice planes. Ourobservations differ from observations made by other authors. However thedifferences between the orientations of crack surfaces in both studiescan be reconciled considering the location of weak bonds in the unit celland specimen geometry as well as elastic stress fields ofdislocation.

  19. 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.

  20. Improved battery performance using Pd nanoparticles synthesized on the surface of LiFePO4/C by ultrasound irradiation

    NASA Astrophysics Data System (ADS)

    Saliman, Muhammad Ali; Okawa, Hirokazu; Takai, Misaki; Ono, Yuki; Kato, Takahiro; Sugawara, Katsuyasu; Sato, Mineo

    2016-07-01

    LiFePO4 has been attracting interest as a cathode material for Li-ion batteries due to its high energy density, low cost, and eco-friendliness. The electrochemical performance of LiFePO4 is limited because it exhibits low Li-ion diffusivity and low electronic conductivity. Numerous solutions have been considered, such as carbon coating, which is widely known to improve the electronic conductivity of LiFePO4. The deposition of metal nanoparticles (NPs) on the surface of carbon-coated LiFePO4 further enhances the electronic conductivity. In this study, we deposited Pd NPs onto the surface of LiFePO4/C and investigated the resulting electrochemical performance. Sonochemical synthesis was used to prepare the metal NPs; the procedure did not require any surfactants and the reaction was rapid.

  1. Hierarchical LiFePO4 with a controllable growth of the (010) facet for lithium-ion batteries

    PubMed Central

    Guo, Binbin; Ruan, Hongcheng; Zheng, Cheng; Fei, Hailong; Wei, Mingdeng

    2013-01-01

    Hierarchically structured LiFePO4 was successfully synthesized by ionic liquid solvothermal method. These hierarchically structured LiFePO4 samples were constructed from nanostructured platelets with their (010) facets mainly exposed. To the best of our knowledge, facet control of a hierarchical LiFePO4 crystal has not been reported yet. Based on a series of experimental results, a tentative mechanism for the formation of these hierarchical structures was proposed. After these hierarchically structured LiFePO4 samples were coated with a thin carbon layer and used as cathode materials for lithium-ion batteries, they exhibited excellent high-rate discharge capability and cycling stability. For instance, a capacity of 95% can be maintained for the LiFePO4 sample at a rate as high as 20 C, even after 1000 cycles. PMID:24071818

  2. Structural and Electrical Properties of Lithium-Ion Rechargeable Battery Using the LiFePO4/Carbon Cathode Material.

    PubMed

    Kim, Young-Sung; Jeoung, Tae-Hoon; Nam, Sung-Pill; Lee, Seung-Hwan; Kim, Jea-Chul; Lee, Sung-Gap

    2015-03-01

    LiFePO4/C composite powder as cathode material and graphite powder as anode material for Li-ion batteries were synthesized by using the sol-gel method. An electrochemical improvement of LiFePO4 materials has been achieved by adding polyvinyl alcohol as a carbon source into as-prepared materials. The samples were characterized by elemental analysis (EA), X-ray diffraction (XRD), and field emission scanning electron microscopy (FE-EM). The chemical composition of LiFePO4/C powders was in a good agreement with that of the starting solution. The capacity loss after 500 cycles of LiFePO4/C cell is 11.1% in room temperature. These superior electrochemical properties show that LiFePO4/C composite materials are promising candidates as cathode materials. PMID:26413683

  3. LiFePO4 - 3D carbon nanofiber composites as cathode materials for Li-ions batteries

    NASA Astrophysics Data System (ADS)

    Dimesso, L.; Spanheimer, C.; Jaegermann, W.; Zhang, Y.; Yarin, A. L.

    2012-03-01

    The characterization of carbon nanofiber 3D nonwovens, prepared by electrospinning process, coated with olivine structured lithium iron phosphate is reported. The LiFePO4 as cathode material for lithium ion batteries was prepared by a Pechini-assisted reversed polyol process. The coating has been successfully performed on carbon nanofiber 3D nonwovens by soaking in aqueous solution containing lithium, iron salts and phosphates at 70 °C for 2-4 h. After drying-out, the composites were annealed at 600 °C for 5 h under nitrogen. The surface investigation of the prepared composites showed a uniform coating of the carbon nonwoven nanofibers as well as the formation of cauliflower-like crystalline structures which are uniformly distributed all over the surface area of the carbon nanofibers. The electrochemical measurements on the composites showed good performances delivering a discharge specific capacity of 156 mAhg- 1 at a discharging rate of C/25 and 152 mAhg- 1 at a discharging rate of C/10 at room temperature.

  4. Mössbauer study on LiFePO4 cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Hannoyer, B.; Prince, A. A. M.; Jean, M.; Liu, R. S.; Wang, G. X.

    2006-01-01

    Crystalline LiFePO4 has been synthesized using solid-state, spray pyrolysis, and wet chemical methods. The crystal parameters were obtained from Rietveld’s refinement methods of the X-ray diffraction patterns. A detailed investigation of the Fe valency carried out using Mössbauer spectroscopy at room temperature indicates that Fe is predominantly present in its bivalent state.

  5. Mössbauer study on LiFePO4 cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Hannoyer, B.; Prince, A. A. M.; Jean, M.; Liu, R. S.; Wang, G. X.

    Crystalline LiFePO4 has been synthesized using solid-state, spray pyrolysis, and wet chemical methods. The crystal parameters were obtained from Rietveld's refinement methods of the X-ray diffraction patterns. A detailed investigation of the Fe valency carried out using Mössbauer spectroscopy at room temperature indicates that Fe is predominantly present in its bivalent state.

  6. Microbundles of carbon nanostructures as binder free highly conductive matrix for LiFePO4 battery cathode

    NASA Astrophysics Data System (ADS)

    Lalia, Boor Singh; Shah, Tushar; Hashaikeh, Raed

    2015-03-01

    Microbundles of carbon nanostructures (CNS) have been used to fabricate binder-free LiFePO4 electrodes. The inherent ability of CNS to form a nano-porous structure after the reassembly of CNS dispersion from solution to film-forming state is used to encapsulate the LiFePO4 particles. The LiFePO4/CNS electrode shows high electrical conductivity of 9.1 S cm-1 compared to 0.4 S cm -1 for conventional LiFePO4/carbon electrodes. LiFePO4/CNS flexible electrodes shows specific discharge capacity of 56 mAh g-1, 41 mAh g-1 and 37 mAh g-1 at 1C, 3C and 5C rates respectively. These specific discharge capacities are higher than that of conventional LiFePO4/carbon electrodes i.e. 40 mAh g-1, 13 mAh g-1 and 0.01 mAh g-1 at 1C, 3C and 5C rates respectively. Improvements in the specific discharge capacity at high C-rate is attributed to highly conductive pathways between the CNS and LiFePO4 particles, which assist fast transport of electrons at the electrode/CNS interfaces and between the electrode particles for rapid electrochemical reactions.

  7. Can Vanadium Be Substituted into LiFePO4

    SciTech Connect

    Omenya F.; Nam K.; Chernova N.A.; Upreti S.; Zavalij P.Y.; Nam K.-W.; Yang X.-Q.; Whittingham M.S.

    2011-11-08

    Vanadium is shown to substitute for iron in the olivine LiFePO{sub 4} up to at least 10 mol %, when the synthesis is carried out at 550 C. In the solid solution LiFe{sub 1-3y/2}V{sub y}PO{sub 4}, the a and b lattice parameters and cell volume decrease with increasing vanadium content, while the c lattice parameter increases slightly. However, when the synthesis is performed at 650 C, a NASICON phase, Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}, is also formed, showing that solid solution is a function of the synthesis temperature. X-ray absorption near-edge structure indicates vanadium is in the 3+ oxidation state and in an octahedral environment. Magnetic studies reveal a shift of the antiferromagnetic ordering transition toward lower temperatures with increasing vanadium substitution, confirming solid solution formation. The addition of vanadium enhances the electrochemical performance of the materials especially at high current densities.

  8. The development of low cost LiFePO4-based high power lithium-ion batteries

    SciTech Connect

    Shim, Joongpyo; Sierra, Azucena; Striebel, Kathryn A.

    2003-11-25

    The cycling performance of low-cost LiFePO4-based high-power lithium-ion cells was investigated and the components were analyzed after cycling to determine capacity fade mechanisms. Pouch type LiFePO4/natural graphite cells were assembled and evaluated by constant C/2 cycling, pulse-power and impedance measurements. From post-test electrochemical analysis after cycling, active materials, LiFePO4 and natural graphite, showed no degradation structurally or electrochemically. The main reasons for the capacity fade of cell were lithium inventory loss by side reaction and possible lithium deposition on the anode.

  9. A novel nano structured LiFePO4/C composite as cathode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Huang; Liu, Dong; Qian, Xiuzhen; Zhao, Chongjun; Xu, Yunlong

    2014-03-01

    A novel network LiFePO4/C composite was prepared by mixing precursor solution with carbon aerogel (CA) via a simple solution impregnation method, characterized by XRD, SEM, EDS and electrochemical analysis. The results revealed that the LiFePO4 nanowire forming on the ektexine of CA intertwined with LiFePO4/CA particles and formed a special web structure. The initial discharge capacity was improved to be 139.3 mAh g-1 at 10 C and the capacity retention is near 100% after 50 cycles. The web structure could improve electron transport and electrochemical activity effectively.

  10. Mesoscale phase distribution in single particles of LiFePO4 following lithium deintercalation.

    PubMed

    Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin; Shukla, Alpesh K; Dell'anna, Rossana; Tyliszczak, Tolek; Chen, Guoying; Andrews, Joy C; Richardson, Thomas J; Kostecki, Robert; Cabana, Jordi

    2013-05-14

    The chemical phase distribution in hydrothermally grown micrometric single crystals LiFePO4 following partial chemical delithiation was investigated. Full field and scanning X-ray microscopy were combined with X-ray absorption spectroscopy at the Fe K- and O K-edges, respectively, to produce maps with high chemical and spatial resolution. The resulting information was compared to morphological insight into the mechanics of the transformation by scanning transmission electron microscopy. This study revealed the interplay at the mesocale between microstructure and phase distribution during the redox process, as morphological defects were found to kinetically determine the progress of the reaction. Lithium deintercalation was also found to induce severe mechanical damage in the crystals, presumably due to the lattice mismatch between LiFePO4 and FePO4. Our results lead to the conclusion that rational design of intercalation-based electrode materials, such as LiFePO4, with optimized utilization and life requires the tailoring of particles that minimize kinetic barriers and mechanical strain. Coupling TXM-XANES with TEM can provide unique insight into the behavior of electrode materials during operation, at scales spanning from nanoparticles to ensembles and complex architectures. PMID:23745016

  11. Mesoscale phase distribution in single particles of LiFePO4 following lithium deintercalation

    PubMed Central

    Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin; Shukla, Alpesh K.; Dell’Anna, Rossana; Tyliszczak, Tolek; Chen, Guoying; Andrews, Joy C.; Richardson, Thomas J.; Kostecki, Robert; Cabana, Jordi

    2013-01-01

    The chemical phase distribution in hydrothermally grown micrometric single crystals LiFePO4 following partial chemical delithiation was investigated. Full field and scanning X-ray microscopy were combined with X-ray absorption spectroscopy at the Fe K- and O K-edges, respectively, to produce maps with high chemical and spatial resolution. The resulting information was compared to morphological insight into the mechanics of the transformation by scanning transmission electron microscopy. This study revealed the interplay at the mesocale between microstructure and phase distribution during the redox process, as morphological defects were found to kinetically determine the progress of the reaction. Lithium deintercalation was also found to induce severe mechanical damage in the crystals, presumably due to the lattice mismatch between LiFePO4 and FePO4. Our results lead to the conclusion that rational design of intercalation-based electrode materials, such as LiFePO4, with optimized utilization and life requires the tailoring of particles that minimize kinetic barriers and mechanical strain. Coupling TXM-XANES with TEM can provide unique insight into the behavior of electrode materials during operation, at scales spanning from nanoparticles to ensembles and complex architectures. PMID:23745016

  12. Optimized Operating Range for Large-Format LiFePO4/Graphite Batteries

    SciTech Connect

    Jiang, Jiuchun; Shi, Wei; Zheng, Jianming; Zuo, Pengjian; Xiao, Jie; Chen, Xilin; Xu, Wu; Zhang, Jiguang

    2014-06-01

    e investigated the long-term cycling performance of large format 20Ah LiFePO4/graphite batteries when they are cycled in various state-of-charge (SOC) ranges. It is found that batteries cycled in the medium SOC range (ca. 20~80% SOC) exhibit superior cycling stability than batteries cycled at both ends (0-20% or 80-100%) of the SOC even though the capcity utilized in the medium SOC range is three times as large as those cycled at both ends of the SOC. Several non-destructive techniques, including a voltage interruption approach, model-based parameter identification, electrode impedance spectra analysis, ΔQ/ΔV analysis, and entropy change test, were used to investigate the performance of LiFePO4/graphite batteries within different SOC ranges. The results reveal that batteries at the ends of SOC exhibit much higher polarization impedance than those at the medium SOC range. These results can be attributed to the significant structural change of cathode and anode materials as revealed by the large entropy change within these ranges. The direct correlation between the polarization impedance and the cycle life of the batteries provides an effective methodology for battery management systems to control and prolong the cycle life of LiFePO4/graphite and other batteries.

  13. The influence of reduced graphene oxide on electrical conductivity of LiFePO4-based composite as cathode material

    NASA Astrophysics Data System (ADS)

    Arifin, Muhammad; Aimon, Akfiny Hasdi; Winata, Toto; Abdullah, Mikrajuddin; Iskandar, Ferry

    2016-02-01

    LiFePO4 is fascinating cathode active materials for Li-ion batteries application because of their high electrochemical performance such as a stable voltage at 3.45 V and high specific capacity at 170 mAh.g-1. However, their low intrinsic electronic conductivity and low ionic diffusion are still the hindrance for their further application on Li-ion batteries. Therefore, the efforts to improve their conductivity are very important to elevate their prospecting application as cathode materials. Herein, we reported preparation of additional of reduced Graphene Oxide (rGO) into LiFePO4-based composite via hydrothermal method and the influence of rGO on electrical conductivity of LiFePO4-based composite by varying mass of rGO in composition. Vibration of LiFePO4-based composite was detected on Fourier Transform Infrared Spectroscopy (FTIR) spectra, while single phase of LiFePO4 nanocrystal was observed on X-Ray Diffraction (XRD) pattern, it furthermore, Scanning Electron Microscopy (SEM) images showed that rGO was distributed around LiFePO4-based composite. Finally, the 4-point probe measurement result confirmed that the optimum electrical conductivity is in additional 2 wt% rGO for range 1 to 2 wt% rGO.

  14. Enhanced electrochemical performance in LiFePO4/graphene nanocomposite cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Dhindsa, Kulwinder; Mandal, B.; Lin, M. W.; Nazri, M.; Vaishnava, P.; Naik, V.; Nazri, G. A.; Naik, R.; Zhou, Z. X.

    2012-02-01

    We synthesized LiFePO4/graphene nano-composite employing a sol-gel method, where graphene oxide solution was added to the LiFePO4 precursors during the synthesis. Electrical measurement reveals that the addition of 10% graphene (by weight) to LiFePO4 increases its conductivity by 5 orders of magnitude. SEM images of the composite show that the material consists of LiFePO4 nanoparticles (with a mean particle size ˜ 50 nm) homogeneously mixed with graphene sheets; the latter provides a three-dimensional conducting network for Li+ ion and electron transport. A large specific capacity of 170 mAh/g was observed at a discharge rate of C/2. To further increase the conductivity and inhibit particle size growth of LiFePO4 (thus to increase the rate capacity), we coated the nanoparticles with a thin carbon layer by adding 0.25M lauric acid as precursor in addition to graphene oxide during the synthesis. The respective roles of graphene and lauric-acid-induced carbon coating in the specific capacity and charge-discharge rate of the LiFePO4 cathode material will be discussed.

  15. A high performance hybrid battery based on aluminum anode and LiFePO4 cathode

    DOE PAGESBeta

    Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Bridges, Craig A.; Paranthaman, Mariappan Parans; Dai, Sheng; Brown, Gilbert M.

    2015-12-07

    A unique battery hybrid utilizes an aluminum anode, a LiFePO4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl 3) (EMImCl-AlCl 3, 1-1.1 in molar ratio) with or without LiAlCl4 is proposed. This hybrid ion battery delivers an initial high capacity of 160 mAh g-1 at a current rate of C/5. It also shows good rate capability and cycling performance.

  16. A high performance hybrid battery based on aluminum anode and LiFePO4 cathode.

    PubMed

    Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Fang, Youxing; Bridges, Craig A; Paranthaman, M Parans; Dai, Sheng; Brown, Gilbert M

    2016-01-28

    A novel hybrid battery utilizing an aluminum anode, a LiFePO4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl3) (EMImCl-AlCl3, 1-1.1 in molar ratio) with or without LiAlCl4 is proposed. The hybrid ion battery delivers an initial high capacity of 160 mA h g(-1) at a current rate of C/5. It also shows good rate capability and cycling performance. PMID:26666453

  17. Enhancement of the Rate Capability of LiFePO4 by a New Highly Graphitic Carbon-Coating Method.

    PubMed

    Song, Jianjun; Sun, Bing; Liu, Hao; Ma, Zhipeng; Chen, Zhouhao; Shao, Guangjie; Wang, Guoxiu

    2016-06-22

    Low lithium ion diffusivity and poor electronic conductivity are two major drawbacks for the wide application of LiFePO4 in high-power lithium ion batteries. In this work, we report a facile and efficient carbon-coating method to prepare LiFePO4/graphitic carbon composites by in situ carbonization of perylene-3,4,9,10-tetracarboxylic dianhydride during calcination. Perylene-3,4,9,10-tetracarboxylic dianhydride containing naphthalene rings can be easily converted to highly graphitic carbon during thermal treatment. The ultrathin layer of highly graphitic carbon coating drastically increased the electronic conductivity of LiFePO4. The short pathway along the [010] direction of LiFePO4 nanoplates could decrease the Li(+) ion diffusion path. In favor of the high electronic conductivity and short lithium ion diffusion distance, the LiFePO4/graphitic carbon composites exhibit an excellent cycling stability at high current rates at room temperature and superior performance at low temperature (-20 °C). PMID:27238368

  18. Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca(2.).

    PubMed

    Paolella, Andrea; Turner, Stuart; Bertoni, Giovanni; Hovington, Pierre; Flacau, Roxana; Boyer, Chad; Feng, Zimin; Colombo, Massimo; Marras, Sergio; Prato, Mirko; Manna, Liberato; Guerfi, Abdelbast; Demopoulos, George P; Armand, Michel; Zaghib, Karim

    2016-04-13

    Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances. PMID:26966938

  19. Preparation of V-Doped LiFePO4/C as the Optimized Cathode Material for Lithium Ion Batteries.

    PubMed

    Sun, Pingping; Zhang, Haiyang; Shen, Kai; Fan, Qi; Xu, Qingyu

    2015-04-01

    LiFe1-x,Vx,PO4/C composites were synthesized by solid state reaction. The effect of carbon coating and V doping on the performance of LiFePO4 has been systematically investigated by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), charge/discharge and cyclic voltammetry (CV) measurement. The results show that carbon coating and proper amount of V incorporation do not significantly change the host crystal structure of LiFePO4, while the electrochemical performance of LiFePO4 can be significantly improved. Particularly, the LiFe0.96V0.04PO4/C exhibits the best performance with a specific discharge capacity of 105.5 mA h/g at 5.0 C, 90.3 mA h/g at 10 C and 66.7 mA h/g at 30 C with stable cycle performance, which is significantly improved compared with the pure LiFePO4/C. The cyclic voltammograms result reveals that V doping could decrease the resistance of LiFePO4/C composite electrode drastically and improve its reversibility. PMID:26353479

  20. Effects of imbalanced currents on large-format LiFePO4/graphite batteries systems connected in parallel

    NASA Astrophysics Data System (ADS)

    Shi, Wei; Hu, Xiaosong; Jin, Chao; Jiang, Jiuchun; Zhang, Yanru; Yip, Tony

    2016-05-01

    With the development and popularization of electric vehicles, it is urgent and necessary to develop effective management and diagnosis technology for battery systems. In this work, we design a parallel battery model, according to equivalent circuits of parallel voltage and branch current, to study effects of imbalanced currents on parallel large-format LiFePO4/graphite battery systems. Taking a 60 Ah LiFePO4/graphite battery system manufactured by ATL (Amperex Technology Limited, China) as an example, causes of imbalanced currents in the parallel connection are analyzed using our model, and the associated effect mechanisms on long-term stability of each single battery are examined. Theoretical and experimental results show that continuously increasing imbalanced currents during cycling are mainly responsible for the capacity fade of LiFePO4/graphite parallel batteries. It is thus a good way to avoid fast performance fade of parallel battery systems by suppressing variations of branch currents.

  1. Preparation and electrochemical properties of carbon-coated LiFePO4 hollow nanofibers

    NASA Astrophysics Data System (ADS)

    Wei, Bin-bin; Wu, Yan-bo; Yu, Fang-yuan; Zhou, Ya-nan

    2016-04-01

    Carbon-coated LiFePO4 hollow nanofibers as cathode materials for Li-ion batteries were obtained by coaxial electrospinning. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller specific surface area analysis, galvanostatic charge-discharge, and electrochemical impedance spectroscopy (EIS) were employed to investigate the crystalline structure, morphology, and electrochemical performance of the as-prepared hollow nanofibers. The results indicate that the carbon-coated LiFePO4 hollow nanofibers have good long-term cycling performance and good rate capability: at a current density of 0.2C (1.0C = 170 mA·g-1) in the voltage range of 2.5-4.2 V, the cathode materials achieve an initial discharge specific capacity of 153.16 mAh·g-1 with a first charge-discharge coulombic efficiency of more than 97%, as well as a high capacity retention of 99% after 10 cycles; moreover, the materials can retain a specific capacity of 135.68 mAh·g-1, even at 2C.

  2. Redirected charge transport arising from diazonium grafting of carbon coated LiFePO4.

    PubMed

    Madec, L; Seid, K A; Badot, J-C; Humbert, B; Moreau, P; Dubrunfaut, O; Lestriez, B; Guyomard, D; Gaubicher, J

    2014-11-01

    The morphological and the electrical properties of carbon coated LiFePO4 (LFPC) active material functionalized by 4-ethynylbenzene tetrafluoroboratediazonium salt were investigated. For this purpose, FTIR, Raman, XPS, High Resolution Transmission Electron Microscopy (HRTEM) and Broadband Dielectric Spectroscopy (BDS) were considered. Electronic conductivities of LFPC samples at room temperature were found to decrease in a large frequency range upon simple immersion in polar solvents and to decrease further upon functionalization. Due to their high dipole moment, strongly physisorbed molecules detected by XPS likely add barriers to electron hopping. Significant alteration of the carbon coating conductivity was only observed, however, upon functionalization. This effect is most presumably associated with an increase in the sp(3) content determined by Raman spectroscopy, which is a strong indication of the formation of a covalent bond between the organic layer and the carbon coating. In this case, the electron flux appears to be redirected and relayed by short-range (intra chain) and long-range (inter chain) electron transport through molecular oligomers anchored at the LFPC surface. The latter are controlled by tunnelling and slightly activated hopping, which enable higher conductivity at low temperature (T < 250 K). Alteration of the electron transport within the carbon coating also allows detection of a relaxation phenomenon that corresponds to small polaron hopping in bulk LiFePO4. XPS and HRTEM images allow a clear correlation of these findings with the island type oligomeric structure of grafted molecules. PMID:25234701

  3. Electrochemical and kinetic studies of ultrafast laser structured LiFePO4 electrodes

    NASA Astrophysics Data System (ADS)

    Mangang, M.; Gotcu-Freis, P.; Seifert, H. J.; Pfleging, W.

    2015-03-01

    Due to a growing demand of cost-efficient lithium-ion batteries with an increased energy and power density as well as an increased life-time, the focus is set on intercalation cathode materials like LiFePO4. It has a high practical capacity, is environmentally friendly and has low material costs. However, its low electrical conductivity and low ionic diffusivity are major drawbacks for its use in electrochemical storage devices or electric vehicles. By adding conductive agents, the electrical conductivity can be enhanced. By increasing the surface of the cathode material which is in direct contact with the liquid electrolyte the lithium-ion diffusion kinetics can be improved. A new approach to increase the surface of the active material without changing the active particle packing density or the weight proportion of carbon black is the laser-assisted generation of 3D surface structures in electrode materials. In this work, ultrafast laser radiation was used to create a defined surface structure in LiFePO4 electrodes. It was shown that by using ultrashort laser pulses instead of nanosecond laser pulses, the ablation efficiency could be significantly increased. Furthermore, melting and debris formation were reduced. To investigate the diffusion kinetics, electrochemical methods such as cyclic voltammetry and galvanostatic intermittent titration technique were applied. It could be shown that due to a laser generated 3D structure, the lithium-ion diffusion kinetic, the capacity retention and cell life-time can be significantly improved.

  4. Synthesis, characterization and vibrational spectroscopic study of Co, Mg co-doped LiMnPO4

    NASA Astrophysics Data System (ADS)

    Sronsri, Chuchai; Noisong, Pittayagorn; Danvirutai, Chanaiporn

    2016-01-01

    The isostructural olivine-like LiM(II)PO4 compounds [M(II) = Mn, Mn0.9Co0.1, Mn0.8Co0.1Mg0.1] were successfully generated through the solid state reaction from the synthesized NH4M(II)PO4• H2O precursors. The TG/DTG/DTA, AAS/AES, FTIR and XRD methods were employed to confirm both NH4M(II)PO4• H2O and LiM(II)PO4 compounds. Their morphologies were studied by SEM method. The shift of two theta angle of XRD to higher values was observed in metal doping compounds, which indicate the formation of the single phase of isodivalent doping of Co2 + and Mg2 + ions according to the change in the lattice parameters and cell volumes. Their infrared spectra are reported and discussed with respect to the normal vibrations of NH4+, PO43 -, P2O74 - and H2O molecules using factor group analysis. The correlation field splitting analysis of PO43 - in NH4M(II)PO4• H2O (orthorhombic system, Pmn21, C2v7 and Z = 2, [(3 × 5) - 6] × 2 = 18 internal modes) symbolized as Td - Cs - C2v7 suggested the number of vibrational modes to be: ΓVib = A1(6) + A2(3) + B1(6) + B2(3) and A1(6) + A2(3) + B1(3) + B2(6) for zx and yz plane respectively. While, LiM(II)PO4 crystallizes in the orthorhombic system the space group Pnma (D2h16), Z = 4 and the site symmetry of PO43 - is Cs. The correlation field splitting of type Td - Cs - D2h16 were reported in relation to [(3 × 5) - 6] × 4 = 36 internal modes for PO43 - unit in the structure.

  5. Synthesis of carbon-coated LiFePO 4 nanoparticles with high rate performance in lithium secondary batteries

    NASA Astrophysics Data System (ADS)

    Konarova, Muxina; Taniguchi, Izumi

    A novel preparation technique was developed for synthesizing carbon-coated LiFePO 4 nanoparticles through a combination of spray pyrolysis (SP) with wet ball milling (WBM) followed by heat treatment. Using this technique, the preparation of carbon-coated LiFePO 4 nanoparticles was investigated for a wide range of process parameters such as ball-milling time and ball-to-powder ratio. The effect of process parameters on the physical and electrochemical properties of the LiFePO 4/C composite was then discussed through the results of X-ray diffraction (XRD) analysis, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), the Brunauer-Emmet-Teller (BET) method and the use of an electrochemical cell of Li|1 M LiClO 4 in EC:DEC = 1:1|LiFePO 4. The carbon-coated LiFePO 4 nanoparticles were prepared at 500 °C by SP and then milled at a rotating speed of 800 rpm, a ball-to-powder ratio of 40/0.5 and a ball-milling time of 3 h in an Ar atmosphere followed by heat treatment at 600 °C for 4 h in a N 2 + 3% H 2 atmosphere. SEM observation revealed that the particle size of LiFePO 4 was significantly affected by the process parameters. Furthermore, TEM observation revealed that the LiFePO 4 nanoparticles with a geometric mean diameter of 146 nm were coated with a thin carbon layer of several nanometers by the present method. Electrochemical measurement demonstrated that cells containing carbon-coated LiFePO 4 nanoparticles could deliver markedly improved battery performance in terms of discharge capacity, cycling stability and rate capability. The cells exhibited first discharge capacities of 165 mAh g -1 at 0.1 C, 130 mAh g -1 at 5 C, 105 mAh g -1 at 20 C and 75 mAh g -1 at 60 C with no capacity fading after 100 cycles.

  6. Emergence of Metallic Properties at LiFePO4 Surfaces and LiFePO4/Li2S Interfaces: An Ab Initio Study.

    PubMed

    Timoshevskii, Vladimir; Feng, Zimin; Bevan, Kirk H; Zaghib, Karim

    2015-08-26

    The atomic and electronic structures of the LiFePO4 (LFP) surface, both bare and reconstructed upon possible oxygenation, are theoretically studied by ab initio methods. On the basis of total energy calculations, the atomic structure of the oxygenated surface is proposed, and the effect of surface reconstruction on the electronic properties of the surface is clarified. While bare LFP(010) surface is insulating, adsorption of oxygen leads to the emergence of semimetallic behavior by inducing the conducting states in the band gap of the system. The physical origin of these conducting states is investigated. We further demonstrate that deposition of Li2S layers on top of oxygenated LFP(010) surface leads to the formation of additional conducting hole states in the first layer of Li2S surface because of the charge transfer from sulfur p-states to the gap states of LFP surface. This demonstrates that oxygenated LFP surface not only provides conducting layers itself, but also induces conducting channels in the top layer of Li2S. These results help to achieve further understanding of potential role of LFP particles in improving the performance of Li-S batteries through emergent interface conductivity. PMID:26237114

  7. Tailored surface structure of LiFePO4/C nanofibers by phosphidation and their electrochemical superiority for lithium rechargeable batteries.

    PubMed

    Lee, Yoon Cheol; Han, Dong-Wook; Park, Mihui; Jo, Mi Ru; Kang, Seung Ho; Lee, Ju Kyung; Kang, Yong-Mook

    2014-06-25

    We offer a brand new strategy for enhancing Li ion transport at the surface of LiFePO4/C nanofibers through noble Li ion conducting pathways built along reduced carbon webs by phosphorus. Pristine LiFePO4/C nanofibers composed of 1-dimensional (1D) LiFePO4 nanofibers with thick carbon coating layers on the surfaces of the nanofibers were prepared by the electrospinning technique. These dense and thick carbon layers prevented not only electrolyte penetration into the inner LiFePO4 nanofibers but also facile Li ion transport at the electrode/electrolyte interface. In contrast, the existing strong interactions between the carbon and oxygen atoms on the surface of the pristine LiFePO4/C nanofibers were weakened or partly broken by the adhesion of phosphorus, thereby improving Li ion migration through the thick carbon layers on the surfaces of the LiFePO4 nanofibers. As a result, the phosphidated LiFePO4/C nanofibers have a higher initial discharge capacity and a greatly improved rate capability when compared with pristine LiFePO4/C nanofibers. Our findings of high Li ion transport induced by phosphidation can be widely applied to other carbon-coated electrode materials. PMID:24786736

  8. Experimental and numerical study of phase transition of LiFePO 4 material in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Siddique, Md Noor E. Alam

    Phase transition behavior of LiFePO4 material has been studied in this work. During electrochemical charge/discharge processes, LiFePO 4 transforms into FePO4 and this electrochemically driven phase transition of the two-phase system results in a potential plateau in a battery discharge curve. Besides, battery performance, especially under high rates, depends critically on this two-phase transition. However, this phase transition mechanism in the LiFePO4 crystal structure has yet not been understood in details. Developing better understanding is essential for designing high performing, safe and stable batteries. Currently available phase transition models for LiFePO4, such as the classical `core-shrinking model' and recently the `domino cascade model', have shed lights on the phase transition mechanism, however, with somewhat contradicting conclusions. The former predicted a continuous phase transition between LiFePO4 and FePO4 within an individual particle. In contrast, the latter, based on the fact of anisotropic diffusion of Li, provided a microscopically heterogeneous picture of phase transition: phase transition is abrupt, and de-lithiated and lithiated particles co-exist in a battery electrode. To achieve a better understanding of the two-phase transition phenomena, two specially designed sophisticated methods, i.e., in-situ Raman spectroscopy and in-situ X-ray Diffraction (XRD), have been developed in this work. The particle level phase transition of LiFePO4 was probed in the in-situ Raman study. Under slow-rate discharge/charge, it was found that the particles were either fully transformed or untransformed indicating that the phase transition in LiFePO4 material was not uniform at the particle level. Electronic conductivity and local electrode microstructure determined the preferred sequence of phase transition of the particles. This study also revealed that non-equilibrium phase transition occurred as a result of delayed phase transition. The in-situ XRD study attempted to investigate the bulk level phase transition behavior of LiFePO4 and was conducted at four different discharge rates. Analysis of the high-resolution diffraction patterns showed a gradual and continuous change in phase transition. Again, a delayed phase transition was observed at high-rate discharge due to the non-equilibrium pathway. From both in-situ Raman and in-situ XRD experiments, only two stoichiometric compounds (LiFePO4 and FePO4) was detected, indicating that during electrochemical charge/discharge processes once Li ion de-intercalates/intercalates, it immediately forms the end-members and no intermediate compounds exist. Particle size and morphology of LiFePO4 were also studied using numerical models in the phase transition behavior. At a slow discharge rate, plate shaped particles showed higher capacity than spherical particles and the opposite trend was observed at high discharge rates above some critical discharge rates. Big particles and high discharge rates induced non-equilibrium phase transition in the LiFePO4 particles which expands the miscibility gap between the end-members and gave sharp narrow two-phase interfaces.

  9. Effect of precursor concentration on the electrical properties of LiFePO4 prepared by solvothermal method

    NASA Astrophysics Data System (ADS)

    Rabbani, Ahmad Yasin; Fakhri, Hafizh A.; Arifin, Muhammad; Aimon, Akfiny Hasdi; Iskandar, Ferry

    2016-02-01

    Lithium iron phosphate (LiFePO4) is frequently used for Li-ion battery cathode. LiFePO4 has the high specific capacity at 170 mAhg-1, stable voltage at 3.45 V, stable structure, cheap, and low toxicity. The objective of this research is investigating the effect of precursor concentration on the electrical properties of LiFePO4 prepared by solvothermal method. LiOH, FeSO4, H3PO4, and citric acid were used as the precursors. The LiOH concentration was varied from 0.3 M to 1.8 M. The Fourier Transform Infrared Spectroscopy (FTIR) measurement identified the Fe-O, O-P-O, and P-O bonds which corresponding to LiFePO4. The result of 4-point probe measurement shows that, among the prepared samples, the sample from the precursor concentration of 1.8 M has the highest electrical conductivity.

  10. Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity.

    PubMed

    Jena, Ajit; Nanda, B R K

    2016-01-01

    Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)(3-). The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator. PMID:26791249

  11. Water based processing of LiFePO4/C cathode material for Li-ion batteries utilizing freeze granulation

    NASA Astrophysics Data System (ADS)

    Orlenius, J.; Lyckfeldt, O.; Kasvayee, K. A.; Johander, P.

    2012-09-01

    A water based solid state synthesis of LiFePO4 has been conducted by utilizing freeze granulation. Various processing conditions were tested and achieved powder properties were characterized by density, XRD, specific surface area, carbon content, conductivity and SEM. Freeze granulation, a novel method for precursor preparation was shown to be an effective method to provide high degree of homogeneity prior to calcination and high ultimate yield of pure LiFePO4. Cathodes were manufactured by water based as well as NMP system based tape casting. A commercial LiFePO4/C powder was also characterized and used to manufacture cathodes as comparison in this study. Charge cycling tests showed promising results with high capacity and long term stability, well in the range of what the commercial powder provided. Post-milling of calcined powder prior to paste preparation for tape casting tended, however, to retard the capacity owing to disturbed carbon distribution and loss of conductivity of the LiFePO4/C. In comparison with the solvent system for cathode manufacturing, the water based system gave similar cell performance, illustrating the possibility to apply a more environmentally sustainable processing of Li-battery cells.

  12. Morphological characterization of LiFePO 4/C composite cathode materials synthesized via a carboxylic acid route

    NASA Astrophysics Data System (ADS)

    Fey, George Ting-Kuo; Lu, Tung-Lin

    A new type of LiFePO 4/C composite surrounded by a web containing both amorphous and crystalline carbon phases was synthesized by incorporating malonic acid as a carbon source using a high temperature solid-state method. SEM, TEM/SAED/EDS and HRTEM were used to analyze surface morphology and confirmed for the first time that crystalline carbon was present in LiFePO 4/C composites. The composite was effective in enhancing the electrochemical properties such as capacity and rate capability, because its active component consists of nanometer-sized particles containing pores with a wide range of sizes. An EDS elemental map showed that carbon was uniformly distributed on the surface of the composite crystalline particles. TEM/EDS results clearly show a dark region that is LiFePO 4 with a trace of carbon and a gray region that is carbon only. To evaluate the materials' electrochemical properties, galvanostatic cycling and conductivity measurements were performed. The best cell performance was delivered by the material coated with 60 wt.% malonic acid, which delivered first cycle discharge capacity of 149 mAh g -1 at a C/5 rate and sustained 222 cycles at 80% of capacity retention. When carboxylic acid was used as a carbon source to produce LiFePO 4, overall conductivity increased from 10 -5 to 10 -4 S cm -1, since particle growth was prevented during the final sintering process.

  13. Effect of surfactants on the electrochemical behavior of LiFePO4 cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Mandal, B. P.; Nazri, M.; Naik, V. M.; Garg, V. K.; Oliveira, A. C.; Vaishnava, P. P.; Nazri, G. A.; Naik, R.

    2014-11-01

    The application of lithium iron phosphate as positive electrode material for lithium ion batteries has been challenged by its poor electronic conductivity. To improve its conductivity and electrochemical performance, we have synthesized LiFePO4/C composite cathode materials by sol gel technique using long chain fatty acids, such as, lauric, myristic, and oleic acids, as surfactants for carbon coating. The phase purity of the three LiFePO4/C composites was confirmed by X-ray diffraction. The Raman spectroscopy, scanning electron microscopy and transmission electron microscopy measurements show that the surfactants coat the LiFePO4 particles with carbon with varying degree of uniformity depending on the surfactant used. The sample prepared in presence of lauric acid shows smaller particle size and the lowest charge transfer resistance, higher Li-ion diffusion coefficient, higher discharge capacity (∼155 mAh g-1 at C/3 rate), better rate capability and cyclic stability compared to the other two samples. We found the smaller particle size, uniformity of carbon coating, reduced agglomeration, and a lower amount of Fe3+ impurity phase in the samples to be major contributing factors for better electrochemical properties in the LiFePO4/C cathode material.

  14. Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity

    PubMed Central

    Jena, Ajit; Nanda, B. R. K.

    2016-01-01

    Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)3−. The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator. PMID:26791249

  15. Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity

    NASA Astrophysics Data System (ADS)

    Jena, Ajit; Nanda, B. R. K.

    2016-01-01

    Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)3-. The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator.

  16. Crystal structure analysis and first principle investigation of F doping in LiFePO4

    NASA Astrophysics Data System (ADS)

    Milović, Miloš; Jugović, Dragana; Cvjetićanin, Nikola; Uskoković, Dragan; Milošević, Aleksandar S.; Popović, Zoran S.; Vukajlović, Filip R.

    2013-11-01

    This work presents the synthesis of F-doped LiFePO4/C composite by the specific modification of the recently suggested synthesis procedure based on an aqueous precipitation of precursor material in molten stearic acid, followed by a high temperature treatment. Besides the lattice parameters and the primitive cell volume reductions, compared to the undoped sample synthesized under the same conditions, the Rietveld refinement also shows that fluorine ions preferably occupy specific oxygen sites. Particularly, the best refinement is accomplished when fluorine ions occupy O(2) sites exclusively. By means of up-to-date electronic structure and total energy calculations this experimental finding is theoretically confirmed. Such fluorine doping also produces closing of the gap in the electronic structure and consequently better conductivity properties of the doped compound. In addition, the morphological and electrochemical performances of the synthesized powder are fully characterized.

  17. Electrochemical performance of LiFePO4 cylinder cell battery

    NASA Astrophysics Data System (ADS)

    Honggowiranto, Wagiyo; Sudaryanto, Kartini, Evvy; Purwanto, Agus

    2016-02-01

    A study on the electrochemical performance of LiFePO4 based cylinder cell battery has been done. The measurements have been carried out using cyclic voltametry (CV), charge-discharge (CD), and electrochemical impedance spectroscopy (EIS). The CV profiles showed that the battery exhibited anodic (charge) peak and chatodic (discharge) peak when scanned between 2.5 and 4.2V at various scan rate of 1 to 0.05 mV/s. The CD result showed that the battery capacity was 700 mAh exhibited excellent capacity retention with efficiency was about 100% after 100 cycles. From EIS measurement, it was also observed that the battery resistance decreased with the state of charge.

  18. Characterization of LiFePO4 cathode by addition of graphene for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Honggowiranto, Wagiyo; Kartini, Evvy

    2016-02-01

    The improvement of LiFePO4 (LFP) cathode performance has been performed by addition of Graphene (LFP+Graphene). The cathode was prepared from the active material with 5 wt % graphene and 10 wt % polyvinylidene fluoride in an n-methyl pyrrolidone solvent. Another cathode material used only 5% artificial graphite for comparison (LFP+Graphite). The crystal structure, microstructure, electronic conductivity, electrochemical impedance spectroscopy (EIS) of the cathodes were characterized by X-ray diffraction, SEM, and Impedance spectroscopy, respectively. Two half cell coin batteries were assembled using a lithium metal as an anode and LiPf6 as an electrolyte, and two cathodes (LFP+Graphene) and (LFP+Graphite). Charge discharge performance of battery was characterized by Battery analyser (BTS 8). The electronic conductivity of cathode with grapheme increased of about one order magnitude compared with the only cathode with graphite, namely from 1.97E-7S/cm (LFP+Graphite) to 1.92E-6S/cm (LFP+Graphene). The charge-discharge capacity after 10th cycles of LiFePO4 with graphene decreased of about 0.68% from 114.3 mAh/g to113.1 mAh/g, while LFP with graphite decreased of about 2.84% from 110.2 mAh/g to 107.1 mAh, at 0.1C-rates. It could be concluded that the addition of graphene has increased the ionic conductivity, and improved performance of the LFP lithium ion battery, such as higher capacity and better efficiency.

  19. Li-Ion Batteries from LiFePO4 Cathode and Anatase/Graphene Composite Anode for Stationary Energy Storage

    SciTech Connect

    Choi, Daiwon; Wang, Donghai; Viswanathan, Vilayanur V.; Bae, In-Tae; Wang, Wei; Nie, Zimin; Zhang, Jiguang; Graff, Gordon L.; Liu, Jun; Yang, Zhenguo; Duong, Tien Q.

    2009-11-06

    Li-ion batteries based on LiFePO4 cathode and anatase TiO2/graphene anode were investigated for possible stationary energy storage application. Fine-structured LiFePO4 was synthesized by novel molten surfactant approach. Anatase TiO2/graphene nanocomposite was prepared via self assembly method. The full cell that operated at flat 1.6V demonstrated negligible fade after more than 700 cycles. The LiFePO4/TiO2 combination Li-ion battery is inexpensive, environmentally benign, safe and stable. Therefore, it can be practically applied as stationary energy storage for renewable power sources.

  20. Electrochemical and XPS study of LiFePO4 cathode nanocomposite with PPy/PEG conductive network

    NASA Astrophysics Data System (ADS)

    Fedorková, A.; Oriňáková, R.; Oriňák, A.; Kupková, M.; Wiemhöfer, H.-D.; Audinot, J. N.; Guillot, J.

    2012-08-01

    High performance PPy/PEG-LiFePO4 nanocomposites as cathode materials were synthesized by solvothermal method and simple chemical oxidative polymerization of pyrrole (Py) monomer on the surface of LiFePO4 particles. The samples were characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectrometry (XPS) and charge-discharge tests. PPyPEG hybrid layers decrease particle to particle contact resistance while the impedance measurements confirmed that the coating of PPy-PEG significantly decreases the charge transfer resistance of the electrode material. The initial discharge capacities of this sample at C/5 and 1C are 150 and 128 mAh/g, respectively. The results show that PPy/PEGLiFePO4 composites are more effective than bare LiFePO4 as cathode material.

  1. Why LiFePO4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation.

    PubMed

    Liu, Xiaosong; Wang, Yung Jui; Barbiellini, Bernardo; Hafiz, Hasnain; Basak, Susmita; Liu, Jun; Richardson, Thomas; Shu, Guojiun; Chou, Fangcheng; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Moritz, Brian; Devereaux, Thomas P; Qiao, Ruimin; Chuang, Yi-De; Bansil, Arun; Hussain, Zahid; Yang, Wanli

    2015-10-21

    LiFePO4 is a battery cathode material with high safety standards due to its unique electronic structure. We performed systematic experimental and theoretical studies based on soft X-ray emission, absorption, and hard X-ray Raman spectroscopy of LixFePO4 nanoparticles and single crystals. The results clearly show a non-rigid electron-state reconfiguration of both the occupied and unoccupied Fe-3d and O-2p states during the (de)lithiation process. We focus on the energy configurations of the occupied states of LiFePO4 and the unoccupied states of FePO4, which are the critical states where electrons are removed and injected during the charge and discharge process, respectively. In LiFePO4, the soft X-ray emission spectroscopy shows that, due to the Coulomb repulsion effect, the occupied Fe-3d states with the minority spin sit close to the Fermi level. In FePO4, the soft X-ray absorption and hard X-ray Raman spectroscopy show that the unoccupied Fe-3d states again sit close to the Fermi level. These critical 3d electron state configurations are consistent with the calculations based on modified Becke and Johnson potentials GGA+U (MBJGGA+U) framework, which improves the overall lineshape prediction compared with the conventionally used GGA+U method. The combined experimental and theoretical studies show that the non-rigid electron state reshuffling guarantees the stability of oxygen during the redox reaction throughout the charge and discharge process of LiFePO4 electrodes, leading to the intrinsic safe performance of the electrodes. PMID:26388021

  2. Nanoscale LiFePO4 and Li4Ti5O12 for High Rate Li-ion Batteries

    SciTech Connect

    Jaiswal, A.; Horne, C.R.; Chang, O.; Zhang, W.; Kong, W.; Wang, E.; Chern, T.; Doeff, M. M.

    2009-08-04

    The electrochemical performances of nanoscale LiFePO4 and Li4Ti5O12 materials are described in this communication. The nanomaterials were synthesized by pyrolysis of an aerosol precursor. Both compositions required moderate heat-treatment to become electrochemically active. LiFePO4 nanoparticles were coated with a uniform, 2-4 nm thick carbon-coating using an organic precursor in the heat treatment step and showed high tap density of 1.24 g/cm3, in spite of 50-100 nm particle size and 2.9 wtpercent carbon content. Li4Ti5O12 nanoparticles were between 50-200 nm in size and showed tap density of 0.8 g/cm3. The nanomaterials were tested both in half cell configurations against Li-metal and also in LiFePO4/Li4Ti5O12 full cells. Nano-LiFePO4 showed high discharge rate capability with values of 150 and 138 mAh/g at C/25 and 5C, respectively, after constant C/25 charges. Nano-Li4Ti5O12 also showed high charge capability with values of 148 and 138 mAh/g at C/25 and 5C, respectively, after constant C/25 discharges; the discharge (lithiation) capability was comparatively slower. LiFePO4/Li4Ti5O12 full cells deliver charge/discharge capacity values of 150 and 122 mAh/g at C/5 and 5C, respectively.

  3. Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model

    NASA Astrophysics Data System (ADS)

    Delmas, C.; Maccario, M.; Croguennec, L.; Le Cras, F.; Weill, F.

    2008-08-01

    Lithium iron phosphate is one of the most promising positive-electrode materials for the next generation of lithium-ion batteries that will be used in electric and plug-in hybrid vehicles. Lithium deintercalation (intercalation) proceeds through a two-phase reaction between compositions very close to LiFePO4 and FePO4. As both endmember phases are very poor ionic and electronic conductors, it is difficult to understand the intercalation mechanism at the microscopic scale. Here, we report a characterization of electrochemically deintercalated nanomaterials by X-ray diffraction and electron microscopy that shows the coexistence of fully intercalated and fully deintercalated individual particles. This result indicates that the growth reaction is considerably faster than its nucleation. The reaction mechanism is described by a `domino-cascade model' and is explained by the existence of structural constraints occurring just at the reaction interface: the minimization of the elastic energy enhances the deintercalation (intercalation) process that occurs as a wave moving through the entire crystal. This model opens new perspectives in the search for new electrode materials even with poor ionic and electronic conductivities.

  4. Anomalous magnetic structure and spin dynamics in magnetoelectric LiFePO4

    DOE PAGESBeta

    Toft-Petersen, Rasmus; Reehuis, Manfred; Jensen, Thomas B. S.; Andersen, Niels H.; Li, Jiying; Le, Manh Duc; Laver, Mark; Niedermayer, Christof; Klemke, Bastian; Lefmann, Kim; et al

    2015-07-06

    We report significant details of the magnetic structure and spin dynamics of LiFePO4 obtained by single-crystal neutron scattering. Our results confirm a previously reported collinear rotation of the spins away from the principal b axis, and they determine that the rotation is toward the a axis. In addition, we find a significant spin-canting component along c. Furthermore, the possible causes of these components are discussed, and their significance for the magnetoelectric effect is analyzed. Inelastic neutron scattering along the three principal directions reveals a highly anisotropic hard plane consistent with earlier susceptibility measurements. While using a spin Hamiltonian, we showmore » that the spin dimensionality is intermediate between XY- and Ising-like, with an easy b axis and a hard c axis. As a result, it is shown that both next-nearest neighbor exchange couplings in the bc plane are in competition with the strongest nearest neighbor coupling.« less

  5. Degradation diagnosis of aged Li4Ti5O12/LiFePO4 batteries

    NASA Astrophysics Data System (ADS)

    Castaing, Rémi; Reynier, Yvan; Dupré, Nicolas; Schleich, Donald; Jouanneau Si Larbi, Séverine; Guyomard, Dominique; Moreau, Philippe

    2014-12-01

    Li4Ti5O12/LiFePO4 cells are cycled under 4 different conditions of discharge profile (galvanostatic or driving-based) and cycling rates (C/8 or 1C) during 4-5 months. All the cells exhibit capacity fade whose extent is not correlated with the aging condition. In order to understand aging phenomena, cells are disassembled at the end of cycle life and the recovered electrodes are analyzed using electrochemistry, electron microscopy, XRD and MAS-NMR. Positive and negative electrodes show no loss in active material and no change in electrochemical activity, active material structure and composite electrode structure. This rules out any irreversible electrode degradation. Lithium stoichiometry estimated by both XRD and electrochemistry is unexpectedly low in the positive electrode when the aging is stopped at full discharge. That indicates a loss of cyclable lithium or electrons leading to cell balancing evolution. That loss may have been caused by parasitic reactions occurring at both electrodes, in accordance with their rich surface chemistry as evidenced by MAS-NMR.

  6. Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model.

    PubMed

    Delmas, C; Maccario, M; Croguennec, L; Le Cras, F; Weill, F

    2008-08-01

    Lithium iron phosphate is one of the most promising positive-electrode materials for the next generation of lithium-ion batteries that will be used in electric and plug-in hybrid vehicles. Lithium deintercalation (intercalation) proceeds through a two-phase reaction between compositions very close to LiFePO(4) and FePO(4). As both endmember phases are very poor ionic and electronic conductors, it is difficult to understand the intercalation mechanism at the microscopic scale. Here, we report a characterization of electrochemically deintercalated nanomaterials by X-ray diffraction and electron microscopy that shows the coexistence of fully intercalated and fully deintercalated individual particles. This result indicates that the growth reaction is considerably faster than its nucleation. The reaction mechanism is described by a 'domino-cascade model' and is explained by the existence of structural constraints occurring just at the reaction interface: the minimization of the elastic energy enhances the deintercalation (intercalation) process that occurs as a wave moving through the entire crystal. This model opens new perspectives in the search for new electrode materials even with poor ionic and electronic conductivities. PMID:18641656

  7. Relating the 3D electrode morphology to Li-ion battery performance; a case for LiFePO4

    NASA Astrophysics Data System (ADS)

    Liu, Zhao; Verhallen, Tomas W.; Singh, Deepak P.; Wang, Hongqian; Wagemaker, Marnix; Barnett, Scott

    2016-08-01

    One of the main goals in lithium ion battery electrode design is to increase the power density. This requires insight in the relation between the complex heterogeneous microstructure existing of active material, conductive additive and electrolyte providing the required electronic and Li-ion transport. FIB-SEM is used to determine the three phase 3D morphology, and Li-ion concentration profiles obtained with Neutron Depth Profiling (NDP) are compared for two cases, conventional LiFePO4 electrodes and better performing carbonate templated LiFePO4 electrodes. This provides detailed understanding of the impact of key parameters such as the tortuosity for electron and Li-ion transport though the electrodes. The created hierarchical pore network of the templated electrodes, containing micron sized pores, appears to be effective only at high rate charge where electrolyte depletion is hindering fast discharge. Surprisingly the carbonate templating method results in a better electronic conductive CB network, enhancing the activity of LiFePO4 near the electrolyte-electrode interface as directly observed with NDP, which in a large part is responsible for the improved rate performance both during charge and discharge. The results demonstrate that standard electrodes have a far from optimal charge transport network and that significantly improved electrode performance should be possible by engineering the microstructure.

  8. High-performance LiFePO4/C electrode with polytetrafluoroethylene as an aqueous-based binder

    NASA Astrophysics Data System (ADS)

    Gao, Shiyan; Su, Yuefeng; Bao, Liying; Li, Ning; Chen, Lai; Zheng, Yu; Tian, Jun; Li, Jian; Chen, Shi; Wu, Feng

    2015-12-01

    An environmental-friendly and low-cost polymer, polytetrafluoroethylene (PTFE) has been applied as an aqueous-based binder for the fabrication of LiFePO4/C electrode. The electrode with PTFE has been compared to the electrode with the conventional binder, polyvinylidene fluoride (PVDF) via Rheology test, X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and electrochemical tests. The Rheology test indicates that the viscosity of the slurry prepared with PTFE as a binder is better than that prepared with PVDF. The electrochemical measurements demonstrate that the electrode with PTFE binder displays a higher discharge capacity of 161.1 mAh g-1 compared to the electrode with PVDF binder, which shows a discharge capacity of 150.7 mAh g-1. The EIS analysis indicates the LiFePO4/C electrode with PTFE binder shows a higher ionic conductivity and a smaller increasing in charge transfer rate compared to the LiFePO4/C electrode with PVDF binder. In addition, the electrodes applying the aqueous-based binder have been optimized by controlling the moisture content in the electrodes. The electrochemical enhancement of these electrodes can be achieved by controlling the vacuum drying temperature and time during the preparation of the electrodes.

  9. Role of PO4 tetrahedron in LiFePO4 and FePO4 system.

    PubMed

    Zeng, Yuewu

    2015-06-01

    Using high resolution transmission electron microscopy with image simulation and Fourier analysis, the Li1- x FePO4 (x < 0.01), Li1- x FePO4 (x ∼ 0.5), and FePO4 particles, prepared by charging or discharging the 053048 electrochemical cells (thickness: 5 mm, width: 30 mm, height: 48 mm) and dismantled inside an Ar-filled dry box, were investigated. The high resolution images reveal: (1) the solid solution of Li1- x FePO4 (x < 0.01) contains some missing Li ions leading PO4 group distorted around M1 tunnel of the unit cell; (2) the texture of the particles of Li1- x FePO4 (x ∼0.5) has homogeneously distributed compositional domains of LiFePO4 and FePO4 resulting from spinodal decomposition which promote Li ion easily getting into the particle due to uphill diffusion, (3) the particles of FePO4 formed in charging have heavily distorted lattice and contain some isolated LiFePO4 , (4) interface between LiFePO4 and FePO4 and between amorphous and crystal region provides the lattice distortion of small polarons. PMID:25846750

  10. Investigation on the fly ash thermal treatment on the performance of Lithium Ferriphosphate (LiFePO4) battery

    NASA Astrophysics Data System (ADS)

    Febiolita, Bella; Khoirunnissak, Dewi; Purwanto, Agus

    2016-02-01

    Addition of the fly ash can be used to improve the capacity of LiFePO4 battery. Fly ash was added in Acethylene Black (AB) as 2% of the total weight of Acetylene Black (AB). The effects of temperature variation and fly ash characteristics were analyzed. Fly ash was prepared by heating at 50, 100, 150, and 250°C in muffle furnace for 5 hours and passed in 200 mesh screen prior to mixing it with other compounds. Lithium Ferriphospat (LiFePO4), fly ash, Acethylene Black (AB), Polyvinylidene Fluoride (PVDF) as a binder and N-methyl-2-pyrrolidone (NMP) as a solvent were mixed to be slurry. The slurry were coated, dried and hot pressed to make a cathode film. The performance of battery lithium was examined by eight channel battery analyzer. The composition of the fly ash was examined by X-ray fluorescence spectrometry (XRF) and Fourier Tansform Infrared Spectroscopy (FTIR). The excellent performance was shown in the fly ash addition which were treated by heating at 150°C. The capacity of fly ash added LiFePO4 battery is 94.373 mAh/g, which is higher than that of without fly ash addition, i.e. 67.998 mAh/g.

  11. Synthesis of cage-like LiFePO4/C microspheres for high performance lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Deng, Honggui; Jin, Shuangling; Zhan, Liang; Wang, Yanli; Qiao, Wenming; Ling, Licheng

    2012-12-01

    Cage-like LiFePO4 microspheres are synthesized by a solvothermal reaction-calcination process, using Fe(NO3)3·9H2O as iron source and ethylene glycol/water as co-solvent medium. The microsphere is the assembly of LiFePO4 nanoparticles with an open porous structure, thus the carbon coating can be easily introduced on the surface of the nanoparticles by the chemical vapor deposition of C2H4 during calcination process. When used as the cathode materials for the lithium-ion batteries, the resultant cage-like LiFePO4/C microsphere shows high capacity and good cycle stability (160 mAh g-1 at 0.1 C over 300 cycles), as well as good rate capability (120 mAh g-1 at 10 C). The desirable electrochemical performance can be attributed to high rate of ionic/electronic conduction and the high structural stability arising from the interconnected open pores, carbon-coated nanoparticles and microsized structure.

  12. Surfactant based sol-gel approach to nanostructured LiFePO 4 for high rate Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Choi, Daiwon; Kumta, Prashant N.

    Porous nanostructured LiFePO 4 powder with a narrow particle size distribution (100-300 nm) for high rate lithium-ion battery cathode application was obtained using an ethanol based sol-gel route employing lauric acid as a surfactant. The synthesized LiFePO 4 powders comprised of agglomerates of crystallites <65 nm in diameter exhibiting a specific surface area ranging from 8 m 2 g -1 to 36 m 2 g -1 depending on the absence or presence of the surfactant. The LiFePO 4 obtained using lauric acid resulted in a specific capacity of 123 mAh g -1 and 157 mAh g -1 at discharge rates of 10 C and 1 C with less than 0.08% fade per cycle, respectively. Structural and microstructural characterization were performed using X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) with energy dispersive X-ray (EDX) analysis while electronic conductivity and specific surface area were determined using four-point probe and N 2 adsorption techniques.

  13. In-situ synthesis of monodisperse micro-nanospherical LiFePO4/carbon cathode composites for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Gong, Hao; Xue, Hairong; Wang, Tao; He, Jianping

    2016-06-01

    The LiFePO4 is recognized as the promising cathode material, due to its high specific capacity, excellent, structural stability and environmental benignity. However, it is blamed for the low tap density and poor rate performance when served as the cathode materials for a long time. Here, the microspheric LiFePO4/C composites are successfully synthesized through a one-step in-situ solvothermal method combined with carbothermic reduction. These LiFePO4/C microspheres are assembled by LiFePO4 nanoparticles (∼100 nm) and uniformly coated by the carbon, which show a narrow diameter distribution of 4 μm. As a cathode material for lithium ion batteries, the LiFePO4/C composites can deliver an initiate charge capacity of 155 mAh g-1 and retain 90% of initial capacity after 200 cycles at 0.1 C. When cycled at high current densities up to 20 C, it shows a discharge capacity of ∼60 mAh g-1, exhibiting superior rate performance. The significantly improved electrochemical performance of LiFePO4/C composites material can be attributed to its special micro-nano hierarchical structure. Microspheric LiFePO4/C composites exhibit a high tap density about 1.3 g cm-3. What's more, the well-coated carbon insures the high electrical conductivity and the nano-sized LiFePO4/C particles shorten lithium ion transport, thus exhibiting the high specific capacity, high cycling stability and good rate performance.

  14. A facile route to modify ferrous phosphate and its use as an iron-containing resource for LiFePO4 via a polyol process.

    PubMed

    Li, Shaomin; Liu, Xichuan; Mi, Rui; Liu, Hao; Li, Yinchuan; Lau, Woon-min; Mei, Jun

    2014-06-25

    This study introduces an economical and environmentally friendly way of synthesizing LiFePO4/C to be used as cathode material in lithium ion batteries via two processes: (1) the synthesis of LiFePO4/C cathode material using a low cost divalent precursor ferrous phosphate, Fe3 (PO4)2·8H2O, as iron source in a polyol process and (2) the modification of the morphology of this precursor by varying the reaction time in a coprecipitation process. The study examines the effects of different structures and morphologies of the precursor on the structure and electrochemical performance of the as-synthesized LiFePO4/C. The LiFePO4/C shows an excellent rate capability and cycle performance, with initial discharge capacities of 153, 128, and 106 mA h g(-1) at 1 C, 5 C, and 10 C. The capacity retention is respectively 98.7%, 98.2%, and 98.7%, after 10 cycles at the corresponding rates. The capacity retention remains at 97% even after 300 cycles at the rate of 10 C. The outstanding electrochemical performance can be attributed to the improved rate of Li(+) diffusion and the excellent crystallinity of synthesized LiFePO4/C powders through the modified precursor. Therefore, this is an economical and environmentally friendly way of synthesizing LiFePO4/C to be used as cathode material in lithium ion batteries. PMID:24858212

  15. A simple and novel Si surface modification on LiFePO4@C electrode and its suppression of degradation of lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Yang, Wenyu; Zhuang, Zhenyuan; Chen, Xiang; Zou, Mingzhong; Zhao, Guiying; Feng, Qian; Li, Jiaxin; Lin, Yingbin; Huang, Zhigao

    2015-12-01

    A simple and novel surface modification device of the electrodes based on the ultrasonic spray technique was set up, which is considered to have the enormous prospect of industrial application due to its simpleness and high efficiency. Then, the nano-sized Si nanoparticles were deposited uniformly on the LiFePO4@C electrodes. In comparison with pristine LiFePO4@C electrode, the surface modification of the nano-sized Si with crystalline Si core and amorphous Si shell on the electrode surface exhibits less coarsening degree, higher rate capability, better cyclicity at high charge/discharge rate, especially at elevated temperature. Moreover, Raman spectra of LiFePO4@C, LiFePO4@C/Si electrodes before cycles and after 100 cycles at 1 C and 60 °C were measured. It is found that the FePO4 and α-Fe2O3 phases exist in LiFePO4@C after 100 cycles. On the contrary, there hardly exists the FePO4 and α-Fe2O3 phases, which means that the nano Si surface modification suppresses the degradation of lithium ion batteries. At last, the schematic and phenomenological resistance models of LiFePO4@C electrode modified by the nano-sized silicon particles have been suggested, which is responsible for the enhancement of the electrochemical performances after nano-sized Si surface modification.

  16. Boron and Nitrogen Codoped Carbon Layers of LiFePO4 Improve the High-Rate Electrochemical Performance for Lithium Ion Batteries.

    PubMed

    Zhang, Jinli; Nie, Ning; Liu, Yuanyuan; Wang, Jiao; Yu, Feng; Gu, Junjie; Li, Wei

    2015-09-16

    An evolutionary composite of LiFePO4 with nitrogen and boron codoped carbon layers was prepared by processing hydrothermal-synthesized LiFePO4. This novel codoping method is successfully applied to LiFePO4 for commercial use, and it achieved excellent electrochemical performance. The electrochemical performance can be improved through single nitrogen doping (LiFePO4/C-N) or boron doping (LiFePO4/C-B). When modifying the LiFePO4/C-B with nitrogen (to synthesis LiFePO4/C-B+N) the undesired nonconducting N-B configurations (190.1 and 397.9 eV) are generated. This decreases the electronic conductivity from 2.56×10(-2) to 1.30×10(-2) S cm(-1) resulting in weak electrochemical performance. Nevertheless, using the opposite order to decorate LiFePO4/C-N with boron (to obtain LiFePO4/C-N+B) not only eliminates the nonconducting N-B impurity, but also promotes the conductive C-N (398.3, 400.3, and 401.1 eV) and C-B (189.5 eV) configurations-this markedly improves the electronic conductivity to 1.36×10(-1) S cm(-1). Meanwhile the positive doping strategy leads to synergistic electrochemical activity distinctly compared with single N- or B-doped materials (even much better than their sum capacity at 20 C). Moreover, due to the electron and hole-type carriers donated by nitrogen and boron atoms, the N+B codoped carbon coating tremendously enhances the electrochemical property: at the rate of 20 C, the codoped sample can elevate the discharge capacity of LFP/C from 101.1 mAh g(-1) to 121.6 mAh g(-1), and the codoped product based on commercial LiFePO4/C shows a discharge capacity of 78.4 mAh g(-1) rather than 48.1 mAh g(-1). Nevertheless, the B+N codoped sample decreases the discharge capacity of LFP/C from 101.1 mAh g(-1) to 95.4 mAh g(-1), while the commercial LFP/C changes from 48.1 mAh g(-1) to 40.6 mAh g(-1). PMID:26305802

  17. LiFePO4 nanoparticles enveloped in freestanding sandwich-like graphitized carbon sheets as enhanced remarkable lithium-ion battery cathode.

    PubMed

    Zhang, Yan; Zhang, Huijuan; Li, Xiao; Xu, Haitao; Wang, Yu

    2016-04-15

    A novel nanostructure where LiFePO4 nanoparticles are enveloped in sandwich-like carbon sheets as an enhanced cathode in lithium-ion batteries has successfully been synthesized for the first time. Compared to previous carbon-based nanocomposites, the achieved sandwich-like LiFePO4 nanocomposites exhibit totally different architecture, in which LiFePO4 nanoparticles are tightly entrapped between two carbon layers, instead of being anchored on the carbon sheet surfaces. In other words, the achieved sandwich-like LiFePO4 nanocomposite carbon layers are actually freestanding and can be operated and separated from each other. This is a great breakthrough in the design and synthesis of carbon-based functional materials. The obtained sandwich-like LiFePO4 nanocomposites present excellent electrochemical performance, which is rationally ascribed to the superb and unique structure and architecture. Of particular note is that the freestanding sandwich-like LiFePO4 nanocomposites exhibit enhanced cyclability and rate capability. At a high current density of 0.1 A g(-1), a stable specific capacity of approximately 168.5 mAh g(-1) can be delivered over 1000 cycles, and when the charge-discharge rates increase to 0.6, 2, 5 and 10 A g(-1), the specific capacities still survive at 149, 129, 114 and 91 mAh g(-1), respectively. Meanwhile, the sandwiched nanocomposite demonstrates a significantly improved low-temperature electrochemical energy storage performance. With respect to the excellent Li storage performance, and facility and reliability of production, the freestanding sandwich-like LiFePO4 nanocomposites are reasonably believed to have a great potential for multiple electrochemical energy storage applications. PMID:26934516

  18. LiFePO4 nanoparticles enveloped in freestanding sandwich-like graphitized carbon sheets as enhanced remarkable lithium-ion battery cathode

    NASA Astrophysics Data System (ADS)

    Zhang, Yan; Zhang, Huijuan; Li, Xiao; Xu, Haitao; Wang, Yu

    2016-04-01

    A novel nanostructure where LiFePO4 nanoparticles are enveloped in sandwich-like carbon sheets as an enhanced cathode in lithium-ion batteries has successfully been synthesized for the first time. Compared to previous carbon-based nanocomposites, the achieved sandwich-like LiFePO4 nanocomposites exhibit totally different architecture, in which LiFePO4 nanoparticles are tightly entrapped between two carbon layers, instead of being anchored on the carbon sheet surfaces. In other words, the achieved sandwich-like LiFePO4 nanocomposite carbon layers are actually freestanding and can be operated and separated from each other. This is a great breakthrough in the design and synthesis of carbon-based functional materials. The obtained sandwich-like LiFePO4 nanocomposites present excellent electrochemical performance, which is rationally ascribed to the superb and unique structure and architecture. Of particular note is that the freestanding sandwich-like LiFePO4 nanocomposites exhibit enhanced cyclability and rate capability. At a high current density of 0.1 A g-1, a stable specific capacity of approximately 168.5 mAh g-1 can be delivered over 1000 cycles, and when the charge-discharge rates increase to 0.6, 2, 5 and 10 A g-1, the specific capacities still survive at 149, 129, 114 and 91 mAh g-1, respectively. Meanwhile, the sandwiched nanocomposite demonstrates a significantly improved low-temperature electrochemical energy storage performance. With respect to the excellent Li storage performance, and facility and reliability of production, the freestanding sandwich-like LiFePO4 nanocomposites are reasonably believed to have a great potential for multiple electrochemical energy storage applications.

  19. Excellent Temperature Performance of Spherical LiFePO4/C Composites Modified with Composite Carbon and Metal Oxides

    PubMed Central

    Zhang, Bao; Zeng, Tao; Zhang, Jiafeng; Peng, Chunli; Zheng, Junchao; Chen, Guomin

    2014-01-01

    Nanosized spherical LiFePO4/C composite was synthesized from nanosized spherical FePO4·2H2O, Li2C2O4, aluminum oxide, titanium oxide, oxalic acid, and sucrose by binary sintering process. The phases and morphologies of LiFePO4/C were characterized using SEM, TEM, CV, EIS, EDS, and EDX as well as charging and discharging measurements. The results showed that the as-prepared LiFePO4/C composite with good conductive webs from nanosized spherical FePO4·2H2O exhibits excellent electrochemical performances, delivering an initial discharge capacity of 161.7 mAh·g−1 at a 0.1 C rate, 152.4 mAh·g−1 at a 1 C rate and 131.7 mAh·g−1 at a 5 C rate, and the capacity retention of 99.1%, 98.7%, and 95.8%, respectively, after 50 cycles. Meanwhile, the high and low temperature performance is excellent for 18650 battery, maintaining capacity retention of 101.7%, 95.0%, 88.3%, and 79.3% at 55°C, 0°C, −10°C, and −20°C by comparison withthat of room temperature (25°C) at the 0.5 C rate over a voltage range of 2.2 V to 3.6 V, respectively. PMID:24526888

  20. Excellent temperature performance of spherical LiFePO4/C composites modified with composite carbon and metal oxides.

    PubMed

    Zhang, Bao; Zeng, Tao; Zhang, Jiafeng; Peng, Chunli; Zheng, Junchao; Chen, Guomin

    2014-01-01

    Nanosized spherical LiFePO4/C composite was synthesized from nanosized spherical FePO4 ·2H2O, Li2C2O4, aluminum oxide, titanium oxide, oxalic acid, and sucrose by binary sintering process. The phases and morphologies of LiFePO4/C were characterized using SEM, TEM, CV, EIS, EDS, and EDX as well as charging and discharging measurements. The results showed that the as-prepared LiFePO4/C composite with good conductive webs from nanosized spherical FePO4 ·2H2O exhibits excellent electrochemical performances, delivering an initial discharge capacity of 161.7 mAh·g(-1) at a 0.1 C rate, 152.4 mAh·g(-1) at a 1 C rate and 131.7 mAh·g(-1) at a 5 C rate, and the capacity retention of 99.1%, 98.7%, and 95.8%, respectively, after 50 cycles. Meanwhile, the high and low temperature performance is excellent for 18650 battery, maintaining capacity retention of 101.7%, 95.0%, 88.3%, and 79.3% at 55°C, 0°C, -10°C, and -20°C by comparison withthat of room temperature (25°C) at the 0.5 C rate over a voltage range of 2.2 V to 3.6 V, respectively. PMID:24526888

  1. Etched colloidal LiFePO4 nanoplatelets toward high-rate capable Li-ion battery electrodes.

    PubMed

    Paolella, Andrea; Bertoni, Giovanni; Marras, Sergio; Dilena, Enrico; Colombo, Massimo; Prato, Mirko; Riedinger, Andreas; Povia, Mauro; Ansaldo, Alberto; Zaghib, Karim; Manna, Liberato; George, Chandramohan

    2014-12-10

    LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently "plagued" by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of ∼ 155 mAh/g, ∼ 135 mAh/g, and ∼ 125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of ∼ 70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was ∼ 30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries. PMID:25372361

  2. Engineering 3D bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite for lithium storage with high rate capability and long cycle stability

    PubMed Central

    Zhang, Qian; Huang, Shao-Zhuan; Jin, Jun; Liu, Jing; Li, Yu; Wang, Hong-En; Chen, Li-Hua; Wang, Bin-Jie; Su, Bao-Lian

    2016-01-01

    A highly crystalline three dimensional (3D) bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite constructed by nanoparticles in the range of 50~100 nm via a rapid microwave assisted solvothermal process followed by carbon coating have been synthesized as cathode material for high performance lithium-ion batteries. The abundant 3D macropores allow better penetration of electrolyte to promote Li+ diffusion, the mesopores provide more electrochemical reaction sites and the carbon layers outside LiFePO4 nanoparticles increase the electrical conductivity, thus ultimately facilitating reverse reaction of Fe3+ to Fe2+ and alleviating electrode polarization. In addition, the particle size in nanoscale can provide short diffusion lengths for the Li+ intercalation-deintercalation. As a result, the 3D macro-mesoporous nanosized LiFePO4/C electrode exhibits excellent rate capability (129.1 mA h/g at 2 C; 110.9 mA h/g at 10 C) and cycling stability (87.2% capacity retention at 2 C after 1000 cycles, 76.3% at 5 C after 500 cycles and 87.8% at 10 C after 500 cycles, respectively), which are much better than many reported LiFePO4/C structures. Our demonstration here offers the opportunity to develop nanoscaled hierarchically porous LiFePO4/C structures for high performance lithium-ion batteries through microwave assisted solvothermal method. PMID:27181195

  3. Engineering 3D bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite for lithium storage with high rate capability and long cycle stability

    NASA Astrophysics Data System (ADS)

    Zhang, Qian; Huang, Shao-Zhuan; Jin, Jun; Liu, Jing; Li, Yu; Wang, Hong-En; Chen, Li-Hua; Wang, Bin-Jie; Su, Bao-Lian

    2016-05-01

    A highly crystalline three dimensional (3D) bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite constructed by nanoparticles in the range of 50~100 nm via a rapid microwave assisted solvothermal process followed by carbon coating have been synthesized as cathode material for high performance lithium-ion batteries. The abundant 3D macropores allow better penetration of electrolyte to promote Li+ diffusion, the mesopores provide more electrochemical reaction sites and the carbon layers outside LiFePO4 nanoparticles increase the electrical conductivity, thus ultimately facilitating reverse reaction of Fe3+ to Fe2+ and alleviating electrode polarization. In addition, the particle size in nanoscale can provide short diffusion lengths for the Li+ intercalation-deintercalation. As a result, the 3D macro-mesoporous nanosized LiFePO4/C electrode exhibits excellent rate capability (129.1 mA h/g at 2 C; 110.9 mA h/g at 10 C) and cycling stability (87.2% capacity retention at 2 C after 1000 cycles, 76.3% at 5 C after 500 cycles and 87.8% at 10 C after 500 cycles, respectively), which are much better than many reported LiFePO4/C structures. Our demonstration here offers the opportunity to develop nanoscaled hierarchically porous LiFePO4/C structures for high performance lithium-ion batteries through microwave assisted solvothermal method.

  4. Influence of memory effect on the state-of-charge estimation of large-format Li-ion batteries based on LiFePO4 cathode

    NASA Astrophysics Data System (ADS)

    Shi, Wei; Wang, Jiulin; Zheng, Jianming; Jiang, Jiuchun; Viswanathan, Vilayanur; Zhang, Ji-Guang

    2016-04-01

    In this work, we systematically investigated the influence of the memory effect of LiFePO4 cathodes in large-format full batteries. The electrochemical performance of the electrodes used in these batteries was also investigated separately in half-cells to reveal their intrinsic properties. We noticed that the memory effect of LiFePO4/graphite cells depends not only on the maximum state of charge reached during the memory writing process, but is also affected by the depth of discharge reached during the memory writing process. In addition, the voltage deviation in a LiFePO4/graphite full battery is more complex than in a LiFePO4/Li half-cell, especially for a large-format battery, which exhibits a significant current variation in the region near its terminals. Therefore, the memory effect should be taken into account in advanced battery management systems to further extend the long-term cycling stabilities of Li-ion batteries using LiFePO4 cathodes.

  5. Effect of complexing agents on the electrochemical performance of LiFePO4/C prepared by sol-gel method

    PubMed Central

    2012-01-01

    LiFePO4/C is synthesized via sol-gel method using Fe3+ as iron sources and different complexing agents, followed by sintering at high temperature for crystallization. The amount of carbon in these composites is less than 6.8 wt.%, and the X-ray diffraction experiment confirms that all samples are pure single phase indexed with the orthorhombic Pnma space group. The particle size of the LiFePO4/C synthesized by acetic acid as a complexing agent is very fine with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, is better than those of LiFePO4/C synthesized by other complexing agents. The cell of this sample can deliver a discharge capacity of 161.1 mAh g-1 at the first cycle. After 30 cycles, the capacity decreases to 157.5 mAh g-1, and the capacity fading rate is 2.2%. The mechanism is studied to explain the effect of a complexing agent on the synthesis of LiFePO4/C by sol-gel method. The results show that the complexing agent with a low stability constant may be proper for the synthetic process of LiFePO4/C via sol-gel method. PMID:22221711

  6. Desired crystal oriented LiFePO4 nanoplatelets in situ anchored on a graphene cross-linked conductive network for fast lithium storage.

    PubMed

    Wang, Bo; Liu, Anmin; Abdulla, Wael Al; Wang, Dianlong; Zhao, X S

    2015-05-21

    Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a "platelet-on-sheet" LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (∼56 mA h g(-1) at 60 C) and long life cycling stability (∼87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (∼98% capacity retention over 1000 cycles at 10 C). PMID:25908535

  7. Engineering 3D bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite for lithium storage with high rate capability and long cycle stability.

    PubMed

    Zhang, Qian; Huang, Shao-Zhuan; Jin, Jun; Liu, Jing; Li, Yu; Wang, Hong-En; Chen, Li-Hua; Wang, Bin-Jie; Su, Bao-Lian

    2016-01-01

    A highly crystalline three dimensional (3D) bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite constructed by nanoparticles in the range of 50~100 nm via a rapid microwave assisted solvothermal process followed by carbon coating have been synthesized as cathode material for high performance lithium-ion batteries. The abundant 3D macropores allow better penetration of electrolyte to promote Li(+) diffusion, the mesopores provide more electrochemical reaction sites and the carbon layers outside LiFePO4 nanoparticles increase the electrical conductivity, thus ultimately facilitating reverse reaction of Fe(3+) to Fe(2+) and alleviating electrode polarization. In addition, the particle size in nanoscale can provide short diffusion lengths for the Li(+) intercalation-deintercalation. As a result, the 3D macro-mesoporous nanosized LiFePO4/C electrode exhibits excellent rate capability (129.1 mA h/g at 2 C; 110.9 mA h/g at 10 C) and cycling stability (87.2% capacity retention at 2 C after 1000 cycles, 76.3% at 5 C after 500 cycles and 87.8% at 10 C after 500 cycles, respectively), which are much better than many reported LiFePO4/C structures. Our demonstration here offers the opportunity to develop nanoscaled hierarchically porous LiFePO4/C structures for high performance lithium-ion batteries through microwave assisted solvothermal method. PMID:27181195

  8. Electrochemical performance of NiO-doped LiFePO4/C cathode materials prepared from amorphous FePO4 · xH2O

    NASA Astrophysics Data System (ADS)

    Mahmud, Iqbal; Kim, Dong-Seob; Ur, Soon-Chul

    2016-05-01

    LiFePO4/C composites are prepared from amorphous FePO4 · xH2O and are modified with NiO (0.0, 0.01, 0.02, 0.03, and 0.04 mol) by using a solid-state reaction process with a spex milling system. The crystalline structure and the morphology of synthesized powders have been characterized by using X-ray diffraction (XRD) and scanning electron microscope (SEM). The XRD patterns indicate a complete solid solution for all the NiO-doped LiFePO4/C composites. The SEM images show that the sizes of the particles produced are distributed in the range of 200 - 300 nm. The electrochemical performances have been evaluated by using an impedance measurement and a galvanostatic charge/discharge test. The initial properties and impedance measurement reveal different improvements for different amounts of NiO doping in LiFePO4/C. A maximum capacity of 158.8 mAh/g at 0.1 C has been achieved LiFePO4/C doped with NiO at 0.01 mol. The present work reveals that the newly processed composite of LiFePO4/C doped with a small amount of NiO may be a promising material for using in a lithium-ion battery.

  9. In situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates for superior Li-ion battery cathodes.

    PubMed

    Ma, Zhipeng; Fan, Yuqian; Shao, Guangjie; Wang, Guiling; Song, Jianjun; Liu, Tingting

    2015-02-01

    The low electronic conductivity and one-dimensional diffusion channel along the b axis for Li ions are two major obstacles to achieving high power density of LiFePO4 material. Coating carbon with excellent conductivity on the tailored LiFePO4 nanoparticles therefore plays an important role for efficient charge and mass transport within this material. We report here the in situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates with highly oriented (010) facets by introducing ferrocene as a catalyst during thermal treatment. The as-obtained material exhibits superior performances for Li-ion batteries at high rate (100 C) and low temperature (-20 °C), mainly because of fast electron transport through the graphitic carbon layer and efficient Li(+)-ion diffusion through the thin nanoplates. PMID:25584530

  10. Li-Ion Battery with LiFePO4 Cathode and Li4Ti5O12 Anode for Stationary Energy Storage

    SciTech Connect

    Wang, Wei; Choi, Daiwon; Yang, Zhenguo

    2013-01-01

    i-ion batteries based on commercially available LiFePO4 cathode and Li4Ti5O12 anode were investigated for potential stationary energy storage applications. The full cell that operated at flat 1.85V demonstrated stable cycling for 200 cycles followed by a rapid fade. A significant improvement in cycling stability was achieved via Ketjen black coating of the cathode. A Li-ion full cell with Ketjen black modified LiFePO4 cathode and an unmodified Li4Ti5O12 anode exhibited negligible fade after more than 1200 cycles with a capacity of ~130mAh/g. The improved stability, along with its cost-effectiveness, environmentally benignity and safety, make the LiFePO4/ Li4Ti5O12 Li-ion battery a promising option of storing renewable energy.

  11. Space matters: Li+ conduction versus strain effect at FePO4/LiFePO4 interface

    NASA Astrophysics Data System (ADS)

    Lv, Weiqiang; Niu, Yinghua; Jian, Xian; Zhang, Kelvin H. L.; Wang, Wei; Zhao, Jiyun; Wang, Zhiming; Yang, Weiqing; He, Weidong

    2016-02-01

    FePO4/LiFePO4 (FP/LFP) interfacial strain, giving rise to substantial variation in interfacial energy and lattice volume, is inevitable in the (de)lithiation process of LiFePO4, a prototype of Li ion battery cathodes. Extensive theoretical and experimental research has been focused on the effect of lattice strain energy on FP/LFP interface propagation orientation and cyclic stability of the electrode. However, the essential effect of strain induced lattice distortion on Li+ transport at the FP/LFP interface is typically overlooked. In this report, a coherent interface model is derived to evaluate quantitatively the correlation between FP/LFP lattice distortion and Li+ conduction. The results illustrate that the effect of lattice strain on Li+ conduction depends strongly on FP/LFP interface orientations. Lattice strain induces a 90% decrease of Li+ conductivity in ac-plane oriented (de)lithiation at room temperature. The opposite effect of lattice strain on delithiation and lithiation for ab- and bc-orientations is elucidated. In addition, the effect of lattice strain tends to be more pronounced at a lower working temperature. This study provides an efficient platform to comprehend and manipulate Li+ conduction in the charge and discharge of lithium ion batteries, the large-scale application of which is frequently challenged by limited in-cell ion conduction.

  12. Sequential Monte Carlo filter for state estimation of LiFePO4 batteries based on an online updated model

    NASA Astrophysics Data System (ADS)

    Li, Jiahao; Klee Barillas, Joaquin; Guenther, Clemens; Danzer, Michael A.

    2014-02-01

    Battery state monitoring is one of the key techniques in battery management systems e.g. in electric vehicles. An accurate estimation can help to improve the system performance and to prolong the battery remaining useful life. Main challenges for the state estimation for LiFePO4 batteries are the flat characteristic of open-circuit-voltage over battery state of charge (SOC) and the existence of hysteresis phenomena. Classical estimation approaches like Kalman filtering show limitations to handle nonlinear and non-Gaussian error distribution problems. In addition, uncertainties in the battery model parameters must be taken into account to describe the battery degradation. In this paper, a novel model-based method combining a Sequential Monte Carlo filter with adaptive control to determine the cell SOC and its electric impedance is presented. The applicability of this dual estimator is verified using measurement data acquired from a commercial LiFePO4 cell. Due to a better handling of the hysteresis problem, results show the benefits of the proposed method against the estimation with an Extended Kalman filter.

  13. Impact of carbon structure and morphology on the electrochemical performance of LiFePO4/C composites

    SciTech Connect

    Doeff, Marca M.; Doeff, Marca M.; Wilcox, James D.; Yu, Rong; Aumentado, Albert; Marcinek, Marek; Kostecki, Robert

    2007-09-19

    The electrochemical performance of LiFePO4/C composites in lithium cells is closely correlated to pressed pellet conductivities measured by AC impedance methods. These composite conductivities are a strong function not only of the amount of carbon but of its structure and distribution. Ideally, the amount of carbon in composites should be minimal (less than about 2 wtpercent) so as not to decrease the energy density unduly. This is particularly important for plug-in hybrid electric vehicle applications (PHEVs) where both high power and moderate energy density are required. Optimization of the carbon structure, particularly the sp2/sp3 and disordered/graphene (D/G) ratios, improves the electronic conductivity while minimizing the carbon amount. Manipulation of the carbon structure can be achieved via the use of synthetic additives including ironcontaining graphitization catalysts. Additionally, combustion synthesis techniques allow co-synthesis of LiFePO4 and carbon fibers or nanotubes, which can act as"nanowires" for the conduction of current during cell operation.

  14. Double Carbon Nano Coating of LiFePO4 Cathode Material for High Performance of Lithium Ion Batteries.

    PubMed

    Ding, Yan-Hong; Huang, Guo-Long; Li, Huan-Huan; Xie, Hai-Ming; Sun, Hai-Zhu; Zhang, Jing-Ping

    2015-12-01

    Double carbon-coated LiFePO4 (D-LiFePO4/C) composite with sphere-like structure was synthesized through combination of co-precipitation and solid-state methods. Cetyl-trimethyl-ammonium bromide (CTAB) and citric acid served as two kinds of carbon sources in sequence. SEM images demonstrated that double carbon coating had certain influence on the morphology. The thickness of carbon coating on D-LiFePO4/C was about 1.7 nm and the content of carbon was 2.48 wt%, according to HRTEM and TG analysis. The electrochemical impedance spectroscopy analysis indicated that the D-LiFePO4/C composite presented the charge-transfer resistance of 68 Ω and Li ion diffusion coefficient of 2.68 x 10(-13) cm2 S(-1), while the single carbon-coated LiFePO4 (S-LiFePO4/C) exhibited 135.5Ω and 4.03 x 10(-14) cm2 S(-1). Especially, the prepared D-LiFePO4/C electrode showed discharge capacities of 102.9 (10C) and 87.1 (20C) mA h g(-1), respectively, with almost no capacity lost after 400 cycles at 10C, which were much better than those of S-LiFePO4/C composite. PMID:26682389

  15. Enhancement of electrochemical behavior of nanostructured LiFePO4/Carbon cathode material with excess Li

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Nazri, M.; Naik, V. M.; Garg, V. K.; Oliveira, A. C.; Vaishnava, P. P.; Nazri, G. A.; Naik, R.

    2016-02-01

    We have synthesized carbon coated LiFePO4 (C-LiFePO4) and C-Li1.05FePO4 with 5 mol% excess Li via sol-gel method using oleic acid as a source of carbon for enhancing electronic conductivity and reducing the average particle size. Although the phase purity of the crystalline samples was confirmed by x-ray diffraction (XRD), the 57Fe Mössbauer spectroscopy analyses show the presence of ferric impurity phases in both stoichiometric and non-stoichiometric C-LiFePO4 samples. Transmission electron microscopy measurements show nanosized C-LiFePO4 particles uniformly covered with carbon, with average particle size reduced from ∼100 nm to ∼50 nm when excess lithium is used. Electrochemical measurements indicate a lower charge transfer resistance and better electrochemical performance for C-Li1.05FePO4 compared to that of C-LiFePO4. The aim of this work is to systematically analyze the nature of impurities formed during synthesis of LiFePO4 cathode material, and their impact on electrochemical performance. The correlation between the morphology, charge transfer resistance, diffusion coefficient and electrochemical performance of C-LiFePO4 and C- Li1.05FePO4 cathode materials are discussed.

  16. Physical and electrochemical properties of LiFePO 4 nanoparticles synthesized by a combination of spray pyrolysis with wet ball-milling

    NASA Astrophysics Data System (ADS)

    Konarova, Muxina; Taniguchi, Izumi

    A novel preparation technique was developed to synthesize LiFePO 4 nanoparticles through a combination of spray pyrolysis (SP) with wet ball-milling (WBM). Using this technique, the preparation of LiFePO 4 nanoparticles was investigated for a wide range of process parameters such as ball-milling time and sintering temperature. The effect of process parameters on the physical and electrochemical properties of LiFePO 4 was then discussed through analysis using by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), the Brunauer-Emmet-Teller (BET) method, Raman spectroscopy and using an electrochemical cell of Li|1 M LiClO 4 in EC:DEC = 1:1|LiFePO 4. LiFePO 4 nanoparticles with a geometric mean diameter of 58 nm were prepared at a rotating speed of 800 rpm and a ball-milling time of 12 h in an Ar atmosphere followed by heat treatment at 500 °C for 4 h in a N 2 + 3% H 2 atmosphere. The sample delivered first discharge capacities of 164 and 100 mAh g -1 at charge-discharge rates of 0.1 and 10 C in the test cells, respectively. The electrochemical properties of LiFePO 4 nanoparticles were strongly affected by the formation of Fe 2P, Fe 3P and α-Fe 2O 3 at higher charge-discharge rates.

  17. Etched Colloidal LiFePO4 Nanoplatelets toward High-Rate Capable Li-Ion Battery Electrodes

    PubMed Central

    2014-01-01

    LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently “plagued” by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of ∼155 mAh/g, ∼135 mAh/g, and ∼125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of ∼70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was ∼30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries. PMID:25372361

  18. Current density and state of charge inhomogeneities in Li-ion battery cells with LiFePO4 as cathode material due to temperature gradients

    NASA Astrophysics Data System (ADS)

    Fleckenstein, Matthias; Bohlen, Oliver; Roscher, Michael A.; Bäker, Bernard

    2011-05-01

    Current density distributions and local state of charge (SoC) differences that are caused by temperature gradients inside actively cooled Li-ion battery cells are discussed and quantified. As an example, a cylindrical Li-ion cell with LiFePO4 as cathode material (LiFePO4-cell) is analyzed in detail both experimentally and by means of spatial electro-thermal co-simulations. The reason for current density inhomogeneities is found to be the local electrochemical impedance varying with temperature in different regions of the jelly roll. For the investigated cell, high power cycling and the resulting temperature gradient additionally cause SoC-gradients inside the jelly roll. The local SoCs inside one cell diverge firstly because of asymmetric current density distributions during charge and discharge inside the cell and secondly because of the temperature dependence of the local open circuit potential. Even after long relaxation periods, the SoC distribution in cycled LiFePO4-cells remains inhomogeneous across the jelly roll as a result of hysteresis in the open circuit voltage. The occurring thermal electrical inhomogeneities are expected to influence local aging differences and thus, global cell aging. Additionally the occurrence of inhomogeneous current flow and SoC-development inside non-uniformly cooled battery packs of parallel connected LiFePO4-cells is measured and discussed.

  19. Effect of Surfactants on the Physical Properties and Electrochemical Performance of LiFePO4 Cathode Material for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Naik, R.; Nazri, G. A.; Nazri, M.; Naik, V.; Mandal, B. P.; Vaishnava, P. P.

    2012-10-01

    Use of lithium iron phosphate in lithium ion battery is hampered by the poor electronic conductivity and slow lithium ion diffusion. Several methods have been tried to improve the conductivity. Carbon coating is found to be very suitable way to enhance the electronic conductivity. Here, we report synthesis of carbon coated LiFePO4 composite materials using lauric, myristic, and oleic acid as source of carbon. The phase purity of these three LiFePO4/C composites was confirmed by X-Ray Diffraction. The quality of carbon coating has been investigated by Raman spectroscopy. In all the samples, the carbon content is found to be approximately 10%. SEM and TEM investigations reveal that the surfactants coat the LiFePO4 particles uniformly with carbon and the coating reduces the particle size to approximately 30 nm. Due to high electrical conductivity, controlled particle size and suitable microstructure, among the three LiFePO4 coated samples, the sample prepared in presence of lauric acid exhibited superior electrochemical performance in terms of specific capacity, the cycling stability and delivered high discharge capacity of ˜140 mAhg-1 at C/2 rate.

  20. Why LiFePO4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation

    NASA Astrophysics Data System (ADS)

    Wang, Yung Jui; Liu, Xiaosong; Barbiellini, B.; Hafiz, Hasnain; Basak, Susmita; Liu, Jun; Richardson, Thomas; Shu, Guojiun; Chou, Fangcheng; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Moritz, B.; Devereaux, T. P.; Qiao, Ruimin; Chuang, Yi-De; Bansil, Arun; Hussain, Zahid; Yang, Wanli

    We performed systematic experimental and theoretical studies based on soft X-ray emission, absorption, and hard X-ray Raman spectroscopy of LixFePO4. The results show a non-rigid electron-state reconfiguration of both the occupied and unoccupied Fe-3d and O-2p states during the (de)lithiation process. The critical 3d electron state configurations are consistent with the calculations based on MBJGGA+U framework, which improves the overall lineshape prediction compared with the conventionally used GGA+U method. The combined experimental and theoretical studies show that the non-rigid electron state reshuffling guarantees the stability of oxygen during the redox reaction throughout the charge and discharge process of LiFePO4 electrodes, leading to the intrinsic safe performance of the electrodes. Work supported by the US DOE.

  1. Preparation and characterization of mesoporous LiFePO 4/C microsphere by spray drying assisted template method

    NASA Astrophysics Data System (ADS)

    Yu, Feng; Zhang, Jingjie; Yang, Yanfeng; Song, Guangzhi

    Mesoporous LiFePO 4/C microsphere was successfully prepared by spray drying assisted template method (SDATM) with citric acid as a template. This material has an average pore size of 50 nm and gives large specific surface area (32.2 m 2 g -1) with evenly distributed carbon (4.3 wt.%). It is also easy to bring into contact with electrolyte, facilitate the electric and lithium ion diffusion. It presents large reversible capacity of 158.8 mAh g -1 at C/10, even high rate capacity of 59.7 mAh g -1 at 20 C, and excellent capacity retention rate closed to 95.5% after various current densities.

  2. Simplified electrochemical multi-particle model for LiFePO4 cathodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Mastali Majdabadi, Mehrdad; Farhad, Siamak; Farkhondeh, Mohammad; Fraser, Roydon A.; Fowler, Michael

    2015-02-01

    A simplified physics-based model is developed to predict the performance of an LiFePO4 cathode at various operating and design conditions. Newman's full-order porous-electrode model is simplified using polynomial approximations for electrolyte variables at the electrode-level while a multi-particle model featuring variable solid-state diffusivity is employed at the particle level. The computational time of this reduced-order model is decreased by almost one order of magnitude compared to the full-order model without sacrificing the accuracy of the results. The model is general and can be used to expedite the simulation of any composite electrode with active-material particles of non-uniform properties (e.g., size, contact resistance, material chemistry etc.). In a broader perspective, this model is of practical value for electric vehicle power train simulations and battery management systems.

  3. Vacancy-driven anisotropic defect distribution in the battery-cathode material LiFePO4.

    PubMed

    Lee, Jaekwang; Zhou, Wu; Idrobo, Juan C; Pennycook, Stephen J; Pantelides, Sokrates T

    2011-08-19

    Li-ion mobility in LiFePO(4), a key property for energy applications, is impeded by Fe antisite defects (Fe(Li)) that form in select b-axis channels. Here we combine first-principles calculations, statistical mechanics, and scanning transmission electron microscopy to identify the origin of the effect: Li vacancies (V(Li)) are confined in one-dimensional b-axis channels, shuttling between neighboring Fe(Li). Segregation in select channels results in shorter Fe(Li)-Fe(Li) spans, whereby the energy is lowered by the V(Li)'s spending more time bound to end-point Fe(Li)'s. V(Li)-Fe(Li)-V(Li) complexes also form, accounting for observed electron energy loss spectroscopy features. PMID:21929178

  4. Ink-jet printed porous composite LiFePO4 electrode from aqueous suspension for microbatteries

    NASA Astrophysics Data System (ADS)

    Delannoy, P.-E.; Riou, B.; Brousse, T.; Le Bideau, J.; Guyomard, D.; Lestriez, B.

    2015-08-01

    This work demonstrates ink-jet printed LiFePO4-based composite porous electrodes for microbattery application. As binder and dispersant, we found that aqueous inks with more suitable rheological properties with respect to ink-jet printing are prepared with the low molecular weight poly-acrylic-co-maleic acid copolymer, rather than with the carboxymethyl cellulose standard binder of the lithium-ion technology. The ink-jet printed thin and porous electrode shows very high rate charge/discharge behavior, both in LiPF6/ethylene carbonate-dimethyl carbonate (LP30) and lithium bis(trifluoromethane)sulfonylimide salt (Li-TFSI) in N-methyl-N-propylpyrrolidinium bis(trifluoromethane)suflonylimide ionic liquid (PYR13-TFSI) electrolytes, as well as good cyclability.

  5. Desired crystal oriented LiFePO4 nanoplatelets in situ anchored on a graphene cross-linked conductive network for fast lithium storage

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Liu, Anmin; Abdulla, Wael Al; Wang, Dianlong; Zhao, X. S.

    2015-05-01

    Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a ``platelet-on-sheet'' LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (~56 mA h g-1 at 60 C) and long life cycling stability (~87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (~98% capacity retention over 1000 cycles at 10 C).Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a ``platelet-on-sheet'' LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (~56 mA h g-1 at 60 C) and long life cycling stability (~87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (~98% capacity retention over 1000 cycles at 10 C). Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01831e

  6. Enhancement of electrochemical performances for LiFePO4/C with 3D-grape-bunch structure and selection of suitable equivalent circuit for fitting EIS results

    NASA Astrophysics Data System (ADS)

    Li, Xiangfeng; Luo, Dongmei; Zhang, Xin; Zhang, Zhao

    2015-09-01

    The LiFePO4/C composite with 3D-grape-bunch structure is successfully synthesized through a novel hydrothermal method. Sucrose is used as in-situ coating carbon source, and the hydroxylated MWCNTs are used as connecting carbon wires which can be embedded into the carbon coating via self-assembling of the hydrophilic groups to form 3D-grape-bunch structure. The influences of the 3D-grape-bunch structure on the morphology, structure and electrochemical performance of the LiFePO4/C composites are investigated by XRD, SEM, TEM, BET, galvanostatic charge/discharge tests, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) tests. Especially, four kinds of the equivalent circuit models usually employed to analysis the EISs of LiFePO4 as cathode material for Li-ion battery are discussed, and the suitable equivalent circuit for fitting EIS of LiFePO4/C composite with 3D-grape-bunch structure is selected. The optimal LiFePO4/C composite with 3D-grape-bunch structure owing to its good conductive network and high graphitic degree (low ID/IG value) of residual carbon exhibits a stable and high reversible capacity of 160.5 mAh g-1 at 0.1C and 108.4 mAh g-1 even at 10.0C, and the cycling capacity retention rate reaches 99.9% over 60 cycles. Moreover, it also exhibits high conductivity, good reversibility and excellent stability in EIS and CV tests.

  7. LiFePO4 Nanostructures Fabricated from Iron(III) Phosphate (FePO4 x 2H2O) by Hydrothermal Method.

    PubMed

    Saji, Viswanathan S; Song, Hyun-Kon

    2015-01-01

    Electrode materials having nanometer scale dimensions are expected to have property enhancements due to enhanced surface area and mass/charge transport kinetics. This is particularly relevant to intrinsically low electronically conductive materials such as lithium iron phosphate (LiFePO4), which is of recent research interest as a high performance intercalation electrode material for Li-ion batteries. Many of the reported works on LiFePO4 synthesis are unattractive either due to the high cost of raw materials or due to the complex synthesis technique. In this direction, synthesis of LiFePO4 directly from inexpensive FePO4 shows promise.The present study reports LiFePO4 nanostructures prepared from iron (III) phosphate (FePO4 x 2H2O) by precipitation-hydrothermal method. The sintered powder was characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), Inductive coupled plasma-optical emission spectroscopy (ICP-OES), and Electron microscopy (SEM and TEM). Two synthesis methods, viz. bulk synthesis and anodized aluminum oxide (AAO) template-assisted synthesis are reported. By bulk synthesis, micro-sized particles having peculiar surface nanostructuring were formed at precipitation pH of 6.0 to 7.5 whereas typical nanosized LiFePO4 resulted at pH ≥ 8.0. An in-situ precipitation strategy inside the pores of AAO utilizing the spin coating was utilized for the AAO-template-assisted synthesis. The template with pores filled with the precipitate was subsequently subjected to hydrothermal process and high temperature sintering to fabricate compact rod-like structures. PMID:26328435

  8. A method for state-of-charge estimation of LiFePO4 batteries based on a dual-circuit state observer

    NASA Astrophysics Data System (ADS)

    Tang, Xiaopeng; Wang, Yujie; Chen, Zonghai

    2015-11-01

    Estimation of state-of-charge (SOC) is a key criterion to evaluate the battery management system (BMS). Due to the flat open-circuit voltage (OCV)-SOC curve of LiFePO4 batteries, it is a great challenge to estimate the SOC accurately. Here we present a dual-circuit state observer for SOC estimation of LiFePO4 batteries. It is a combination of an open loop based current integrator and a proportional-integral (PI) based state observer. We also employed an easy but practical drifting current corrector to restrain the influence of the drifting current. The experiment results show that error of the estimated SOC is less than 2.5% by the proposed method when the initial SOC is unknown. We proved that with no matrix operations, the proposed method is lighted-weighted and high efficient, which is suitable for embedded systems.

  9. Electrical and electrochemical characterization of nano-sized LiFePO4 cathode materials synthesized by a lauric acid-based sol--gel method

    NASA Astrophysics Data System (ADS)

    Bazzi, Khadije; Dixit, Ambesh; Naik, Ratna; Naik, Vaman; Vaishnava, Prem; Nazri, Abbas; Nazri, Mariam

    2011-04-01

    We synthesized pure LiFePO4 and C-LiFePO4 nanoparticles by sol-gel technique. Carbon coating was accomplished by including Lauric acid in the sol-gel precursor solution. Three C-LiFePO4 samples of particle sizes 29, 27, 23 nm, were prepared by varying lauric acid concentration in the precursor solution. All the samples were characterized by X-ray diffraction, Raman, conductivity, and electrochemical measurements. The micro-Raman measurements showed two major bands at 1350 and 1590 cm-1 respectively (ID/IG) and the electronic conductivity were found to depend strongly on the amount of surfactant coverage. The 23 nm particle size sample showed minimum (D/G) band ratio and the maximum electrical conductivity among the three samples. The measured value of the capacity for 23 nm sized sample, ˜ 170 mAh/g, approached the theoretical capacity limit value for LiFePO4

  10. Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism.

    PubMed

    Seifitokaldani, Ali; Gheribi, Aïmen E; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

    2016-01-01

    A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures. PMID:27604551

  11. LiFePO 4: From molten ingot to nanoparticles with high-rate performance in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zaghib, K.; Charest, P.; Dontigny, M.; Guerfi, A.; Lagacé, M.; Mauger, A.; Kopec, M.; Julien, C. M.

    LiFePO 4 (LFP) particles were obtained by grinding ingot synthesized in the molten state. This process, followed by jet milling, and then wet milling, provides a simple way to obtain powders with controlled particle size in the range from macroscopic to 25 nm. However, at this time, we find that these particles tend to agglomerate to form secondary particles of size ∼100 nm. The particles obtained by this process are characterized by X-ray diffraction (XRD). In situ and ex situ scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The effect of milling was also investigated by analysis of physical properties using infrared spectroscopy (FTIR) and magnetic measurements. The electrochemical performance was evaluated in cells containing Li/1 M LiPF 6 in EC:DEC (1:1)/C-LiFePO 4. After carbon coating, the LFP particles which are free of impurities, exhibit high-rate capability. Even with a limited amount of carbon (2 wt.%) appropriate for commercial batteries, the capacity is 157 mAh g -1 at 0.1 C, 120 mAh g -1 at 10 C, without capacity fading after 60 cycles.

  12. Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism

    PubMed Central

    Seifitokaldani, Ali; Gheribi, Aïmen E.; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

    2016-01-01

    A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures. PMID:27604551

  13. Fast charging technique for high power LiFePO4 batteries: A mechanistic analysis of aging

    NASA Astrophysics Data System (ADS)

    Anseán, D.; Dubarry, M.; Devie, A.; Liaw, B. Y.; García, V. M.; Viera, J. C.; González, M.

    2016-07-01

    One of the major issues hampering the acceptance of electric vehicles (EVs) is the anxiety associated with long charging time. Hence, the ability to fast charging lithium-ion battery (LIB) systems is gaining notable interest. However, fast charging is not tolerated by all LIB chemistries because it affects battery functionality and accelerates its aging processes. Here, we investigate the long-term effects of multistage fast charging on a commercial high power LiFePO4-based cell and compare it to another cell tested under standard charging. Coupling incremental capacity (IC) and IC peak area analysis together with mechanistic model simulations ('Alawa' toolbox with harvested half-cell data), we quantify the degradation modes that cause aging of the tested cells. The results show that the proposed fast charging technique caused similar aging effects as standard charging. The degradation is caused by a linear loss of lithium inventory, coupled with a less degree of linear loss of active material on the negative electrode. This study validates fast charging as a feasible mean of operation for this particular LIB chemistry and cell architecture. It also illustrates the benefits of a mechanistic approach to understand cell degradation on commercial cells.

  14. Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling

    PubMed Central

    Zhang, Xiaoyu; van Hulzen, Martijn; Singh, Deepak P.; Brownrigg, Alex; Wright, Jonathan P.; van Dijk, Niels H.; Wagemaker, Marnix

    2015-01-01

    Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is hindering fundamental understanding and progress. Here we use synchrotron microbeam diffraction to disclose the cycling rate-dependent phase transition mechanism within individual particles of LiFePO4, a key Li-ion electrode material. At low (dis)charge rates well-defined nanometer thin plate-shaped domains co-exist and transform much slower and concurrent as compared with the commonly assumed mosaic transformation mechanism. As the (dis)charge rate increases phase boundaries become diffuse speeding up the transformation rates of individual grains. Direct observation of the transformation of individual grains reveals that local current densities significantly differ from what has previously been assumed, giving new insights in the working of Li-ion battery electrodes and their potential improvements. PMID:26395323

  15. Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling.

    PubMed

    Zhang, Xiaoyu; van Hulzen, Martijn; Singh, Deepak P; Brownrigg, Alex; Wright, Jonathan P; van Dijk, Niels H; Wagemaker, Marnix

    2015-01-01

    Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is hindering fundamental understanding and progress. Here we use synchrotron microbeam diffraction to disclose the cycling rate-dependent phase transition mechanism within individual particles of LiFePO4, a key Li-ion electrode material. At low (dis)charge rates well-defined nanometer thin plate-shaped domains co-exist and transform much slower and concurrent as compared with the commonly assumed mosaic transformation mechanism. As the (dis)charge rate increases phase boundaries become diffuse speeding up the transformation rates of individual grains. Direct observation of the transformation of individual grains reveals that local current densities significantly differ from what has previously been assumed, giving new insights in the working of Li-ion battery electrodes and their potential improvements. PMID:26395323

  16. State-of-health estimation of LiFePO4/graphite batteries based on a model using differential capacity

    NASA Astrophysics Data System (ADS)

    Torai, Soichiro; Nakagomi, Masaru; Yoshitake, Satoshi; Yamaguchi, Shuichiro; Oyama, Noboru

    2016-02-01

    A model for expressing the differential capacity characteristics of the LiFePO4 (LFP)/graphite battery for the state-of-health (SOH) estimation was proposed. Our model was based on the deformed pseudo-Voigt peak function with several parameters which are directly associated with the phase transition behavior of the active LFP and graphite materials. Charge/discharge cycle tests for accelerated battery fading were performed under a constant high-temperature condition (40 and 45 °C). The SOH estimation was carried out at different fading point of the battery using a part of the responses for the differential capacity versus voltage (dQ/dV vs. V) against the charging process at the rate of C/5 under constant temperature of 25 °C. The changes in the variables of the model with cycling were correlated to the generally mentioned phenomena that the main factors determining the capacity fading of the LFP/graphite battery are the loss of Li+ by a side reaction and that of the active electrode materials. In addition, the robustness related to the charge/discharge history was confirmed, since the memory effect of the LFP/graphite battery, being induced by the previous condition for use, has an influence on the dQ/dV vs. V. The evaluated SOH errors were within ±3%.

  17. Electron microscopy investigations of changes in morphology and conductivity of LiFePO4/C electrodes

    NASA Astrophysics Data System (ADS)

    Scipioni, Roberto; Jørgensen, Peter S.; Ngo, Duc-The; Simonsen, Søren B.; Liu, Zhao; Yakal-Kremski, Kyle J.; Wang, Hongqian; Hjelm, Johan; Norby, Poul; Barnett, Scott A.; Jensen, Søren H.

    2016-03-01

    In this work we study the structural degradation of a laboratory Li-ion battery LiFePO4/Carbon Black (LFP/CB) cathode by various electron microscopy techniques including low kV Focused Ion Beam (FIB)/Scanning Electron Microscopy (SEM) 3D tomography. Several changes are observed in FIB/SEM images of fresh and degraded cathodes, including cracks in the LFP particles, secondary disconnected particles, and agglomeration of CB. Low voltage (1 kV) SEM images show that the CB agglomerates have a different brightness than the fresh CB, due to charging effects. This suggests that the electronic conductivity of the CB agglomerates is low compared to that of the fresh CB particles. HRTEM analysis shows that fresh CB particles are quasi crystalline, whereas the LFP/CB interface in the degraded electrode shows amorphous carbon surrounding the LFP particles. The presence of the amorphous carbon is known to impede the electronic conductivity and thereby decreasing percolation in the cathode and reducing the electrode capacity.

  18. Combined operando X-ray diffraction-electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries.

    PubMed

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

    2015-01-01

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4. PMID:26345306

  19. Combined operando X-ray diffraction-electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries

    NASA Astrophysics Data System (ADS)

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

    2015-09-01

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ~20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4.

  20. Increasing the Affinity Between Carbon-Coated LiFePO4/C Electrodes and Conventional Organic Electrolyte by Spontaneous Grafting of a Benzene-Trifluoromethylsulfonimide Moiety.

    PubMed

    Delaporte, Nicolas; Perea, Alexis; Lebègue, Estelle; Ladouceur, Sébastien; Zaghib, Karim; Bélanger, Daniel

    2015-08-26

    The grafting of benzene-trifluoromethylsulfonimide groups on LiFePO4/C was achieved by spontaneous reduction of in situ generated diazonium ions of the corresponding 4-amino-benzene-trifluoromethylsulfonimide. The diazotization of 4-amino-benzene-trifluoromethylsulfonimide was a slow process that required a high concentration of precursors to promote the spontaneous grafting reaction. Contact angle measurements showed a hydrophilic surface was produced after the reaction that is consistent with grafting of benzene-trifluoromethylsulfonimide groups. Elemental analysis data revealed a 2.1 wt % loading of grafted molecules on the LiFePO4/C powder. Chemical oxidation of the cathode material during the grafting reaction was detected by X-ray diffraction and quantified by inductively coupled plasma atomic emission spectrometry. Surface modification improves the wettability of the cathode material, and better discharge capacities were obtained for modified electrodes at high C-rate. In addition, electrochemical impedance spectroscopy showed the resistance of the modified cathode was lower than that of the bare LiFePO4/C film electrode. Moreover, the modified cathode displayed superior capacity retention after 200 cycles of charge/discharge at 1 C. PMID:26186016

  1. Magnetic susceptibility as a direct measure of oxidation state in LiFePO4 batteries and cyclic water gas shift reactors.

    PubMed

    Kadyk, Thomas; Eikerling, Michael

    2015-08-14

    The possibility of correlating the magnetic susceptibility to the oxidation state of the porous active mass in a chemical or electrochemical reactor was analyzed. The magnetic permeability was calculated using a hierarchical model of the reactor. This model was applied to two practical examples: LiFePO4 batteries, in which the oxidation state corresponds with the state-of-charge, and cyclic water gas shift reactors, in which the oxidation state corresponds to the depletion of the catalyst. In LiFePO4 batteries phase separation of the lithiated and delithiated phases in the LiFePO4 particles in the positive electrode gives rise to a hysteresis effect, i.e. the magnetic permeability depends on the history of the electrode. During fast charge or discharge, non-uniform lithium distributionin the electrode decreases the hysteresis effect. However, the overall sensitivity of the magnetic response to the state-of-charge lies in the range of 0.03%, which makes practical measurement challenging. In cyclic water gas shift reactors, the sensitivity is 4 orders of magnitude higher and without phase separation, no hysteresis occurs. This shows that the method is suitable for such reactors, in which large changes of the magnetic permeability of the active material occurs. PMID:26156571

  2. Core-shell LiFePO4 /carbon-coated reduced graphene oxide hybrids for high-power lithium-ion battery cathodes.

    PubMed

    Ha, Sung Hoon; Lee, Yun Jung

    2015-01-26

    Core-shell carbon-coated LiFePO4 nanoparticles were hybridized with reduced graphene (rGO) for high-power lithium-ion battery cathodes. Spontaneous aggregation of hydrophobic graphene in aqueous solutions during the formation of composite materials was precluded by employing hydrophilic graphene oxide (GO) as starting templates. The fabrication of true nanoscale carbon-coated LiFePO4 -rGO (LFP/C-rGO) hybrids were ascribed to three factors: 1) In-situ polymerization of polypyrrole for constrained nanoparticle synthesis of LiFePO4 , 2) enhanced dispersion of conducting 2D networks endowed by colloidal stability of GO, and 3) intimate contact between active materials and rGO. The importance of conducting template dispersion was demonstrated by contrasting LFP/C-rGO hybrids with LFP/C-rGO composites in which agglomerated rGO solution was used as the starting templates. The fabricated hybrid cathodes showed superior rate capability and cyclability with rates from 0.1 to 60 C. This study demonstrated the synergistic combination of nanosizing with efficient conducting templates to afford facile Li(+) ion and electron transport for high power applications. PMID:25430976

  3. In-situ growth of graphene decorations for high-performance LiFePO4 cathode through solid-state reaction

    NASA Astrophysics Data System (ADS)

    Li, Jing; Zhang, Li; Zhang, Longfei; Hao, Weiwei; Wang, Haibo; Qu, Qunting; Zheng, Honghe

    2014-03-01

    Graphene-decorated LiFePO4 composite is synthesized for the first time through in-situ pyrolysis and catalytic graphitization, in which glucose and a trace amount of FeSO4 are employed as the graphene source and catalyst precursor, respectively. Under Ar/H2 (95:5) atmosphere at 750 °C, FeSO4 is thermally reduced to Fe nano-particles (Fe NPs) and glucose is pyrolyzed to carbon fragments first, followed by the in-situ growth of graphene sheets directly on the LiFePO4 nano-particles (LFP NPs) surface through the realignment of carbon fragments under the catalytic effect of the Fe NPs. The graphene sheets not only form a compact and uniform coating layer throughout the LFP NPs, but also stretch out and cross-link into a conducting network around the LFP particles. The LiFePO4@graphene composite displays a high reversible specific capacity of 167.7 mAh g-1 at 0.1C rate, superb rate performance with discharge capacity of 94.3 mAh g-1 at 100C rate and much prolonged cycle life. The remarkable electrochemical improvement is attributed to both electric and ionic conductivity increase as a result of in-situ grown graphene coatings along the LFP surface and the graphene network intrinsically connecting to the LFP particles.

  4. Combined operando X-ray diffraction–electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries

    PubMed Central

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

    2015-01-01

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4. PMID:26345306

  5. Olivines and olivine coronas in mesosiderites

    NASA Technical Reports Server (NTRS)

    Nehru, C. E.; Zucker, S. M.; Harlow, G. E.; Prinz, M.

    1980-01-01

    The paper presents a study of olivines and their surrounding coronas in mesosiderites texturally and compositionally using optical and microprobe methods. Olivine composition ranges from Fo(58-92) and shows no consistent pattern of distribution within and between mesosiderites; olivine occurs as large single crystals or as partially recrystallized mineral clasts, except for two lithic clasts. These are Emery and Vaca Muerta, and both are shock-modified olivine orthopyroxenites. Fine-grained coronas surround olivine, except for those in impact-melt group mesosiderites and those without tridymite in their matrices. Coronas consist largely of orthopyroxene, plagioclase, clinopyroxene, chromite, merillite, and ilmenite, and are similar to the matrix, but lack metal and tridymite. Texturally the innermost parts of the corona can be divided into three stages of development: (1) radiating acicular, (2) intermediate, and (3) granular.

  6. Particle shapes and surface structures of olivine NaFePO₄ in comparison to LiFePO₄.

    PubMed

    Whiteside, Alexander; Fisher, Craig A J; Parker, Stephen C; Islam, M Saiful

    2014-10-21

    The expansion of batteries into electric vehicle and grid storage applications has driven the development of new battery materials and chemistries, such as olivine phosphate cathodes and sodium-ion batteries. Here we present atomistic simulations of the surfaces of olivine-structured NaFePO4 as a sodium-ion battery cathode, and discuss differences in its morphology compared to the lithium analogue LiFePO4. The calculated equilibrium morphology is mostly isometric in appearance, with (010), (201) and (011) faces dominant. Exposure of the (010) surface is vital because it is normal to the one-dimensional ion-conduction pathway. Platelet and cube-like shapes observed by previous microscopy studies are reproduced by adjusting surface energies. The results indicate that a variety of (nano)particle morphologies can be achieved by tuning surface stabilities, which depend on synthesis methods and solvent conditions, and will be important in optimising electrochemical performance. PMID:25200320

  7. Synthesis and performances of 2LiFePO4·Li3V2(PO4)3/C cathode materials via spray drying method with double carbon sources

    NASA Astrophysics Data System (ADS)

    Zhang, Jia-feng; Shen, Chao; Zhang, Bao; Zheng, Jun-chao; Peng, Chun-li; Wang, Xiao-wei; Yuan, Xin-bo; Li, Hui; Chen, Guo-min

    2014-12-01

    The 2LiFePO4·Li3V2(PO4)3/C samples are synthesized through spray drying method. Glucose and oxalic acid are used as collaborative carbon sources to improve the electrochemical performance of 2LiFePO4·Li3V2(PO4)3/C composites. XRD results reveal the LiFePO4·Li3V2(PO4)3/C samples are composed of orthorhombic LiFePO4 and monoclinic Li3V2(PO4)3 phases. SEM results reveal that the nano-spherical Fe4(VO4)4·5H2O are about 80 nm and the 2LiFePO4·Li3V2(PO4)3/C composites possess a micro-nano spherical morphology with carbon coating layer. The samples show the best electrochemical performance when the mass ration of glucose and oxalic is 6:4, it can deliver a capacity of 147.6 mAh g-1, 145.0 mAh g-1, 134.1 mAh g-1 and 123.0 mAh g-1 at the rates of 0.1C, 1C, 5C and 10C, respectively.

  8. Tungsten diffusion in olivine

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.; Van Orman, J. A.

    2014-03-01

    Diffusion of tungsten has been characterized in synthetic forsterite and natural olivine (Fo90) under dry conditions. The source of diffusant was a mixture of magnesium tungstate and olivine powders. Experiments were prepared by sealing the source material and polished olivine under vacuum in silica glass ampoules with solid buffers to buffer at NNO or IW. Prepared capsules were annealed in 1 atm furnaces for times ranging from 45 min to several weeks, at temperatures from 1050 to 1450 °C. Tungsten distributions in the olivine were profiled by Rutherford Backscattering Spectrometry (RBS). The following Arrhenius relation is obtained for W diffusion in forsterite: D=1.0×10-8exp(-365±28 kJ mol/RT) m s Diffusivities for the synthetic forsterite and natural Fe-bearing olivine are similar, and tungsten diffusion in olivine shows little dependence on crystallographic orientation or oxygen fugacity. The slow diffusivities measured for W in olivine indicate that Hf-W ages in olivine-metal systems will close to diffusive exchange at higher temperatures than other chronometers commonly used in cosmochronology, and that tungsten isotopic signatures will be less likely to be reset by subsequent thermal events.

  9. Phase evolution in single-crystalline LiFePO4 followed by in situ scanning X-ray microscopy of a micrometre-sized battery

    NASA Astrophysics Data System (ADS)

    Ohmer, Nils; Fenk, Bernhard; Samuelis, Dominik; Chen, Chia-Chin; Maier, Joachim; Weigand, Markus; Goering, Eberhard; Schütz, Gisela

    2015-01-01

    LiFePO4 is one of the most frequently studied positive electrode materials for lithium-ion batteries during the last years. Nevertheless, there is still an extensive debate on the mechanism of phase transformation. On the one hand this is due to the small energetic differences involved and hence the great sensitivity with respect to parameters such as size and morphology. On the other hand this is due to the lack of in situ observations with appreciable space and time resolution. Here we present scanning transmission X-ray microscopy measurements following in situ the phase boundary propagation within a LiFePO4 single crystal along the (010) orientation during electrochemical lithiation/delithiation. We follow, on a battery-relevant timescale, the evolution of a two-phase-front on a micrometre scale with a lateral resolution of 30 nm and with minutes of time resolution. The growth pattern is found to be dominated by elastic effects rather than being transport-controlled.

  10. Direct Observation of Active Material Concentration Gradients and Crystallinity Breakdown in LiFePO4 Electrodes During Charge/Discharge Cycling of Lithium Batteries

    PubMed Central

    2014-01-01

    The phase changes that occur during discharge of an electrode comprised of LiFePO4, carbon, and PTFE binder have been studied in lithium half cells by using X-ray diffraction measurements in reflection geometry. Differences in the state of charge between the front and the back of LiFePO4 electrodes have been visualized. By modifying the X-ray incident angle the depth of penetration of the X-ray beam into the electrode was altered, allowing for the examination of any concentration gradients that were present within the electrode. At high rates of discharge the electrode side facing the current collector underwent limited lithium insertion while the electrode as a whole underwent greater than 50% of discharge. This behavior is consistent with depletion at high rate of the lithium content of the electrolyte contained in the electrode pores. Increases in the diffraction peak widths indicated a breakdown of crystallinity within the active material during cycling even during the relatively short duration of these experiments, which can also be linked to cycling at high rate. PMID:24790684

  11. A method for state-of-charge estimation of LiFePO4 batteries at dynamic currents and temperatures using particle filter

    NASA Astrophysics Data System (ADS)

    Wang, Yujie; Zhang, Chenbin; Chen, Zonghai

    2015-04-01

    The state-of-charge (SOC) estimation for LiFePO4 batteries is one of the most important issues in battery management system (BMS) on electric vehicles (EVs). Significant temperature changes and drift current noises are inevitable in EVs and cause strong interference in SOC estimation, therefore a SOC-Particle filter (PF) estimator is proposed for SOC estimation. This paper tries to make three contributions: (1) a temperature composed battery model is established based on commercial LiFePO4 cells which can be used for SOC estimation at dynamic temperatures. (2) A capacity retention ratio (CRR) aging model is established based on the real history statistical analysis of the running mileage of the battery on an urban bus. (3) The proposed models are combined with an electrochemical model and the PF method is employed for SOC estimation to eliminate the drift noise effects. Experiments under dynamic current and temperature conditions are designed and performed to verify the accuracy and robustness of the proposed method. The numeral results of the validation experiments have verified that accurate and robust SOC estimation results can be obtained by the proposed method.

  12. Irreversible phase transition between LiFePO4 and FePO4 during high-rate charge-discharge reaction by operando X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Takahashi, Ikuma; Mori, Takuya; Yoshinari, Takahiro; Orikasa, Yuki; Koyama, Yukinori; Murayama, Haruno; Fukuda, Katsutoshi; Hatano, Masaharu; Arai, Hajime; Uchimoto, Yoshiharu; Terai, Takayuki

    2016-03-01

    LiFePO4 is a practically used cathode material for lithium-ion batteries due to a high theoretical capacity, high cycle capability and the high-rate performance. The metastable LixFePO4 (LxFP) phase with an intermediate composition appears in the non-equilibrium state at high-rate condition. However, the formation process of the metastable LxFP phase and its impact to the electrochemical property are still unclear. In order to elucidate these points, we directly observed the phase transition behavior by applying operando XRD during 10C charge-discharge. LxFP phase does not form in charge reaction but preferentially forms in discharge reaction. The phase transition from LxFP to Li-rich phase is less likely to proceed in the end of discharge reaction. The asymmetric phase transition between LiFePO4 and FePO4 results in decreasing the discharge capacity and increasing the irreversible capacity at high-rate conditions.

  13. Length-Scale-Dependent Phase Transformation of LiFePO4 : An In situ and Operando Study Using Micro-Raman Spectroscopy and XRD.

    PubMed

    Siddique, N A; Salehi, Amir; Wei, Zi; Liu, Dong; Sajjad, Syed D; Liu, Fuqiang

    2015-08-01

    The charge and discharge of lithium ion batteries are often accompanied by electrochemically driven phase-transformation processes. In this work, two in situ and operando methods, that is, micro-Raman spectroscopy and X-ray diffraction (XRD), have been combined to study the phase-transformation process in LiFePO4 at two distinct length scales, namely, particle-level scale (∼1 μm) and macroscopic scale (∼several cm). In situ Raman studies revealed a discrete mode of phase transformation at the particle level. Besides, the preferred electrochemical transport network, particularly the carbon content, was found to govern the sequence of phase transformation among particles. In contrast, at the macroscopic level, studies conducted at four different discharge rates showed a continuous but delayed phase transformation. These findings uncovered the intricate phase transformation in LiFePO4 and potentially offer valuable insights into optimizing the length-scale-dependent properties of battery materials. PMID:26073651

  14. Insights in the electronic structure and redox reaction energy in LiFePO4 battery material from an accurate Tran-Blaha modified Becke Johnson potential

    NASA Astrophysics Data System (ADS)

    B. Araujo, Rafael; S. de Almeida, J.; Ferreira da Silva, A.; Ahuja, Rajeev

    2015-09-01

    The main goals of this paper are to investigate the accuracy of the Tran-Blaha modified Becke Johnson (TB-mBJ) potential to predict the electronic structure of lithium iron phosphate and the related redox reaction energy with the lithium deintercalation process. The computed electronic structures show that the TB-mBJ method is able to partially localize Fe-3d electrons in LiFePO4 and FePO4 which usually is a problem for the generalized gradient approximation (GGA) due to the self interaction error. The energy band gap is also improved by the TB-mBJ calculations in comparison with the GGA results. It turned out, however, that the redox reaction energy evaluated by the TB-mBJ technique is not in good agreement with the measured one. It is speculated that this disagreement in the computed redox energy and the experimental value is due to the lack of a formal expression to evaluate the exchange and correlation energy. Therefore, the TB-mBJ is an efficient method to improve the prediction of the electronic structures coming form the standard GGA functional in LiFePO4 and FePO4. However, it does not appear to have the same efficiency for evaluating the redox reaction energies for the investigated system.

  15. Effect of Surfactants on the Physical Properties and Electrochemical Performance of LiFePO4 Cathode Material for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Nazri, M.; Vaishnava, P.; Naik, V. M.; Nazri, G. A.; Naik, R.

    2012-02-01

    The lithium iron phosphate chemistry is plagued by the poor electronic conductivity and slow lithium ion diffusion in the solid phase. In order to solve these problems, various research groups have adopted different strategies including decreasing the particle size, covering the particles with carbon, and adding dopants to the cathode material. Here, we report synthesis of C-LiFePO4 cathode materials using 0.25M lauric, myristic, and oleic acid as surfactants. The phase purity of all three C-LiFePO4 was confirmed by x-ray diffraction. SEM and TEM investigations reveal that the surfactants coat the LiFePO4 particles uniformly with carbon and the coating reduces the particle size to 20-30 nm. Due to high electrical conductivity, controlled particle size and suitable microstructure, among the three LiFePO4 coated samples, the sample with 0.25M lauric acid exhibited superior electrochemical performance in terms of specific capacity, the cycling stability and delivered high discharge capacity of 155, 150 and 123 mAhg-1 at 0.5 C, 1C and 5C, respectively. The correlation between the ratio of the intensities of the D and G bands observed by micro-Raman spectroscopy, conductivity and electrochemical characteristics will be presented.

  16. Percolation-tunneling modeling for the study of the electric conductivity in LiFePO 4 based Li-ion battery cathodes

    NASA Astrophysics Data System (ADS)

    Awarke, Ali; Lauer, Sven; Pischinger, Stefan; Wittler, Michael

    In this work a percolation-tunneling based model is developed and used to study the electrical conductivity of LiFePO 4 composite Li-ion battery cathodes. The active and conductive additive particles are explicitly represented using a random hybrid geometric-mechanical packing algorithm, while the inter-particle electric transport is achieved by including electron tunneling effects. The model is adjusted to the experimental data of a PVDF/C composite with different mixing ratios. The performed study aims to capture the variation of the conductivity of the LiFePO 4 cathode with particle sizes, carbon black particles wt.% and carbon coating wt.%. It is found that ultra fine carbon-free nanosized particles (∼50 nm), which are favorable for improved diffusion, would require a relatively high amount of carbon black (15 wt.%) putting at risk the gravimetric capacity of the cell. On the other hand, particles with 1 wt.% continuous carbon coating delivers already sufficient conductivity for all particle sizes without any additives. The further addition of conductive phases is at the risk of redundancy in view of conductivity enhancements. Although continuous carbon coating with loading as low as 1 wt.% is thought to be the most efficient way to achieve electric conductivity, its manufacturability and effect on Li ion diffusion remain to be assessed.

  17. A novel dual-salts of LiTFSI and LiODFB in LiFePO4-based batteries for suppressing aluminum corrosion and improving cycling stability

    NASA Astrophysics Data System (ADS)

    Li, Faqiang; Gong, Yan; Jia, Guofeng; Wang, Qinglei; Peng, Zhengjun; Fan, Wei; Bai, Bing

    2015-11-01

    The strong corrosion behavior at the Al current collector restricts the application range of lithium bis (trifluoromethanesulfonylimide) (LiTFSI), despite its high stability against water and thermal. SEM, LSV and Tafel curves proved that adding LiODFB into LiTFSI-based electrolytes could suppress aluminum corrosion caused by LiTFSI-based electrolytes. The cycling stability and rate capability of LiFePO4-based batteries using LiTFSI0.6-LiODFB0.4-based electrolytes is excellent as compared to LiFePO4-based batteries using LiPF6-based electrolytes.

  18. Performance qualification and Raman investigation on cell behavior and aging of LiFePO4 cathodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Salehi, Amir

    This thesis explores the ability of Raman spectroscopy to understand the complex chemistry taking place in LiFePO4 cathodes of Li ion batteries. The performance of Li ion batteries was optimized through electrode fabrication and assembling procedures. Various amounts of Timcal Super P carbon were used to construct a conductive network of C-LiFePO4 particles and the performance of the cathodes was examined during battery cycling. Raman spectroscopy along with electrochemical characterization such as charge/ discharge curves, electrochemical impedance spectroscopy and Cyclic Voltammetry was employed for detailed investigation of battery performance and aging. It is found that both quantity and quality of the conductive carbon affect the rate performance and cyclic behavior of the cells. The cathodes with 2% additive carbon showed a faster capacity fading during cycling than that with 10% additive carbon due to a quicker degradation of the conductive network as indicated by sp2/sp3 and ID/IG ratios in Raman spectroscopy results. The rate performance of cathodes with 2%, 10% and 20 % carbon was also compared and a better rate performance was found for 2% carbon. It showed a proper electronic network which is mostly provided by carbon coating along with a large pore size of the cathode which facilitates the electrolyte penetration. Furthermore, in situ Raman spectroscopy was employed to probe electrolyte concentration variation at the cathode LiFePO4 particle surface in an optically transparent lithium ion cell. A Raman laser spot size of 2 microm was applied so that transport dynamics at individual particle surface could be investigated. The variation of Li+ concentration in the LiPF6/ethylene carbonate (EC) + dimethyl carbonate (DMC) electrolyte was determined, for the first time. This was done by monitoring the C--O stretching vibration signal intensity and the corresponding relationship to EC solvation. The electrolyte concentration at the LiFePO 4 particle surface was found to fluctuate during the battery charge/discharge cycle. Particularly, near the end of battery discharge, it reached to a minimum value which was far less than its initial balanced value (1 mol.dm -3).

  19. Pilot-scale continuous synthesis of a vanadium-doped LiFePO4/C nanocomposite high-rate cathodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Johnson, Ian D.; Lübke, Mechthild; Wu, On Ying; Makwana, Neel M.; Smales, Glen J.; Islam, Husn U.; Dedigama, Rashmi Y.; Gruar, Robert I.; Tighe, Christopher J.; Scanlon, David O.; Corà, Furio; Brett, Dan J. L.; Shearing, Paul R.; Darr, Jawwad A.

    2016-01-01

    A high performance vanadium-doped LiFePO4 (LFP) electrode is synthesized using a continuous hydrothermal method at a production rate of 6 kg per day. The supercritical water reagent rapidly generates core/shell nanoparticles with a thin, continuous carbon coating on the surface of LFP, which aids electron transport dynamics across the particle surface. Vanadium dopant concentration has a profound effect on the performance of LFP, where the composition LiFe0.95V0.05PO4, achieves a specific discharge capacity which is among the highest in the comparable literature (119 mA h g-1 at a discharge rate of 1500 mA g-1). Additionally, a combination of X-ray absorption spectroscopy analysis and hybrid-exchange density functional theory, suggest that vanadium ions replace both phosphorous and iron in the structure, thereby facilitating Li+ diffusion due to Li+ vacancy generation and changes in the crystal structure.

  20. Enhanced electrochemical properties of LiFePO4 (LFP) cathode using the carboxymethyl cellulose lithium (CMC-Li) as novel binder in lithium-ion battery.

    PubMed

    Qiu, Lei; Shao, Ziqiang; Wang, Daxiong; Wang, Wenjun; Wang, Feijun; Wang, Jianquan

    2014-10-13

    Novel water-based binder CMC-Li is synthesized using cotton as raw material. The mechanism of the CMC-Li as a binder is reported. Electrochemical properties of batteries cathodes based on commercially available lithium iron phosphate (LiFePO4, LFP) and CMC-Li as a water-soluble binder are investigated. CMC-Li is a novel lithium-ion binder. Compare with conventional poly(vinylidene fluoride) (PVDF) binder, and the battery with CMC-Li as the binder retained 97.8% of initial reversible capacity after 200 cycles at 176 mAh g(-1), which is beyond the theoretical specific capacity of LFP. Constant current charge-discharge test results demonstrate that the LFP electrode using CMC-Li as the binder has the highest rate capability, follow closely by that using PVDF binder. The batteries have good electrochemical property, outstanding pollution-free and excellent stability. PMID:25037391

  1. Mixed salts of LiTFSI and LiBOB for stable LiFePO4-based batteries at elevated temperatures

    SciTech Connect

    Chen, Xilin; Xu, Wu; Engelhard, Mark H.; Zheng, Jianming; Zhang, Yaohui; Ding, Fei; Qian, Jiangfeng; Zhang, Ji-Guang

    2014-01-01

    To achieve stable long-term cycling stability at elevated temperatures, mixed salts of LiTFSI and LiBOB are used to replace LiPF6 salt in non-aqueous electrolytes for LiFePO4-based batteries. It is found that adding LiBOB in LiTFSI-based electrolytes effectively prevents the severe corrosion to Al current collectors that often is observed in LiTFSI-based electrolytes, which have high thermal stability. The cells using LiTFSI-LiBOB-based electrolytes demonstrate superior high temperature (60 °C) stability and very similar room temperature performance (i.e., cycling stability and rate capability) when compared to cells using the LiPF6-based electrolyte.

  2. Nanosized LiFePO4-decorated emulsion-templated carbon foam for 3D micro batteries: a study of structure and electrochemical performance

    NASA Astrophysics Data System (ADS)

    Asfaw, Habtom D.; Roberts, Matthew R.; Tai, Cheuk-Wai; Younesi, Reza; Valvo, Mario; Nyholm, Leif; Edström, Kristina

    2014-07-01

    In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm-2 at 0.1 mA cm-2 (lowest rate) and 1.1 mA h cm-2 at 6 mA cm-2 (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium.In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm-2 at 0.1 mA cm-2 (lowest rate) and 1.1 mA h cm-2 at 6 mA cm-2 (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01682c

  3. Artificial meteor ablation studies: Olivine

    NASA Technical Reports Server (NTRS)

    Blanchard, M. B.; Cunningham, G. G.

    1973-01-01

    Artificial meteor ablation was performed on a Mg-rich olivine sample using an arc-heated plasma of ionized air. Experimental conditions simulated a meteor traveling about 12 km/sec at an altitude of 70 km. The mineral content of the original olivine sample was 98% olivine (including traces of olivine alteration products) and 2% chromite. Forsterite content of the original olivine was Fo-89. After ablation, the forsterite content had increased to Fo-94 in the recrystallized olivine. In addition, lamella-like intergrowths of magnetite were prevalent constituents. Wherever magnetite occurred, there was an increase in Mg and a corresponding decrease in Fe for the recrystallized olivine. The Allende fusion crust consisted of a recrystallized olivine, which was more Mg-rich and Fe-deficient than the original meteorite's olivine, and abundant magnetite grains. Although troilite and pentlandite were the common opaque mineral constituents in this meteorite, magnetite was the principal opaque mineral found in the fusion crust.

  4. Microbial Weathering of Olivine

    NASA Technical Reports Server (NTRS)

    McKay, D. S.; Longazo, T. G.; Wentworth, S. J.; Southam, G.

    2002-01-01

    Controlled microbial weathering of olivine experiments displays a unique style of nanoetching caused by biofilm attachment to mineral surfaces. We are investigating whether the morphology of biotic nanoetching can be used as a biosignature. Additional information is contained in the original extended abstract.

  5. Surface-orientation-dependent distribution of subsurface cation-exchange defects in olivine-phosphate nanocrystals.

    PubMed

    Chung, Sung-Yoon; Choi, Si-Young; Kim, Tae-Hwan; Lee, Seongsu

    2015-01-27

    Atomic-scale exchange between two different cations of similar size in crystalline oxides is one of the major types of point defects when multiple cations in oxygen interstitials are arrayed in an ordered manner. Although a number of studies have been performed on a variety of Li-intercalation olivine phosphates to determine the distribution of exchange defects in bulk, understanding of the thermodynamic stability of the defects in subsurface regions and its dependency on the crystallographic orientation at the surface has remained elusive. Through a combination of small-angle neutron scattering, atomic-scale direct probing with scanning transmission electron microscopy, and theoretical ab initio calculations, we directly demonstrate that the antisite exchange defects are distributed in a highly anisotropic manner near the surfaces of LiFePO4 crystals. Moreover, a substantial amount of cation exchanges between Li and Fe sites is identified as an energetically favorable configuration in some surface regions, showing excellent agreement with the calculation results of negative defect formation energies. The findings in this study provide insight into developing better ways to avoid degradation of lithium mobility through the surface as well as scientifically notable features regarding the distribution of exchange defects in olivine phosphates. PMID:25565086

  6. Vacuum welding of olivine.

    PubMed

    Bell, P R

    1966-07-22

    Welding of olivine was demonstrated by grinding it in a ball mill in an atmosphere of about 2 x 10(-7) torr. Most of the sample adhered strongly to the container and grinding balls although adhesion in air is only slight. Similar adhesion should be expected on the lunar surface and may account for the roughness needed to explain the optical properties of the moon and the detail of the una 9 photographs. PMID:17839712

  7. "Black-colored olivines" in peridotites: dehydrogenation from hydrous olivines

    NASA Astrophysics Data System (ADS)

    Arai, Shoji; Hoshikawa, Chihiro; Miura, Makoto

    2015-04-01

    Fresh olivines that are black to the naked eye are found in some dunites. Peridotites are easily converted to be black in color, when serpentinized, due to production of secondary fine magnetite particles. The dunites that contain fresh but black-colored olivines are usually coarse-grained. These coarse olivine grains are sometimes very heterogeneous in color; the blackish part grades to whitish parts in single grains. The black color is due to homegeneous distribution of minute (< 10 microns) black particles in olivine. They are rod-like or plate-like in shape in thin section, sometimes being aligned under crystallographic control of the host olivine. Olivines are clear and free of these inclusions around primary chromian spinel inclusions or chromian spinel lamellae (Arai, 1978). Raman spectroscopy indicates the minute black particles are magnetite always associated with diopside. It is interesting to note that olivine in mantle peridotites accompanied by the black-colored dunites is totally free of the black inclusions, giving the ordinary colors (pale yellow to whitish) of Mg-rich olivine. It is not likely that the magnetite inclusions formed through secondary oxidation of olivine by invasion of oxygen, which is possible along cracks or grain boundaries. They most probably formed due to dehydrogenation from primary OH-bearing olivines upon cooling. Hydrogen was quickly diffused out from the olivines to leave magnetite and excess silica. The excess silica was possibly combined with a monticellite component to form diopside. The OH-bearing (hydrous) olivines can be precipitated from hydrous magmas, and the hydrous nature of the magma can promote an increase in grain size due to faster diffusion of elements. The minute inclusions of magnetite + diopside is thus an indicator of primary hydrous character of host olivine.

  8. Porous α-Fe2O3 nanostructures and their lithium storage properties as full cell configuration against LiFePO4

    NASA Astrophysics Data System (ADS)

    Veluri, P. S.; Shaligram, A.; Mitra, S.

    2015-10-01

    A two step approach for synthesis of porous α-Fe2O3 nanostructures has been realized via polyol method by complexing iron oxalate with ethylene glycol. Crystalline Fe2O3 samples with different porosities are obtained by calcination of Fe-Ethylene glycol complex at various temperatures. The as-prepared porous Fe2O3 structures exhibit promising lithium storage performance at high current rates. It is observed that the calcination temperature and the resultant porosity have a significant effect on capacity and cycling stability. Samples calcined at high temperature (600 °C) demonstrates stable cycle life with capacity retention of 1077 mAh g-1 at 500 mA g-1 current rate after 50 charge-discharge cycles. Samples calcined at temperatures of 500 and 600 °C display stable cycle life and high rate capability with reversible capacity of 930 mAh g-1 and 688 mAh g-1 at 5 A g-1, respectively. Impregnation of electrodes with electrolyte before cell fabrication shows enhanced electrochemical performance. The viability of Fe2O3 porous nanostructures as prospective anode material examined against commercial LiFePO4 cathode shows promising electrochemical performance.

  9. Conformal Coating Strategy Comprising N-doped Carbon and Conventional Graphene for Achieving Ultrahigh Power and Cyclability of LiFePO4.

    PubMed

    Zhang, Kan; Lee, Jeong-Taik; Li, Ping; Kang, Byoungwoo; Kim, Jung Hyun; Yi, Gi-Ra; Park, Jong Hyeok

    2015-10-14

    Surface carbon coating to improve the inherent poor electrical conductivity of lithium iron phosphate (LiFePO4, LFP) has been considered as most efficient strategy. Here, we also report one of the conventional methods for LFP but exhibiting a specific capacity beyond the theoretical value, ultrahigh rate performance, and excellent long-term cyclability: the specific capacity is 171.9 mAh/g (70 μm-thick electrode with ∼10 mg/cm(2) loading mass) at 0.1 C (17 mA/g) and retains 143.7 mAh/g at 10 C (1.7 A/g) and 95.8% of initial capacity at 10 C after 1000 cycles. It was found that the interior conformal N-C coating enhances the intrinsic conductivity of LFP nanorods (LFP NR) and the exterior reduced graphene oxide coating acts as an electrically conducting secondary network to electrically connect the entire electrode. The great electron transport mutually promoted with shorten Li diffusion length on (010) facet exposed LFP NR represents the highest specific capacity value recorded to date at 10 C and ultralong-term cyclability. This conformal carbon coating approach can be a promising strategy for the commercialization of LFP cathode in lithium ion batteries. PMID:26389552

  10. Effects of Laser Energy and Wavelength on the Analysis of LiFePO4 Using Laser Assisted Atom Probe Tomography

    SciTech Connect

    Santhanagopalan, Dhamodaran; Schreiber, Daniel K.; Perea, Daniel E.; Martens, Rich; Janssen, Yuri; Kalifah, Peter; Meng, Ying S.

    2015-01-21

    The effects of laser wavelength (355 nm and 532 nm) and laser pulse energy on the quantitative accuracy of atom probe tomography (APT) examinations of LiFePO4 (LFP) are considered. A systematic investigation of ultraviolet (UV, 355 nm) and green (532 nm) laser assisted APT of LFP has revealed distinctly different behaviors. With the use of UV laser the major issue was identified as the preferential loss of oxygen (up to 10 at. %) while other elements (Li, Fe and P) were observed to be close to nominal ratios. Lowering the laser energy per pulse to 1 pJ increased the observed oxygen concentration to near its correct stoichiometry and was well correlated with systematically higher concentrations of 16O2+ ions. This observation supports the premise that lower laser energies lead to a higher probability of oxygen molecule ionization. Conversely, at higher laser energies the resultant lower effective electric field reduces the probability of oxygen molecule ionization. Green laser assisted field evaporation led to the selective loss of Li (~50% deficiency) and correct ratios of the remaining elements, including the oxygen concentration. The loss of Li is explained by selective dc evaporation of lithium between laser pulses and relatively negligible oxygen loss as neutrals during green-laser pulsing. Lastly, plotting of multihit events on a Saxey plot for the straight-flight path data (green laser only) revealed a surprising dynamic recombination process for some molecular ions mid-flight.

  11. Experiment and simulation of a LiFePO4 battery pack with a passive thermal management system using composite phase change material and graphite sheets

    NASA Astrophysics Data System (ADS)

    Lin, Chunjing; Xu, Sichuan; Chang, Guofeng; Liu, Jinling

    2015-02-01

    A passive thermal management system (TMS) for LiFePO4 battery modules using phase change material (PCM) as the heat dissipation source to control battery temperature rise is developed. Expanded graphite matrix and graphite sheets are applied to compensate low thermal conductivity of PCM and improve temperature uniformity of the batteries. Constant current discharge and mixed charge-discharge duties were applied on battery modules with and without PCM on a battery thermal characteristics test platform. Experimental results show that PCM cooling significantly reduces the battery temperature rise during short-time intense use. It is also found that temperature uniformity across the module deteriorates with the increasing of both discharge time and current rates. The maximum temperature differences at the end of 1C and 2C-rate discharges are both less than 5 °C, indicating a good performance in battery thermal uniformity of the passive TMS. Experiments on warm-keeping performance show that the passive TMS can effectively keep the battery within its optimum operating temperature for a long time during cold weather uses. A three dimensional numerical model of the battery pack with the passive TMS was conducted using ANSYS Fluent. Temperature profiles with respect to discharging time reveal that simulation shows good agreement with experiment at 1C-discharge rate.

  12. On the complex ageing characteristics of high-power LiFePO4/graphite battery cells cycled with high charge and discharge currents

    NASA Astrophysics Data System (ADS)

    Groot, Jens; Swierczynski, Maciej; Stan, Ana Irina; Kær, Søren Knudsen

    2015-07-01

    Li-ion batteries are known to undergo complex ageing processes, where the operating conditions have a profound and non-linear effect on both calendar life and cycle life. This is especially a challenge for the automotive industry, where the requirements on product lifetime and reliability are demanding. The aim of the present work is to quantify the ageing in terms of capacity fade and impedance growth as a function of operating conditions typical to high-power automotive applications; high charge and discharge rate, elevated temperatures and wide state-of-charge windows. The cycle life of 34 power-optimised LiFePO4/graphite cells was quantified by testing with charge and discharge rates between 1 and 4C-rate, temperatures between +23 °C and +53 °C, and a depth-of-discharge of either 100% or 60%. Although all cells show similar ageing pattern in general, the cycle life and the impedance growth is remarkably different for the tested cases. In addition, it is concluded that high charging rates, high temperatures or intensive cycling do not always lead to a shorter cycle life. One specifically interesting finding is that the combination of 1C-rate discharge in combination with 3.75C-rate charging was found to degrade the tested cells more rapidly than a symmetric cycle with 3.75C-rate in both directions.

  13. High power Nb-doped LiFePO4 Li-ion battery cathodes; pilot-scale synthesis and electrochemical properties

    NASA Astrophysics Data System (ADS)

    Johnson, Ian D.; Blagovidova, Ekaterina; Dingwall, Paul A.; Brett, Dan J. L.; Shearing, Paul R.; Darr, Jawwad A.

    2016-09-01

    High power, phase-pure Nb-doped LiFePO4 (LFP) nanoparticles are synthesised using a pilot-scale continuous hydrothermal flow synthesis process (production rate of 6 kg per day) in the range 0.01-2.00 at% Nb with respect to total transition metal content. EDS analysis suggests that Nb is homogeneously distributed throughout the structure. The addition of fructose as a reagent in the hydrothermal flow process, followed by a post synthesis heat-treatment, affords a continuous graphitic carbon coating on the particle surfaces. Electrochemical testing reveals that cycling performance improves with increasing dopant concentration, up to a maximum of 1.0 at% Nb, for which point a specific capacity of 110 mAh g-1 is obtained at 10 C (6 min for the charge or discharge). This is an excellent result for a high power cathode LFP based material, particularly when considering the synthesis was performed on a large pilot-scale apparatus.

  14. Online state of charge and model parameters estimation of the LiFePO4 battery in electric vehicles using multiple adaptive forgetting factors recursive least-squares

    NASA Astrophysics Data System (ADS)

    Duong, Van-Huan; Bastawrous, Hany Ayad; Lim, KaiChin; See, Khay Wai; Zhang, Peng; Dou, Shi Xue

    2015-11-01

    This paper deals with the contradiction between simplicity and accuracy of the LiFePO4 battery states estimation in the electric vehicles (EVs) battery management system (BMS). State of charge (SOC) and state of health (SOH) are normally obtained from estimating the open circuit voltage (OCV) and the internal resistance of the equivalent electrical circuit model of the battery, respectively. The difficulties of the parameters estimation arise from their complicated variations and different dynamics which require sophisticated algorithms to simultaneously estimate multiple parameters. This, however, demands heavy computation resources. In this paper, we propose a novel technique which employs a simplified model and multiple adaptive forgetting factors recursive least-squares (MAFF-RLS) estimation to provide capability to accurately capture the real-time variations and the different dynamics of the parameters whilst the simplicity in computation is still retained. The validity of the proposed method is verified through two standard driving cycles, namely Urban Dynamometer Driving Schedule and the New European Driving Cycle. The proposed method yields experimental results that not only estimated the SOC with an absolute error of less than 2.8% but also characterized the battery model parameters accurately.

  15. Minor elements in Marjalahti olivine

    NASA Astrophysics Data System (ADS)

    Ryder, G.

    1984-06-01

    Precise microprobe determinations of minor elements in olivine from Marjalahti show averages of 0.0267 percent CaO; 0.0211 percent Cr2O3; less than 0.0045 percent TiO2; 0.288 percent MnO; and 30 ppm Ni. The calcium is as high as in some terrestrial plutonic olivines (e.g. Stillwater) but lower than in terrestrial nodule (high-temperature mantle?) olivines, consistent with very slow cooling to low temperatures. The chromium is discrepant with some earlier determinations, and possibly chromium is zoned in most pallasitic olivines. The Ti, Mn, and Ni data are consistent with previous determinations.

  16. Magnetism in olivine-type LiCo(1-x)Fe(x)PO4 cathode materials: bridging theory and experiment.

    PubMed

    Singh, Vijay; Gershinsky, Yelena; Kosa, Monica; Dixit, Mudit; Zitoun, David; Major, Dan Thomas

    2015-12-14

    In the current paper, we present a non-aqueous sol-gel synthesis of olivine type LiCo1-xFexPO4 compounds (x = 0.00, 0.25, 0.50, 0.75, 1.00). The magnetic properties of the olivines are measured experimentally and calculated using first-principles theory. Specifically, the electronic and magnetic properties are studied in detail with standard density functional theory (DFT), as well as by including spin-orbit coupling (SOC), which couples the spin to the crystal structure. We find that the Co(2+) ions exhibit strong orbital moment in the pure LiCoPO4 system, which is partially quenched upon substitution of Co(2+) by Fe(2+). Interestingly, we also observe a non-negligible orbital moment on the Fe(2+) ion. We underscore that the inclusion of SOC in the calculations is essential to obtain qualitative agreement with the observed effective magnetic moments. Additionally, Wannier functions were used to understand the experimentally observed rising trend in the Néel temperature, which is directly related to the magnetic exchange interaction paths in the materials. We suggest that out of layer M-O-P-O-M magnetic interactions (J⊥) are present in the studied materials. The current findings shed light on important differences observed in the electrochemistry of the cathode material LiCoPO4 compared to the already mature olivine material LiFePO4. PMID:26548581

  17. Olivine flotation in mantle melt

    NASA Astrophysics Data System (ADS)

    Agee, Carl B.; Walker, David

    1993-01-01

    Molten komatiite and peridotite have been compressed in an octahedral multi-anvil device up to 10 GPa. Densities of the melts were measured at pressure intervals in the range 7 to 10 GPa by observing sinking and floating San Carlos olivines and synthetic forsterite marker spheres. The multi-anvil results for komatiite, when combined with piston-cylinder measurements done at 4 to 6 GPa and a calculated reference density at 10 5 Pa, yield a Birch-Murnaghan isothermal bulk modulus of (K 1900C) = 26 GPa and pressure derivative K' = 4.25. The pressure of neutral buoyancy for olivine in komatiite is confirmed to be near 8 GPa as predicted in earlier work. Olivine flotation in the experimental komatiite commences at a pressure close to where the liquidus phase changes from olivine to denser garnet, leading to the possibility of density driven crystal sorting during fractionation. Molten peridotite (KLB-1) shows an isothermal compression (2000°C) of 0.065 g cm -3 GPa -1 in the interval 10 5 Pa to 8.2 GPa. The olivine/liquid peridotite density crossover is predicted to lie between 9 and 11 GPa, indicating that olivine flotation can operate at depths of 300-500 km in a molten peridotitic mantle.

  18. Porous micro-spherical aggregates of LiFePO 4/C nanocomposites: A novel and simple template-free concept and synthesis via sol-gel-spray drying method

    NASA Astrophysics Data System (ADS)

    Yu, Feng; Zhang, Jingjie; Yang, Yanfeng; Song, Guangzhi

    Porous micro-spherical aggregates of LiFePO 4/C nanocomposites were prepared with a process of spray drying at 200 °C and subsequent heat treatment at 700 °C for 12 h by a novel and simple template-free sol-gel-SD method independent of surfactants or templates. The results indicate that the as-obtained LiFePO 4 porous microspheres have the mean diameter of 19.8 μm, average pore size of 45 nm, and large specific surface area (20.2 m 2 g -1) with evenly distributed carbon (4.5 wt.%). The particles can be easily brought into contact with electrolyte, facilitating electric and lithium ion diffusion. They present large reversible discharge capacity of 137.5 mAh g -1 at the current density of 0.1 C, good rate capacity of 53.8 mAh g -1 at 10 C, and excellent capacity retention rate closed to 100% after various current densities in the region of 2.0-4.3 V.

  19. The characteristic of carbon-coated LiFePO4 as cathode material for lithium ion battery synthesized by sol-gel process in one step heating and varied pH

    NASA Astrophysics Data System (ADS)

    Triwibowo, J.; Yuniarti, E.; Suharyadi, E.

    2014-09-01

    This research has been done on the synthesis of carbon coated LiFePO4 through sol-gel process. Carbon layer serves for improving electronic conductivity, while the variation of pH in the sol-gel process is intended to obtain the morphology of the material that may improve battery performance. LiFePO4/C precursors are Li2CO3, NH4H2PO4 and FeC2O4˙H2O and citric acid. In the synthesis process, consisting of a colloidal suspension FeC2O4˙H2O and distilled water mixed with a colloidal suspension consisting of NH4H2PO4, Li2CO3, and distilled water. Variations addition of citric acid is used to control the pH of the gel formed by mixing two colloidal suspensions. Sol in this study had a pH of 5, 5.4 and 5.8. The obtained wet gel is further dried in the oven and then sintered at a temperature 700°C for 10 hours. The resulting material is further characterized by XRD to determine the phases formed. The resulting powder morphology is observed through SEM. Specific surface area of the powder was tested by BET, while the electronic conductivity characterized with EIS.

  20. Studies on graphene enfolded olivine composite electrode material via polyol technique for high rate performance lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Muruganantham, Rasu; Sivakumar, Marimuthu; Subadevi, Rengapillai; Ramaprabhu, Sundara; Wu, Nae-Lih

    2015-09-01

    The graphene enfolded LiFePO4/C composite cathode material has been prepared via low temperature polyol process, followed by a simple chemical reaction method. The low viscous polyol solvent (DEG) (35.7 mPa s at 25°C) and usage of low temperature process (below 245°C) aid the graphene tightly encapsulated on the LiFePO4 surface that plays an important role, especially in the high rate performances over long cycles, efficiently preventing the separation of the graphene and LiFePO4 during the reaction processes, hence realizing the full potential of the active materials. The graphitization on LiFePO4/C remarkably increased the electronic conductivity of LiFePO4. The layered sheets of graphene wrapped on LiFePO4 particles provide void between graphene sheets and LiFePO4 surfaces, which facilitate the diffusion of Li+. This approach opens up a method to attain the theoretical capacity of LiFePO4. The material exhibits a superior electrochemical performance such as initial discharge capacities of 169.6 and 92 mAhg-1 at 0.1 and 30 C rates, respectively. It has an excellent capacity retention and diminutive capacity fading. The nanosize of LiFePO4 particle causes a shorter diffusion path, which reduces the time for Li+ migration between cathode and electrolyte. [Figure not available: see fulltext.

  1. Origin of olivine at Copernicus

    NASA Technical Reports Server (NTRS)

    Pieters, C. M.; Wilhelms, D. E.

    1985-01-01

    The central peaks of Copernicus are among the few lunar areas where near-infrared telescopic reflectance spectra indicate extensive exposures of olivine. Other parts of Copernicus crater and ejecta, which were derived from highland units in the upper parts of the target site, contain only low-Ca pyroxene as a mafic mineral. The exposure of compositionally distinct layers including the presence of extensive olivine may result from penetration to an anomalously deep layer of the crust or to the lunar mantle. It is suggested that the Procellarum basin and the younger, superposed Insularum basin have provided access to these normally deep-seated crustal or mantle materials by thinning the upper crustal material early in lunar history. The occurrences of olivine in portions of the compositionally heterogeneous Aristarchus Region, in a related geologic setting, may be due to the same sequence of early events.

  2. Performance and kinetics of LiFePO4-carbon bi-material electrodes for hybrid devices: A comparative study between activated carbon and multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Varzi, Alberto; Ramirez-Castro, Claudia; Balducci, Andrea; Passerini, Stefano

    2015-01-01

    Activated Carbon (AC) and multi-walled carbon nanotubes (CNT) are investigated as components of LiFePO4 (LFP)-based bi-material electrodes for hybrid devices. Firstly, the influence of their different morphological and porosimetric characteristics is correlated to the electrochemical performance. Furthermore, kinetic aspects are carefully studied (by means of galvanostatic cycling and cyclic voltammetry), in order to address the processes which determine the power performance. The results indicate that, independently from the carbon, under high current loads the electrode kinetics are limited by the transport of reactant to the LFP particles. In such conditions CNT allow, better than AC, rapid electrons and Li+ ions flow through the open network established in the electrode, thus enabling superior high rate performance, especially during pulsed operation.

  3. More on the performance of LiFePO 4 electrodes-The effect of synthesis route, solution composition, aging, and temperature

    NASA Astrophysics Data System (ADS)

    Koltypin, M.; Aurbach, D.; Nazar, L.; Ellis, B.

    Three types of olivine compounds were prepared by three different routes: sol-gel, solid-state, and hydrothermal syntheses, showing the expected structure and containing a small amount of carbon and iron phosphide for maintaining sufficient intrinsic electrical conductivity. These materials were tested in LiClO 4, and in dry and wet LiPF 6 solutions in mixtures of ethylene and dimethyl carbonate (EC-DMC, 1:1) at 30 and 60 °C. Iron dissolution from these materials, upon storage in the three solutions at these two temperatures, was measured by ICP. Aged electrodes were measured by XRD and SEM: the electrochemical performance of the three types of olivine compounds in the three solutions and at the two temperatures was measured by voltammetry and impedance spectroscopy. The behavior of pristine and aged electrodes was systematically compared. It was found that there is a strong correlation between the rate of iron dissolution and the performance of these systems in terms of high capacity, low capacity fading, and low and stable impedance upon aging. The material prepared by sol-gel synthesis demonstrated a low iron dissolution rate, even in a corrosive solution such as wet LiPF 6 solutions, and high performance, even in these solutions. When the solutions contain no acidic contaminants, all the compounds demonstrated negligible iron dissolution rates, even at 60 °C, and a good electrochemical performance. The electrochemical comparison described herein shows a pronounced impact of the solution composition on the electrodes' impedance, due to the unique surface chemistry developed in each solution.

  4. High-Performance Olivine NaFePO4 Microsphere Cathode Synthesized by Aqueous Electrochemical Displacement Method for Sodium Ion Batteries.

    PubMed

    Fang, Yongjin; Liu, Qi; Xiao, Lifen; Ai, Xinping; Yang, Hanxi; Cao, Yuliang

    2015-08-19

    Olivine NaFePO4/C microsphere cathode is prepared by a facile aqueous electrochemical displacement method from LiFePO4/C precursor. The NaFePO4/C cathode shows a high discharge capacity of 111 mAh g(-1), excellent cycling stability with 90% capacity retention over 240 cycles at 0.1 C, and high rate capacity (46 mAh g(-1) at 2 C). The excellent electrochemical performance demonstrates that the aqueous electrochemical displacement method is an effective and promising way to prepare NaFePO4/C material for Na-based energy storage applications. Moreover, the Na2/3FePO4 intermediate is observed for the first time during the Na intercalation process through conventional electrochemical techniques, corroborating an identical two-step phase transition reaction both upon Na intercalation and deintercalation processes. The clarification of the electrochemical reaction mechanism of olivine NaFePO4 could inspire more attention on the investigation of this material for Na ion batteries. PMID:26207862

  5. Supernova olivine from cometary dust

    NASA Technical Reports Server (NTRS)

    Messenger, Scott; Keller, Lindsay P.; Lauretta, Dante S.

    2005-01-01

    An interplanetary dust particle contains a submicrometer crystalline silicate aggregate of probable supernova origin. The grain has a pronounced enrichment in 18O/16O (13 times the solar value) and depletions in 17O/16O (one-third solar) and 29Si/28Si (<0.8 times solar), indicative of formation from a type II supernova. The aggregate contains olivine (forsterite 83) grains <100 nanometers in size, with microstructures that are consistent with minimal thermal alteration. This unusually iron-rich olivine grain could have formed by equilibrium condensation from cooling supernova ejecta if several different nucleosynthetic zones mixed in the proper proportions. The supernova grain is also partially encased in nitrogen-15-rich organic matter that likely formed in a presolar cold molecular cloud.

  6. Unveil the Chemistry of Olivine FePO4 as Magnesium Battery Cathode.

    PubMed

    Zhang, Ruigang; Ling, Chen

    2016-07-20

    Despite growing interest in magnesium batteries, it is still a challenge to find a cathode that fulfills requirements such as high capacity and good cyclability. Because of their positions in the periodic table and the similar ionic sizes of lithium and magnesium, it was naturally postulated that a classical intercalation-type Li-ion battery cathode may also accommodate the intercalation of Mg. On the contrary, many Li-ion battery cathodes performed very poorly in Mg cells, although the mechanism behind such phenomena is still unclear. Here we provide first-hand evidence about the chemistry of olivine FePO4 as Mg battery cathode using a combined theoretical and experimental approach. Although LiFePO4 is a commercial cathode with extraordinary good performance in Li-ion batteries, the measured capacity of FePO4 in nonaqueous Mg cell was only ∼13 mAh/g. Density functional theory calculations predicted sufficient mobility of Mg(2+) in FePO4 lattice to support the insertion of Mg at a reasonable rate, suggesting the poor performance cannot be simply attributed to the limitation of Mg(2+) diffusion. Instead, the recorded low capacity was the result of surface amorphorization that prohibited the electrochemical reaction from penetrating deeply into the bulk phase. The amorphorization had a thermodynamic origin from the instability of intercalated product, which was predicted from DFT calculations and supported by the failure to synthesize magnesiated FePO4 in the solid state reaction route. These results highlighted the importance of a thermodynamically preferred intercalation in order to achieve successful Mg battery cathode. PMID:27355741

  7. Influence of lithium vacancies on the polaronic transport in olivine phosphate structure

    NASA Astrophysics Data System (ADS)

    Murugavel, Sevi; Sharma, Monika; Shahid, Raza

    2016-01-01

    Intercalation and deintercalation of lithium ions in cathode materials are of principal to the operation of current rechargeable lithium ion batteries. The performance of lithium ion batteries highly relies on the active cathode material which includes cell potential, power/energy density, capacity, etc. An important issue in this class of material is to resolve the factors governing the electron and ion transport in olivine phosphate structure. In this class of material, there is still an open debate on the mechanism of charge transport including both polarons and lithium ions. On the one hand, this is due to the large disparity between the experimental results and the theoretical model predictions. On the other hand, this is also due to the lack of precise experimental measurement without any parasitic phases in a given cathode material. Here, we present the polaronic conduction in lithiated triphylite LiFePO4 (LFP) and delithiated heterosite FePO4 (FP) by means of broadband ac impedance spectroscopy over wide range temperatures and frequency. It is found that the LFP phase possess two orders of higher polaronic conductivity than FP phase despite having similar mobility of polarons in both phases. We show that the differences in the polaronic conductivity of two phases are due to the significant differences in concentration of polarons. It is found that the formation energy of polarons in individual phases is mainly determined by the corresponding defect state associated with it. The temperature dependent dc conductivity has been analyzed within the framework of Mott model of polaronic conduction and explored the origin of polaronic conduction mechanism in this class of material.

  8. Multiple origins for olivine at Copernicus crater

    NASA Astrophysics Data System (ADS)

    Dhingra, Deepak; Pieters, Carle M.; Head, James W.

    2015-06-01

    Multiple origins for olivine-bearing lithologies at Copernicus crater are recognized based on integrated analysis of data from Chandrayaan-1 Moon Mineralogy Mapper (M3), Lunar Reconnaissance Orbiter (LRO) Narrow Angle Camera (NAC) and Kaguya Terrain Camera (TC). We report the diverse morphological and spectral character of previously known olivine-bearing exposures as well as the new olivine occurrences identified in this study. Prominent albedo differences exist between olivine-bearing exposures in the central peaks and a northern wall unit (the latter being ∼40% darker). The low-albedo wall unit occurs as a linear mantling deposit and is interpreted to be of impact melt origin, in contrast with the largely unmodified nature of olivine-bearing peaks. Small and localized occurrences of olivine-bearing lithology have also been identified on the impact melt-rich floor, representing a third geologic setting (apart from crater wall and peaks). Recent remote sensing missions have identified olivine-bearing exposures around lunar basins (e.g. Yamamoto et al., 2010; Pieters et al., 2011; Kramer et al., 2013) and at other craters (e.g. Sun and Li, 2014), renewing strong interest in its origin and provenance. A direct mantle exposure has commonly been suggested in this regard. Our detailed observations of the morphological and spectral diversity in the olivine-bearing exposures at Copernicus have provided critical constraints on their origin and source regions, emphasizing multiple formation mechanisms. These findings directly impact the interpretation of olivine exposures elsewhere on the Moon. Olivine can occur in diverse environments including an impact melt origin, and therefore it is unlikely for all olivine exposures to be direct mantle occurrences as has generally been suggested.

  9. A reduced order electrochemical and thermal model for a pouch type lithium ion polymer battery with LiNixMnyCo1-x-yO2/LiFePO4 blended cathode

    NASA Astrophysics Data System (ADS)

    Li, Xueyan; Choe, Song-Yul; Joe, Won Tae

    2015-10-01

    LiNixMnyCo1-x-yO2 (NMC) and LiFePO4 (LFP) as a cathode material have been widely employed for cells designed for high power applications. However, NMC needs further improvements in rate capability and stability that can be accomplished by blending it with LFP. Working mechanism of the blended cells is very complex and hard to understand. In addition, characteristics of the blended cells, particularly the plateau and path dependence of LFP materials, make it extremely difficult to estimate the state of charge and state of health using classical electric equivalent circuit models. Therefore, a reduced order model based on electrochemical and thermal principles is developed with objectives for real time applications and validated against experimental data collected from a large format pouch type of lithium ion polymer battery. The model for LFP is based on a shrinking core model along with moving boundary and then integrated into NMC model. Responses of the model that include SOC estimation and responses of current and voltage are compared with those of experiments at CC/CV charging and CC discharging along with different current rates and temperatures. In addition, the model is used to analyze effects of mass ratios between two materials on terminal voltage and heat generation rate.

  10. The ascent of kimberlite: Insights from olivine

    NASA Astrophysics Data System (ADS)

    Brett, R. C.; Russell, J. K.; Andrews, G. D. M.; Jones, T. J.

    2015-08-01

    Olivine xenocrysts are ubiquitous in kimberlite deposits worldwide and derive from the disaggregation of mantle-derived peridotitic xenoliths. Here, we provide descriptions of textural features in xenocrystic olivine from kimberlite deposits at the Diavik Diamond Mine, Canada and at Igwisi Hills volcano, Tanzania. We establish a relative sequence of textural events recorded by olivine during magma ascent through the cratonic mantle lithosphere, including: xenolith disaggregation, decompression fracturing expressed as mineral- and fluid-inclusion-rich sealed and healed cracks, grain size and shape modification by chemical dissolution and abrasion, late-stage crystallization of overgrowths on olivine xenocrysts, and lastly, mechanical milling and rounding of the olivine cargo prior to emplacement. Ascent through the lithosphere operates as a "kimberlite factory" wherein progressive upward dyke propagation of the initial carbonatitic melt fractures the overlying mantle to entrain and disaggregate mantle xenoliths. Preferential assimilation of orthopyroxene (Opx) xenocrysts by the silica-undersaturated carbonatitic melt leads to deep-seated exsolution of CO2-rich fluid generating buoyancy and supporting rapid ascent. Concomitant dissolution of olivine produces irregular-shaped relict grains preserved as cores to most kimberlitic olivine. Multiple generations of decompression cracks in olivine provide evidence for a progression in ambient fluid compositions (e.g., from carbonatitic to silicic) during ascent. Numerical modelling predicts tensile failure of xenoliths (disaggregation) and olivine (cracks) over ascent distances of 2-7 km and 15-25 km, respectively, at velocities of 0.1 to >4 m s-1. Efficient assimilation of Opx during ascent results in a silica-enriched, olivine-saturated kimberlitic melt (i.e. SiO2 >20 wt.%) that crystallizes overgrowths on partially digested and abraded olivine xenocrysts. Olivine saturation is constrained to occur at pressures <1 GPa; an

  11. Aligned olivine in the Springwater pallasite

    NASA Astrophysics Data System (ADS)

    Fowler-Gerace, Neva A.; Tait, Kimberly T.; Moser, Desmond E.; Barker, Ivan; Tian, Bob Y.

    2016-04-01

    The mechanism by which olivine grains became embedded within iron-nickel alloy in pallasite meteorites continues to be a matter of scientific debate. Geochemical and textural observations have failed to fully elucidate the origin and history of the olivine crystals; however, little research attention has been devoted to their crystallographic orientations within the metal matrix. Using electron backscatter diffraction, we have collected crystallographic orientation data for 296 crystals within ˜65 cm2 sample surface from Springwater. Though no global crystallographic preferred orientation exists, very low misorientations are observed among [100] axes of olivine crystals within specific texturally defined domains. Combined with a thorough characterization of large-scale Springwater textures, the definitively nonrandom spatial distribution of olivine orientations provides clues regarding the nature of the olivine's initial formation environment as well as the sequence of events subsequent to metal incorporation.

  12. Aligned olivine in the Springwater pallasite

    NASA Astrophysics Data System (ADS)

    Fowler-Gerace, Neva A.; Tait, Kimberly T.; Moser, Desmond E.; Barker, Ivan; Tian, Bob Y.

    2016-06-01

    The mechanism by which olivine grains became embedded within iron-nickel alloy in pallasite meteorites continues to be a matter of scientific debate. Geochemical and textural observations have failed to fully elucidate the origin and history of the olivine crystals; however, little research attention has been devoted to their crystallographic orientations within the metal matrix. Using electron backscatter diffraction, we have collected crystallographic orientation data for 296 crystals within ˜65 cm2 sample surface from Springwater. Though no global crystallographic preferred orientation exists, very low misorientations are observed among [100] axes of olivine crystals within specific texturally defined domains. Combined with a thorough characterization of large-scale Springwater textures, the definitively nonrandom spatial distribution of olivine orientations provides clues regarding the nature of the olivine's initial formation environment as well as the sequence of events subsequent to metal incorporation.

  13. Experimental Study of Olivine-rich Troctolites

    NASA Astrophysics Data System (ADS)

    Mu, S.; Faul, U.

    2014-12-01

    This experimental study is designed to complement field observations of olivine-rich troctolites in ophiolites and from mid-ocean ridges. The olivine-rich troctolites are characterized by high volume proportion of olivine with interstitial plagioclase and clinopyroxene. Typically the clinopyroxene occurs in the form of few large, poikilitic grains. The primary purpose of this study is to investigate the effects of cooling process on the geometry of the interstitial phases (clinopyroxene and plagioclase). Experiments are conducted in a piston cylinder apparatus by first annealing olivine plus a basaltic melt with a composition designed to be in equilibrium with four phases at ~ 1 GPa and 1250ºC. Initially, we anneal the olivine-basalt aggregates at 1350 °C and 0.7 GPa for one week to produce a steady state microstructure. At this temperature only olivine and minor opx are present as crystalline phases. We then cool the samples over two weeks below their solidus temperature, following different protocols. The post-run samples are sectioned, polished, and imaged at high resolution and analyzed by using a field emission SEM. Initial observations show that under certain conditions clinopyroxene nucleates distributed throughout the aggregate at many sites, forming relatively small, rounded to near euhedral grains. Under certain conditions few cpx grains nucleate and grow with a poikilitic shape, partially or fully enclosing olivine grains, as is observed in natural samples. As for partially molten aggregates quenched form the annealing temperature, the microstructure will be characterized by tracing phase boundaries on screen by using ImageJ software. The geometry of the interstitial phases will be quantified by determining the grain boundary wetness, in this case the ratio of the length of polyphase to single phase (olivine-olivine) boundaries. Compositional data will also be used to study the change in major element compositions before and after the cooling process.

  14. Crystallization kinetics of olivine-phyric shergottites

    NASA Astrophysics Data System (ADS)

    Ennis, Megan E.; McSween, Harry Y.

    2014-08-01

    Crystal size distribution (CSD) and spatial distribution pattern (SDP) analyses are applied to the early crystallizing phases, olivine and pyroxene, in olivine-phyric shergottites (Elephant moraine [EET] 79001A, Dar al Gani [DaG] 476, and dhofar [Dho] 019) from each sampling locality inferred from Mars ejection ages. Trace element zonation patterns (P and Cr) in olivine are also used to characterize the crystallization history of these Martian basalts. Previously reported 2-D CSDs for these meteorites are re-evaluated using a newer stereographically corrected methodology. Kinks in the olivine CSD plots suggest several populations that crystallized under different conditions. CSDs for pyroxene in DaG 476 and EET 79001A reveal single populations that grew under steady-state conditions; pyroxenes in Dho 019 were too intergrown for CSD analysis. Magma chamber residence times of several days for small grains to several months for olivine megacrysts are calculated using the CSD slopes and growth rates inferred from previous experimental data. Phosphorus imaging in olivines in DaG 476 and Dho 019 indicate rapid growth of skeletal, sector-zoned, or patchy cores, probably in response to delayed nucleation, followed by slow growth, and finally rapid dendritic growth with back-filling to form oscillatory zoning in rims. SPD analyses indicate that olivine and pyroxene crystals grew or accumulated in clusters rather than as randomly distributed grains. These data reveal complex solidification histories for Martian basalts, and are generally consistent with the formation at depth of olivine megacryst cores, which were entrained in ascending magmas that crystallized pyroxenes, small olivines, and oscillatory rims on megacrysts.

  15. Olivine-dominated asteroids: Mineralogy and origin

    NASA Astrophysics Data System (ADS)

    Sanchez, Juan A.; Reddy, Vishnu; Kelley, Michael S.; Cloutis, Edward A.; Bottke, William F.; Nesvorný, David; Lucas, Michael P.; Hardersen, Paul S.; Gaffey, Michael J.; Abell, Paul A.; Corre, Lucille Le

    2014-01-01

    Olivine-dominated asteroids are a rare type of objects formed either in nebular processes or through magmatic differentiation. The analysis of meteorite samples suggest that at least 100 parent bodies in the main belt experienced partial or complete melting and differentiation before being disrupted. However, only a few olivine-dominated asteroids, representative of the mantle of disrupted differentiated bodies, are known to exist. Due to the paucity of these objects in the main belt their origin and evolution have been a matter of great debate over the years. In this work we present a detailed mineralogical analysis of twelve olivine-dominated asteroids. We have obtained near-infrared (NIR) spectra (0.7-2.4 μm) of asteroids (246) Asporina, (289) Nenetta, (446) Aeternitas, (863) Benkoela, (4125) Lew Allen and (4490) Bamberry. Observations were conducted with the Infrared Telescope Facility (IRTF) on Mauna Kea, Hawai'i. This sample was complemented with spectra of six other olivine-dominated asteroids including (354) Eleonora, (984) Gretia, (1951) Lick, (2501) Lohja, (3819) Robinson and (5261) Eureka obtained by previous workers. Within our sample we distinguish two classes, one that we call monomineralic-olivine asteroids, which are those whose spectra only exhibit the 1 μm feature, and another referred to as olivine-rich asteroids, whose spectra exhibit the 1 μm feature and a weak (Band II depth ˜4%) 2 μm feature. For the monomineralic-olivine asteroids the olivine chemistry was found to range from ˜Fo49 to Fo70, consistent with the values measured for brachinites and R chondrites. In the case of the olivine-rich asteroids we determined their olivine and low-Ca pyroxene abundance using a new set of spectral calibrations derived from the analysis of R chondrites spectra. We found that the olivine abundance for these asteroids varies from 0.68 to 0.93, while the fraction of low-Ca pyroxene to total pyroxene ranges from 0.6 to 0.9. A search for dynamical

  16. Drastically Enhanced High-Rate Performance of Carbon-Coated LiFePO4 Nanorods Using a Green Chemical Vapor Deposition (CVD) Method for Lithium Ion Battery: A Selective Carbon Coating Process.

    PubMed

    Tian, Ruiyuan; Liu, Haiqiang; Jiang, Yi; Chen, Jiankun; Tan, Xinghua; Liu, Guangyao; Zhang, Lina; Gu, Xiaohua; Guo, Yanjun; Wang, Hanfu; Sun, Lianfeng; Chu, Weiguo

    2015-06-01

    Application of LiFePO4 (LFP) to large current power supplies is greatly hindered by its poor electrical conductivity (10(-9) S cm(-1)) and sluggish Li+ transport. Carbon coating is considered to be necessary for improving its interparticle electronic conductivity and thus electrochemical performance. Here, we proposed a novel, green, low cost and controllable CVD approach using solid glucose as carbon source which can be extended to most cathode and anode materials in need of carbon coating. Hydrothermally synthesized LFP nanorods with optimized thickness of carbon coated by this recipe are shown to have superb high-rate performance, high energy, and power densities, as well as long high-rate cycle lifetime. For 200 C (18s) charge and discharge, the discharge capacity and voltage are 89.69 mAh g(-1) and 3.030 V, respectively, and the energy and power densities are 271.80 Wh kg(-1) and 54.36 kW kg(-1), respectively. The capacity retention of 93.0%, and the energy and power density retention of 93.6% after 500 cycles at 100 C were achieved. Compared to the conventional carbon coating through direct mixing with glucose (or other organic substances) followed by annealing (DMGA), the carbon phase coated using this CVD recipe is of higher quality and better uniformity. Undoubtedly, this approach enhances significantly the electrochemical performance of high power LFP and thus broadens greatly the prospect of its applications to large current power supplies such as electric and hybrid electric vehicles. PMID:25970716

  17. Investigation of sodium insertion-extraction in olivine NaxFePO4 (0 ≤x≤ 1) using first-principles calculations.

    PubMed

    Saracibar, A; Carrasco, J; Saurel, D; Galceran, M; Acebedo, B; Anne, H; Lepoitevin, M; Rojo, T; Casas Cabanas, M

    2016-05-14

    Olivine NaFePO4 has recently attracted the attention of the scientific community as a promising cathode material for Na-ion batteries. In this work we combine density functional theory (DFT) calculations and high resolution synchrotron X-ray diffraction (HRXRD) experiments to study the phase stability of NaxFePO4 along the whole range of sodium compositions (0 ≤x≤ 1). DFT calculations reveal the existence of two intermediate structures governing the phase stability at x = 2/3 and x = 5/6. This is in contrast to isostructural LiFePO4, which is a broadly used cathode in Li-ion batteries. Na2/3FePO4 and Na5/6FePO4 ground states both align vacancies diagonally within the ab plane, coupled to a Fe(2+)/Fe(3+) alignment. HRXRD data for NaxFePO4 (2/3 < x < 1) materials show common superstructure reflections up to x = 5/6 within the studied compositions. The computed intercalation voltage profile shows a voltage difference of 0.16 V between NaFePO4 and Na2/3FePO4 in agreement with the voltage discontinuity observed experimentally during electrochemical insertion. PMID:27110665

  18. An Amoeboid Olivine Aggregate in LEW 85300

    NASA Technical Reports Server (NTRS)

    Komatsu, M. D.; Yamaguchi, A.; Fagan, T. J.; Zolensky, M. E.; Shiran, N.; Mikouchi, T.

    2016-01-01

    Amoeboid Olivine aggregates (AOAs) are irregularly shaped objects commonly observed in carbonaceous chondrites. Because they are composed of fine-grained olivine and Ca-Al-rich minerals, they are sensitive indicators for nebular process and parent body alteration of their parent bodies. Recently an AOA was found in a carbonaceous clast in polymict eucrite LEW 85300. The bulk major element composition of the clast matrix in LEW 85300 suggests a relation to CM, CO and CV chondrites, whereas bulk clast trace and major element compositions do not match any carbonaceous chondrite, suggesting they have a unique origin. Here we characterize the mineralogy of AOA in LEW 85300 and discuss the origin of the carbonaceous clasts. Results and Discussion: The AOA is located in an impact melt vein. Half of the aggregate shows recrystallization textures (euhedral pyroxene and molten metal/FeS) due to impact melting, but the remaining part preserves the original texture. The AOA is composed of olivine, FeS and Mg,Al-phyllosilicate. Individual olivine grains measure 1-8 microns, with Fe-rich rims, probably due to impact heating. Olivines in the AOA are highly forsteritic (Fo95-99), indicating that the AOA escaped thermal metamorphism [4]. Although no LIME (Low-Fe, Mn-Enriched) olivine is observed, forsterite composition and the coexistence of Mg,Al-phyllosilicate suggest that the AOA is similar to those in the Bali-type oxidized CV (CVoxB) and CR chondrites. However, it should be noted that fayalitic olivine, which commonly occurs in CVoxB AOA, is not observed in this AOA. Also, the smaller grain size (<8 microns) of olivine suggests they may be related to CM or CO chondrites. Therefore, we cannot exclude the possibility that the AOA originated from a unique carbonaceous chondrite.

  19. Olivine in Almahata Sitta - Curiouser and Curiouser

    NASA Technical Reports Server (NTRS)

    Zolensky, M. E.; Herrin, J.; Mikouchi, T.; Satake, W.; Kurihara, T.; Sandford, S. A.; Milam, S. N.; Hagiya, K.; Ohsumi, K.; Friedrich, J. M.; Jeniskens, P.; Shaddad, M. H.; Le, L.; Robinson, G. A.

    2010-01-01

    Almahata Sitta (hereafter Alma) is an anomalous, polymict ureilite. Anomalous features include low abundance of olivine, large compositional range of silicates, high abundance and large size of pores, crystalline pore wall linings, and overall finegrained texture. Tomography suggests the presence of foliation, which is known from other ureilites. Alma pyroxenes and their interpretation are discussed in two companion abstracts. In this abstract we discuss the composition of olivine in Alma, which is indicative of the complexity of this meteorite.

  20. Aligned Olivine in the Springwater Pallasite

    NASA Astrophysics Data System (ADS)

    Fowler-Gerace, N.; Tait, K.; Moser, D.; Barker, I.; Tian, B. Y.

    2014-12-01

    The mechanism by which olivine grains became embedded within iron-nickel alloy in pallasite meteorites continues to be a matter of scientific debate. Geochemical and textural observations have failed to fully elucidate the origin and history of the olivine crystals; however, little research attention has been devoted to their crystallographic orientations within the metal matrix. Klosterman and Buseck [1] found no crystallographic preferred orientation of olivine in nine pallasites, but the Leitz five-axis universal stage method imposed limitations on precision (estimated within ˜4◦) and sample size (only 10 crystals were measured in the Springwater pallasite, for instance). Using Electron Backscatter Diffraction, we have collected crystallographic orientation data (accurate to ±0.5◦ [2]) for 343 crystals within ˜65 cm2 sample surface from Springwater. Though no global crystallographic preferred orientation exists, very low misorientations are observed among [100] axes of olivine crystals within specific texturally-defined domains. Combined with our thorough characterization of large-scale Springwater textures, the definitively non-random spatial distribution of olivine orientations reveals the nature of the olivine's initial formation environment as well as the sequence of events subsequent to metal incorporation. [1] Klosterman and Buseck. 1973. J Geophys Res 78(32):7581-7588. [2] Oxford Instruments. 2013. http://www.ebsd.com/.

  1. Incompatible Trace Element Abundances in Hawaiian Olivines

    NASA Astrophysics Data System (ADS)

    Yu, G.; Huang, S.; Mukhopadhyay, S.; Jacobsen, S. B.

    2009-12-01

    Our understanding of trace elements partitioning between olivine and silicate melt is clouded by large variations in values of partition coefficients presented in the literature. In general, partition coefficients from phenocryst-matrix results are higher than those from experimental equilibration and in-situ measurements (such as LA-ICP-MS and Ion-probe) (Blard and Farley, 2008; Lee et al., 2007). This discrepancy is possibly caused by the presence of melt or micromineral inclusions in the analyzed phenocrysts, or contamination of grain boundaries by enriched glasses or accessory phases or uranium pick up from alteration of olivines. To further investigate why analysis of natural phenocrysts usually results in relative high apparent D’s for incompatible trace elements, six aliquots of olivine grains from a single sediment sample of Waimea river watershed, on the western side of the island of Kauai, Hawaii, were analyzed by solution ICP-MS at Harvard University for trace element concentrations. Two aliquots of olivines were leached in 1% oxalic acid for 45-60 min at 90 OC before dissolution. Leached and unleached olivines mostly show positive linear correlations in plots of incompatible trace elements versus La, which possibly indicates mixing lines between olivine and one end-member with higher incompatible element concentration (possibly melt inclusion). Assuming La concentration in olivine is zero, we estimate concentration of other incompatible elements in olivines using intercepts of these mixing lines. We obtain that U and Th concentration in the olivines to be about 1 ppb and 0.1 ppb respectively, corresponding to apparent DUol/melt and DThol/melt of 0.003 and 0.0001 if host lave has U of 0.3 ppm and Th of 1ppm (Gayer et al.,2008). Recently, helium isotopic measurements were made in these olivines (Gayer et al., 2008) and the results yield a basin-wide average erosion rate of 0.056 mma-1 for Waimea river watershed. Gayer et al. (2008) argued that

  2. Diffusion of highly charged cations in olivine

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.; Watson, E. B.; Liang, Y.

    2012-12-01

    Diffusion of tungsten, titanium and phosphorus have been measured in natural iron-bearing olivine (~Fo90) and synthetic forsterite. Experiments were run under buffered conditions (with iron-wustite or Ni-NiO buffers) in 1-atm furnaces. The sources of diffusant for experiments were MgWO4 for tungsten diffusion, Mg2TiO4 for Ti diffusion, and AlPO4 for P diffusion; in all cases these compounds were pre-reacted at high temperature with Mg2SiO4 or Fe-bearing olivine prior to diffusion anneals. Samples were placed with the source materials in noble metal or silica capsules, which were sealed under vacuum in silica glass ampoules with solid buffers. Rutherford backscattering spectrometry (RBS) was used to measure depth profiles for all sets of experiments; measurements of P were also made with Nuclear Reaction Analysis using the 31P(α,p)34S reaction. These new data suggest marked differences among diffusivities of these cations, with titanium diffusion faster than diffusion of tungsten, but slower than diffusion of phosphorus over the conditions investigated. Diffusivities of all of these elements appear significantly slower than those of divalent cations in olivine. These results will be discussed in context with extant diffusion data for major, trace and minor elements in olivine. The effects of oxygen fugacity and olivine composition on diffusion, and potential implications for diffusion mechanisms will also be considered.

  3. Raman spectra of shocked minerals. I - Olivine

    NASA Technical Reports Server (NTRS)

    Heymann, D.; Celucci, T. A.

    1988-01-01

    The Raman spectra of olivine contained in a chip of the Twin Sisters Peak (Washington) dunite shocked to 22.2 GPa is shown to be identical to that of unshocked olivine in the same rock. The Raman spectra of powder of the rock shocked to 20.1 GPa and of chips shocked to 59.5 GPa and 60.7 GPa display strong and broad low-frequency features with crests at 475/cm, 556/cm, and 572/cm, and broad high-frequency features near 1100/cm. It is suggested that these features are due to the formation of olivine glass with a considerable degree of three-dimensional Si-O-Si linkage having scattered domains of greatly variable grain size, internal structure, and chemical composition.

  4. Olivines: revelation of tracks of charged particles.

    PubMed

    Krishnaswami, S; Lal, D; Prabhu, N; Tamhane, A S

    1971-10-15

    A one-step, three-component aqueous etchant was developed for revealing the tracks of charged particles in olivine. The etchant reveals tracks of small cone angle, which are equally well developed in all the crystallographic directions. The scope of fossil cosmic-ray track studies in extraterrestrial samples has thus been increased, because olivine is often an abundant constituent and because it has a higher threshold ionization for track registration and has lower uranium, thorium, and trace element concentrations as compared with pyroxenes and feldspars. The etchant does not attack any of the principal rock-forming minerals in normal etching time, which allows a nondestructive study of fossil tracks in thin-section mounts. The study of fossil cosmic-ray tracks in olivine is particularly valuable for investigations of very, very heavy cosmic-ray nuclei and for highly irradiated samples such as those found in the lunar regolith. PMID:17778062

  5. Olivine-FeS Partial-Melt

    SciTech Connect

    Roberts, J; Siebert, J; Ryerson, F J; Kinney, J

    2006-10-02

    The figure shows Fe-S-filled melt channels in olivine created at high temperature and pressure. The 3D image was obtained on Beamline 8.3.2 at the Advanced Light Source, Lawrence Berkeley Laboratory, with a spatial resolution of better than two microns (bar is 10 microns). Permeability of Fe-S melts in olivine at high temperatures and pressures provides an important constraint on models of planetary core formation. Permeability must be inferred from empirical relationships based on microstructure. To date, estimates of permeability have varied by more than five orders of magnitude. To provide more accurate constraints, we used high-resolution synchrotron radiation computed tomography to image the three-dimensional network of melt-containing pores in an olivine matrix, and calculated the permeability directly by solving the equations of Stokes flow through the actual pore network using a lattice-Boltzmann approach. These calculations provide an independent constraint on models of planetary core formation.

  6. Shock-produced olivine glass - First observation

    NASA Technical Reports Server (NTRS)

    Jeanloz, R.; Ahrens, T. J.; Lally, J. S.; Nord, G. L., Jr.; Christie, J. M.; Heuer, A. H.

    1977-01-01

    Transmission electron microscope (TEM) observations of an experimentally shock-deformed single crystal of natural peridot, /Mg(0.88)Fe(0.12)/2SiO4, recovered from peak pressures of about 56 billion pascals revealed the presence of amorphous zones located within crystalline regions with a high density of tangled dislocations. This is the first reported observation of olivine glass. The shocked sample exhibits a wide variation in the degree of shock deformation on a small scale, and the glass appears to be intimately associated with the highest density of dislocations. This study suggests that olivine glass may be formed as a result of shock at pressures above about 50 to 55 billion pascals and that further TEM observations of naturally shocked olivines may demonstrate the presence of glass.

  7. Water-induced fabric transitions in olivine.

    PubMed

    Jung, H; Karato S

    2001-08-24

    The interpretation of seismic anisotropy in Earth's upper mantle has traditionally been based on the fabrics (lattice-preferred orientation) of relatively water-poor olivine. Here we show that when a large amount of water is added to olivine, the relation between flow geometry and seismic anisotropy undergoes marked changes. Some of the puzzling observations of seismic anisotropy in the upper mantle, including the anomalous anisotropy in the central Pacific and the complicated anisotropy in subduction zones, can be attributed to the enrichment of water in these regions. PMID:11520979

  8. The origin of ferrous zoning in Allende chondrule olivines

    NASA Astrophysics Data System (ADS)

    Peck, J. A.; Wood, J. A.

    1987-06-01

    Very similar major and minor element compositions are noted in the ferrous olivine occurring in chondrules at olivine grain boundaries, along cracks in olivine grains, interleaved with enstatite, and in the inner portions of exposed olivine grain surface rims; simultaneous formation by a single process is therefore suggested. The ferrous chondrule olivine probably formed by the reaction of chondrules with very hot nebular vapors over a period of several hours, followed by the condensation of residual metal vapors onto those olivine surfaces that were in direct contact with the gas as the system cooled. The ferrous chondrule olivine that occurs interleaved with enstatite in Allende does not have a composition identical to, and is not the precursor of, matrix olivine.

  9. Defect chemistry of phospho-olivine nanoparticles synthesized by a microwave-assisted solvothermal process

    NASA Astrophysics Data System (ADS)

    Bridges, Craig A.; Harrison, Katharine L.; Unocic, Raymond R.; Idrobo, Juan-Carlos; Parans Paranthaman, M.; Manthiram, Arumugam

    2013-09-01

    Nanocrystalline LiFePO4 powders synthesized by a microwave-assisted solvothermal (MW-ST) process have been structurally characterized with a combination of high resolution powder neutron diffraction, synchrotron X-ray diffraction, and aberration-corrected HAADF STEM imaging. A significant level of defects has been found in the samples prepared at 255 and 275 °C. These temperatures are significantly higher than what has previously been suggested to be the maximum temperature for defect formation in LiFePO4, so the presence of defects is likely related to the rapid MW-ST synthesis involving a short reaction time (˜5 min). A defect model has been tentatively proposed, though it has been shown that powder diffraction data alone cannot conclusively determine the precise defect distribution in LiFePO4 samples. The model is consistent with other literature reports on nanopowders synthesized at low temperatures, in which the unit cell volume is significantly reduced relative to defect-free, micron-sized LiFePO4 powders.

  10. Diffusive behavior in LiMPO4 with M=Fe, Co, Ni probed by muon-spin relaxation

    NASA Astrophysics Data System (ADS)

    Sugiyama, Jun; Nozaki, Hiroshi; Harada, Masashi; Kamazawa, Kazuya; Ikedo, Yutaka; Miyake, Yasuhiro; Ofer, Oren; Månsson, Martin; Ansaldo, Eduardo J.; Chow, Kim H.; Kobayashi, Genki; Kanno, Ryoji

    2012-02-01

    In order to study the diffusive nature of lithium transition-metal phospho-olivines, we measured muon-spin relaxation (μ+SR) spectra for the polycrystalline LiMPO4 samples with M=Mn, Fe, Co, or Ni in the temperature range between 50 and 500 K. The μ+SR spectra under zero applied field are strongly affected by the magnetic moments of the 3d electrons in the M2+ ions so that, for LiMnPO4, it was difficult to detect the relaxation change caused by the diffusion due to the large Mn2+(S=5/2) moments. However, diffusive behavior was clearly observed via the relaxation due to nuclear dipolar fields above ˜150 K for LiFePO4, LiCoPO4, and LiNiPO4 as S decreased from 2 to 1. From the temperature dependence of the nuclear field fluctuation rate, self-diffusion coefficients of Li+ ions (DLi) at 300 K and its activation energy (Ea) were estimated, respectively, as ˜3.6(2)×10-10 cm2/s and Ea=0.10(2) eV for LiFePO4, ˜1.6(1)×10-10 cm2/s and Ea=0.10(1) eV for LiCoPO4, and ˜2.7(4)×10-10 cm2/s and Ea=0.17(2) eV for LiNiPO4, assuming that the diffusing Li+ ions jump between the regular site and interstitial sites.

  11. Direct Shear of Olivine Single Crystals

    NASA Astrophysics Data System (ADS)

    Tielke, Jacob; Zimmerman, Mark; Kohlstedt, David

    2016-04-01

    Knowledge of the strength of individual dislocation slip systems in olivine is fundamental to understanding the flow behavior and the development of lattice-preferred orientation in olivine-rich rocks. The most direct measurements of the strengths of individual slip systems are from triaxial compression experiments on olivine single crystals. However, such experiments only allow for determination of flow laws for two of the four dominate slip systems in olivine. In order to measure the strengths of the (001)[100] and (100)[001] slip systems independently, we performed deformation experiments on single crystals of San Carlos olivine in a direct shear geometry. Experiments were carried out at temperatures of 1000° to 1300°C, a confining pressure of 300 MPa, shear stresses of 60 to 334 MPa, and resultant shear strain rates of 7.4 x 10‑6 to 6.7 x 10‑4 s‑1. At high-temperature (≥1200°C) and low-stress (≤200 MPa) conditions, the strain rate of crystals oriented for direct shear on either the (001)[100] or the (100)[001] slip system follows a power law relationship with stress, whereas at lower temperatures and higher stresses, strain rate depends exponentially on stress. The flow laws derived from the mechanical data in this study are consistent with a transition from the operation of a climb-controlled dislocation mechanism during power-law creep to the operation of a glide-controlled dislocation mechanism during exponential creep. In the climb-controlled regime, crystals oriented for shear on the (001)[100] slip system are weaker than crystals orientated for shear on the (100)[001] slip system. In contrast, in the glide-controlled regime the opposite is observed. Extrapolation of flow laws determined for crystals sheared in orientations favorable for slip on these two slip systems to upper mantle conditions reveals that the (001)[100] slip system is weaker at temperatures and stresses that are typical of the asthenospheric mantle, whereas the (100

  12. Water loss from olivine hosted melt inclusions

    NASA Astrophysics Data System (ADS)

    Chen, Y.; Provost, A.; Schiano, P.; Cluzel, N.

    2009-12-01

    Water content in melt inclusions has long been used as an important index for the water content of the hosting magma. However, many studies have shown that post-entrapment diffusive re-equilibration can affect the water content of melt inclusions. This process must be considered when using melt inclusions to infer water content of the hosting magma. Theoretical model on the diffusive re-equilibration between melt inclusions and external melts showed that the re-equilibration rate depends on the diffusivity of the re-equilibrating species in the host mineral, the partition coefficient of this species between the host mineral and melt, and the geometry of the melt inclusion and host mineral. The water diffusivity in olivine and water partition coefficient between melt and olivine have been measured by recent studies, therefore the diffusive re-equilibration model can be tested by experiments. In this study, we carried out in-situ Fourier transform infrared spectroscopy (FTIR) measurements on the water content of olivine hosted melt inclusions at high temperatures. Initial water content of the melt inclusions is about 4 wt%. A heating stage system is combined with a microscope FTIR and the absorption spectrum through the olivine and melt inclusion is repeatedly measured. Although the absorption band at around 3540 cm-1 has not be calibrated at high temperatures, it is assumed that the absorbance is linearly related to the total water concentration in the melt inclusion, and the relative water content can be inferred. Cautions have been exercised to maintain a consistent measurement spot such that the thickness of the melt inclusion within the beam path did not change significantly during each experiment. Oxygen fugacity in the heating stage is controlled by Zr purified Ar gas to be about 7 logarithm units below the QFM buffer and about 1 logarithm unit above the QIF buffer at 1473 K. Preliminary results showed that at 1430 and 1581 K, the total water content of the

  13. Shock-produced olivine glass: First observation

    USGS Publications Warehouse

    Jeanloz, R.; Ahrens, T.J.; Lally, J.S.; Nord, G.L., Jr.; Christie, J.M.; Heuer, A.H.

    1977-01-01

    Transmission electron microscope (TEM) observations of an experimentally shock-deformed single crystal of natural peridot, (Mg0.88Fe 0.12SiO4 recovered from peak pressures of about 56 ?? 109 pascals revealed the presence of amorphous zones located within crystalline regions with a high density of tangled dislocations. This is the first reported observation ofolivine glass. The shocked sample exhibits a wide variation in the degree of shock deformation on a small scale, and the glass appears to be intimately associated with the highest density of dislocations. This study suggests that olivine glass may be formed as a result of shock at pressures above about 50 to 55 ?? 109 pascals and that further TEM observations of naturally shocked olivines may demonstrate the presence of glass.

  14. H in olivine: How much and where?

    NASA Astrophysics Data System (ADS)

    Withers, A. C.; Umemoto, K.; Hirschmann, M. M.

    2011-12-01

    Hydrous defects in nominally anhydrous minerals are known to play a fundamental role in influencing the mechanisms and extent of deformation in mantle rocks. The extent of water weakening in olivine, in particular, may dictate the nature of upper mantle deformation, thereby controlling the very processes of tectonism. Infrared spectroscopy (IR) is a powerful tool commonly used to analyze these extrinsic defects. In addition to determining defect concentrations, and in contrast to other analytical techniques such as secondary ion mass spectroscopy (SIMS), IR offers the possibility of determining the location of H atoms in the crystal structure. In the case of olivine, however, the relationships between the IR spectrum and the concentrations and locations of hydrous defects are widely disputed, with recent estimates of calibration coefficients varying by more than a factor of 3, and the same absorption bands being thought variously to represent substitutions on tetrahedral or on octahedral crystallographic sites. New analytical and theoretical results will be used to refine our view of the location and concentration of H in olivine. Elastic recoil detection analysis (ERDA) measurements are used to determine the infrared absorption coefficient (k) for OH bands in Fo90 olivines with 240-2000 ppm H2O, synthesised at 3-10 GPa in multianvil experiments that were optimised for growth of large, homogeneous crystals. On the basis of 20 ERDA and >200 FTIR analyses of olivines from 7 experiments, the H content (in ppm H2O) is given by 0.120±0.008×total integral absorption, corresponding to an integral extinction coefficient of 45,000 L/(mol cm2), i.e. k is ~35% smaller than the value previously derived by Bell et al. (2003)[1] for natural olivines. This implies that the H contents of experimental olivines have been generally overestimated. The samples that were analysed using ERDA are used as SIMS standards, thereby providing a direct calibration that avoids the baseline

  15. Investigation of sodium insertion–extraction in olivine Na x FePO 4 (0 ≤ x ≤ 1) using first-principles calculations

    SciTech Connect

    Saracibar, A.; Carrasco, J.; Saurel, D.; Galceran, M.; Acebedo, B.; Anne, H.; Lepoitevin, M.; Rojo, T.; Casas Cabanas, M.

    2016-01-01

    Olivine NaFePO4 has recently attracted the attention of the scientific community as a promising cathode material for Na-ion batteries. In this work we combine density functional theory (DFT) calculations and high resolution synchrotron X-ray diffraction (HRXRD) experiments to study the phase stability of NaxFePO4 along the whole range of sodium compositions (0 ≤ x ≤ 1). DFT calculations reveal the existence of two intermediate structures governing the phase stability at x = 2/3 and x = 5/6. This is in contrast to isostructural LiFePO4, which is a broadly used cathode in Li-ion batteries. Na2/3FePO4 and Na5/6FePO4 ground states both align vacancies diagonally within the ab plane, coupled to a Fe2+/Fe3+ alignment. HRXRD data for NaxFePO4 (2/3 < x < 1) materials show common superstructure reflections up to x = 5/6 within the studied compositions. The computed intercalation voltage profile shows a voltage difference of 0.16 V between NaFePO4 and Na2/3FePO4 in agreement with the voltage discontinuity observed experimentally during electrochemical insertion.

  16. Exploring exogenic sources for the olivine on Asteroid (4) Vesta

    NASA Astrophysics Data System (ADS)

    Le Corre, Lucille; Reddy, Vishnu; Sanchez, Juan A.; Dunn, Tasha; Cloutis, Edward A.; Izawa, Matthew R. M.; Mann, Paul; Nathues, Andreas

    2015-09-01

    The detection of olivine on Vesta is interesting because it may provide critical insights into planetary differentiation early in our Solar System's history. Ground-based and Hubble Space Telescope (HST) observations of Asteroid (4) Vesta have suggested the presence of olivine on the surface. These observations were reinforced by the discovery of olivine-rich HED meteorites from Vesta in recent years. However, analysis of data from NASA's Dawn spacecraft has shown that this "olivine-bearing unit" is actually impact melt in the ejecta of Oppia crater. The lack of widespread mantle olivine, exposed during the formation of the 19 km deep Rheasilvia basin on Vesta's South Pole, further complicated this picture. Ammannito et al. (Ammannito, E. et al. [2013a]. Nature 504, 122-125) reported the discovery of local scale olivine-rich units in the form of excavated material from the mantle using the Visible and InfraRed spectrometer (VIR) on Dawn. These sites are concentrated in the walls and ejecta of craters Arruntia (10.5 km in diameter) and Bellicia (41.7 km in diameter), located in the northern hemisphere, 350-430 km from Rheasilvia basin's rim. Here we explore alternative sources for the olivine in the northern hemisphere of Vesta by reanalyzing the data from the VIR instrument using laboratory spectral measurements of meteorites. Our rationale for using the published dataset was to bypass calibration issues and ensure a consistent dataset between the two studies. Our analysis of the VIR data shows that while the interpretation of their spectra as an olivine-rich unit is correct, the nature and origin of that olivine could be more complicated. We suggest that these olivine exposures could also be explained by the delivery of olivine-rich exogenic material. This hypothesis is supported by meteoritical evidence in the form of exogenic xenoliths containing significant amount of olivine in some of the HED meteorites from Vesta. Previous laboratory work on HEDs show that

  17. 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.

  18. Water and Carbon Dioxide Adsorption at Olivine Surfaces

    SciTech Connect

    Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

    2013-11-14

    Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbon dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.

  19. Search for Olivine Spectral Signatures on the Surface of Vesta

    NASA Technical Reports Server (NTRS)

    Palomba, E.; De Sanctis, M. C.; Ammannito, E.; Capaccioni, F.; Capria, M. T.; Farina, M.; Frigeri, A.; Longobardo, A.; Tosi, F.; Zambon, F.; McSween, H. Y.; Mittlefehldt, D. W.; Russell, C. T.; Raymond, C. A.; Sunshine, J.; McCord, T. B.

    2012-01-01

    The occurrence of olivines on Vesta were first postulated from traditional petrogenetic models which suggest the formation of olivine as lower crustal cumulates. An indirect confirmation is given by their presence as a minor component in some samples of diogenite meteorites, the harzburgitic diogenites and the dunitic diogenites, and as olivine mineral clasts in howardites. Another indication for this mineral was given by interpretations of groundbased and Hubble Space Telescope observations that suggested the presence of local olivine-bearing units on the surface of Vesta. The VIR instrument onboard the DAWN mission has been mapping Vesta since July 2011. VIR acquired hyperspectral images of Vesta s surface in the wavelength range from 0.25 to 5.1 m during Approach, Survey and High Altitude Mapping (HAMO) orbits that allowed a 2/3 of the entire asteroid surface to be mapped. The VIR operative spectral interval, resolution and coverage is suitable for the detection and mapping of any olivine rich regions that may occur on the Vesta surface. The abundance of olivine in diogenites is typically lower than 10% but some samples richer in olivine are known. However, we do not expect to have extensive exposures of olivine-rich material on Vesta. Moreover, the partial overlap of olivine and pyroxene spectral signatures will make olivine difficult to detect. Different spectral parameters have been used to map olivine on extraterrestrial bodies, and here we discuss the different approaches used, and develop new ones specifically for Vesta. Our new methods are based on combinations of the spectral parameters relative to the 1 and 2 micron bands (the most prominent spectral features of Vesta surface in the visible and the infrared), such as band center locations, band depths, band areas, band area ratios. Before the direct application to the VIR data, the efficiency of each approach is evaluated by means of analysis of laboratory spectra of HED meteorites, pyroxenes, olivines

  20. Diffusive Fractionation of Lithium Isotopes in Olivine

    NASA Astrophysics Data System (ADS)

    Homolova, V.; Richter, F. M.; Watson, E. B.; Chaussidon, M.

    2014-12-01

    Systematic lithium isotope variations along concentration gradients found in olivine and pyroxene grains from terrestrial, lunar and martian rocks have been attributed to diffusive isotopic fractionation [Beck et al., 2006; Tang et al., 2007]. In some cases, these isotopic excursions are so large that a single grain may display isotopic variability that spans almost the entire range of documented terrestrial values [Jeffcoate et al., 2007]. In this study, we present the results of experiments to examine diffusive isotopic fractionation of lithium in olivine. The experiments comprised crystallographically oriented slabs of San Carlos olivine juxtaposed with either spodumene powder or a lithium rich pyroxene crystal. Experiments were conducted at 1 GPa and 0.1MPa over a temperature range of 1000 to 1125⁰C. Oxygen fugacity in the 0.1MPa experiments was controlled using the wustite-magnetite and nickel-nickel oxide solid buffer assemblages. Lithium concentrations generally decrease smoothly away from the edges of the grains; however, experiments involving diffusion parallel to the a-axis consistently show peculiar wavy or segmented concentration profiles. Lithium diffusivity parallel to the c-axis is on the order of 1E-14m2/s at 1100⁰C. The diffusivity parallel to the c-axis is more than an order of magnitude faster than diffusion parallel to the b-axis and correlates positively with oxygen fugacity. The lithium isotopic composition, δ7Li = 1000‰ * ((δ7Lisample- δ7Ligrain center)/ δ7Ligrain center), shows a decrease away from the edge of the grain to a minimum value (up to 70‰ lighter) and then an abrupt increase back to the initial isotopic composition of the olivine grain. This isotopic profile is similar to those found in natural grains and an experimental study on diffusive fractionation of lithium isotopes in pyroxene [Richter et al., 2014]. Results from the present study are modeled using the approach of Dohmen et al. [2010], which assumes lithium

  1. Discovery of Olivine in the Nili Fossae Region of Mars

    USGS Publications Warehouse

    Hoefen, T.M.; Clark, R.N.; Bandfield, J.L.; Smith, M.D.; Pearl, J.C.; Christensen, P.R.

    2003-01-01

    We have detected a 30,000-square-kilometer area rich in olivine in the Nili Fossae region of Mars. Nili Fossae has been interpreted as a complex of grabens and fractures related to the formation of the Isidis impact basin. We propose that post-impact faulting of this area has exposed subsurface layers rich in olivine. Linear mixture analysis of Thermal Emission Spectrometer spectra shows surface exposures of 30% olivine, where the composition of the olivine ranges from Fo30 to Fo70.

  2. Vaporization Studies of Olivine via Knudsen Effusion Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Costa, G. C. C.; Jacobson, N. S.

    2014-01-01

    Olivine is the major mineral in the Earth's upper mantle occurring predominantly in igneous rocks and has been identified in meteorites, asteroids, the Moon and Mars. Among many other important applications in planetary and materials sciences, the thermodynamic properties of vapor species from olivine are crucial as input parameters in computational modelling of the atmospheres of hot, rocky exoplanets (lava planets). There are several weight loss studies of olivine vaporization in the literature and one Knudsen Effusion Mass Spectrometry (KEMS) study. In this study, we examine a forsterite-rich olivine (93% forsterite and 7% fayalite, Fo93Fa7) with KEMS to further understand its vaporization and thermodynamic properties.

  3. A scanning electron microscope study of olivine crystal surfaces

    NASA Technical Reports Server (NTRS)

    Olsen, E. J.; Grossman, L.

    1974-01-01

    SEM photographs were taken of euhedral olivine grains from the Murchison C2 chondrite and several terrestrial and lunar occurrences. In general, the crystal faces of the meteorite grains are rough and uneven, with irregular growth patterns. They are very similar to crystal faces on terrestrial olivine grains that formed by sublimation from a vapor phase. They are very different from the relatively smooth and featureless surfaces of magmatic olivine crystals that precipitated from igneous melts. Qualitatively, the surface morphology of the crystal supports the contention that many euhedral crystals of olivine in C2 meteorites condensed from a gas phase.

  4. Olivine diogenites - The mantle of the eucrite parent body

    NASA Technical Reports Server (NTRS)

    Sack, Richard O.; Azeredo, William J.; Lipschutz, Michael E.

    1991-01-01

    Two olivine-rich Antarctic diogenites (ALH A77256 and ALH 84001) of the howardite-eucrite-diogenite (HED) meteorite association have olivine/pyroxene ratios similar to normative ratios in devolatilized ordinary chondrites. Based on chemical data and petrological analysis, these meteorites represent the residuum of partial melting of the mantle in the eucrite parent body (EPB). Mineral assemblages in these olivine-rich diogenites record a continuum in thermal histories from initial partial melting (1150-1200 C) to subsolidus reequilibration (795 + or - 55 C). The small number of olivine-rich diogenites known hints that only the outer portion of the EPB has been sampled.

  5. Anisotropy of electrical conductivity in dry olivine

    SciTech Connect

    Du Frane, W L; Roberts, J J; Toffelmier, D A; Tyburczy, J A

    2005-04-13

    [1] The electrical conductivity ({sigma}) was measured for a single crystal of San Carlos olivine (Fo{sub 89.1}) for all three principal orientations over oxygen fugacities 10{sup -7} < fO{sub 2} < 10{sup 1} Pa at 1100, 1200, and 1300 C. Fe-doped Pt electrodes were used in conjunction with a conservative range of fO{sub 2}, T, and time to reduce Fe loss resulting in data that is {approx}0.15 log units higher in conductivity than previous studies. At 1200 C and fO{sub 2} = 10{sup -1} Pa, {sigma}{sub [100]} = 10{sup -2.27} S/m, {sigma}{sub [010]} = 10{sup -2.49} S/m, {sigma}{sub [001]} = 10{sup -2.40} S/m. The dependences of {sigma} on T and fO{sub 2} have been simultaneously modeled with undifferentiated mixed conduction of small polarons and Mg vacancies to obtain steady-state fO{sub 2}-independent activation energies: Ea{sub [100]} = 0.32 eV, Ea{sub [010]} = 0.56 eV, Ea{sub [001]} = 0.71 eV. A single crystal of dry olivine would provide a maximum of {approx}10{sup 0.4} S/m azimuthal {sigma} contrast for T < 1500 C. The anisotropic results are combined to create an isotropic model with Ea = 0.53 eV.

  6. Mineralogical Comparison of Olivine in Shergottites and A Shocked L Chondrite: Implications for Shock Histories of Brown Olivine

    NASA Technical Reports Server (NTRS)

    Takenouchi, A.; Mikouchi, T.; Yamaguchi, A.; Zolensky, M. E.

    2015-01-01

    Most Martian meteorites are heavily shocked, exhibiting numerous shock features, for example undulatory extinction of olivine and pyroxene, the presence of diaplectic glass ("maskelynite") and the formation of shock melt. Among these shock features, olivine darkening ("brown" olivine) is unique in Martian meteorites because no other meteorite group shows such a feature. Although the presence of brown olivine in shergottites was reported thirty years ago, detailed observation by TEM has not been performed until the NWA 2737 chassignite was discovered, whose olivine is darkened, being completely black in hand specimen. Fe metal nano-particles were found in NWA 2737 olivine which are considered to have been formed by olivine reduction during heavy shock. Subsequently, magnetite nano-particles were also found in other Martian meteorites and the coexistence of Fe metal and magnetite nano-particles was reported in the NWA 1950 shergottite and some Fe metal nano-particles were mantled by magnetite. Therefore, the formation process of nano-particles seems to be complex. Because "brown" olivine is unique to Martian meteorites, they have a potential to constrain their shock conditions. In order to better understand the shock history of Martian meteorites, we compared olivine in several shergottites with that in a highly-shocked L chondrite which contains ringwoodite.

  7. Fast grain growth of olivine in liquid Fe-S and the formation of pallasites with rounded olivine grains

    NASA Astrophysics Data System (ADS)

    Solferino, Giulio F. D.; Golabek, Gregor J.; Nimmo, Francis; Schmidt, Max W.

    2015-08-01

    Despite their relatively simple mineralogical composition (olivine + Fe-Ni metal + FeS ± pyroxene), the origin of pallasite meteorites remains debated. It has been suggested that catastrophic mixing of olivine fragments with Fe-(Ni)-S followed by various degrees of annealing could explain pallasites bearing solely or prevalently fragmented or rounded olivines. In order to verify this hypothesis, and to quantify the grain growth rate of olivine in a liquid metal matrix, we performed a series of annealing experiments on natural olivine plus synthetic Fe-S mixtures. The best explanation for the observed olivine grain size distributions (GSD) of the experiments are dominant Ostwald ripening for small grains followed by random grain boundary migration for larger grains. Our results indicate that olivine grain growth in molten Fe-S is significantly faster than in solid, sulphur-free metal. We used the experimentally determined grain growth law to model the coarsening of olivine surrounded by Fe-S melt in a 100-600 km radius planetesimal. In this model, an impact is responsible for the mixing of olivine and Fe-(Ni)-S. Numerical models suggest that annealing at depths of up to 50 km allow for (i) average grain sizes consistent with the observed rounded olivine in pallasites, (ii) a remnant magnetisation of Fe-Ni olivine inclusions as measured in natural pallasites and (iii) for the metallographic cooling rates derived from Fe-Ni in pallasites. This conclusion is valid even if the impact occurs several millions of years after the differentiation of the target body was completed.

  8. Olivine in the Southern Isidis Basin

    NASA Technical Reports Server (NTRS)

    2007-01-01

    The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) took this observation of the transition region between Libya Montes and the Isidis Basin on Mars at 17:16 UTC (12:16 p.m. EST) on January 2, 2007, near 3.6 degrees north latitude, 84.1 degrees east longitude. The image was taken in 544 colors covering 0.36-3.92 micrometers, and shows features as small as 18 meters (60 feet) across. The image is about 11 kilometers (7 miles) wide at its narrowest point.

    The Isidis Basin resulted from of a gigantic impact on the surface of Mars early in the planet's history. The southern rim, where this target is located, is a region of complex geology and part of the planetary dichotomy boundary that separates the older southern highlands from the lower, younger northern plains. The image on the left was constructed from three visible wavelengths (RGB: 0.71, 0.60, 0.53 microns) and is a close approximation of how the surface would appear to the human eye. The image on the right was constructed from three infrared wavelengths (RGB: 2.49, 1.52, 1.08 microns) chosen to highlight variations in the mineralogy of the area. Of interest is that features in this image not only differ in color, but also in texture and morphology. The gray areas absorb similarly at all wavelengths used in this image, but display absorptions at other wavelengths related to the iron- and magesium-rich mineral pyroxene. The reddest areas absorb strongly at the wavelengths used for green and blue, which is attributable to another iron- and magesium-rich mineral, olivine. The brownish areas show subdued mineral absorptions and could represent some type of mixture between the other two materials. The presence of the mineral olivine is particularly interesting because olivine easily weathers to other minerals; thus, its presence indicates either the lack of weathering in this region or relatively recent exposure.

    CRISM's mission: Find the spectral fingerprints of aqueous and hydrothermal

  9. Development of crystal preferred orientation of olivine during diffusion creep: a matter of olivine crystal shape

    NASA Astrophysics Data System (ADS)

    Miyazaki, T.; Sueyoshi, K.; Hiraga, T.

    2013-12-01

    Crystalloagraphic preferred orientation (CPO) of olivine produced during dislocation creep is considered the primary cause of elastic anisotropy in the upper mantle of Earth and is used by seismologists to determine the direction of flow. Here we show that synthetic Fe-free olivine aggregates with either diopside or melt develop strong to weak CPO during grain boundary sliding (GBS) accommodated by diffusion. GBS on boundaries that correspond to specific crystallographic planes produces CPO. By combining the CPO patterns developed during tension and compression experiments, we predict formation in the mantle of three different CPO patterns depending on temperature and the presence of melt. Strong radial anisotropy is anticipated for GBS accommodated by diffusion during simple shear deformation at temperatures from 0.92*Ts to Ts (Ts: solidus temperature). These conditions correspond to depths where melting initiates to 50-100 km deeper and where strongly anisotropic and low seismic velocities are detected.

  10. Cotectic proportions of olivine and spinel in olivine-tholeiitic basalt and evaluation of pre-eruptive processes

    USGS Publications Warehouse

    Roeder, P.; Gofton, E.; Thornber, C.

    2006-01-01

    The volume %, distribution, texture and composition of coexisting olivine, Cr-spinel and glass has been determined in quenched lava samples from Hawaii, Iceland and mid-oceanic ridges. The volume ratio of olivine to spinel varies from 60 to 2800 and samples with >0.02% spinel have a volume ratio of olivine to spinel of approximately 100. A plot of wt % MgO vs ppm Cr for natural and experimental basaltic glasses suggests that the general trend of the glasses can be explained by the crystallization of a cotectic ratio of olivine to spinel of about 100. One group of samples has an olivine to spinel ratio of approximately 100, with skeletal olivine phenocrysts and small (100 ??m) spinel crystals that show evidence of two stages of growth, and a volume ratio of olivine to spinel of 100 to well over 1000. The olivine and spinel in this group have crystallized more slowly with little physical interaction, and show evidence that they have accumulated in a magma chamber. ?? 2006 Oxford University Press.