Continuous process to produce lithium-polymer batteries

DOEpatents

Chern, T.S.H.; Keller, D.G.; MacFadden, K.O.

1998-05-12

Solid polymer electrolytes are extruded with active electrode material in a continuous, one-step process to form composite electrolyte-electrodes ready for assembly into battery cells. The composite electrolyte electrode sheets are extruded onto current collectors to form electrodes. The composite electrodes, as extruded, are electronically and ionically conductive. The composite electrodes can be over coated with a solid polymer electrolyte, which acts as a separator upon battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte separator has low resistance. 1 fig.

Synthesis of One-Dimensional and Hyperbranched Nanomaterials for Lithium-Ion Battery Solid Electrolytes

NASA Astrophysics Data System (ADS)

Yang, Ting

Lithium-ion batteries can fail and catch fire when overcharged, exposed to high temperatures or short-circuited due to the highly flammable organic liquid used in the electrolyte. Using inorganic solid electrolyte materials can potentially improve the safety factor. Additionally, nanostructured electrolyte materials may further enhanced performance by taking advantage of their large aspect ratio. In this work, the synthesis of two promising nanostructured solid electrolyte materials was explored. Amorphous lithium niobate nanowires were synthesized through the decomposition of a niobium-containing complex in a structure-directing solvent using a reflux method. Lithium lanthanum titanate was obtained via solid state reaction with titanium oxide nanowires as the titanium precursor, but the nanowire morphology could not be preserved due to high temperature sintering. Hyperbranched potassium lanthanum titanate was synthesized through hydrothermal route. This was the first time that hyperbranched nanowires with perovskite structure were made without any catalyst or substrate. This result has the potential to be applied to other perovskite materials.

Extrusion of electrode material by liquid injection into extruder barrel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keller, David Gerard; Giovannoni, Richard Thomas; MacFadden, Kenneth Orville

An electrode sheet product is formed using an extruder having a feed throat and a downstream section by separately mixing an active electrode material and a solid polymer electrolyte composition that contains lithium salt. The active electrode material is fed into the feed throat of the extruder, while a portion of at least one fluid component of the solid polymer electrolyte composition is introduced to the downstream section. The active electrode material and the solid polymer electrolyte composition are compounded in a downstream end of the extruder. The extruded sheets, adhered to current collectors, can be formed into battery cells.

High strength porous support tubes for high temperature solid electrolyte electrochemical cells

DOEpatents

Rossing, Barry R.; Zymboly, Gregory E.

1986-01-01

A high temperature, solid electrolyte electrochemical cell is made, having an electrode and a solid electrolyte disposed on a porous, sintered support material containing thermally stabilized zirconia powder particles and from about 3 wt. % to about 45 wt. % of thermally stable oxide fibers.

Electrochemical Stability of Li 10GeP 2S 12 and Li 7La 3Zr 2O 12 Solid Electrolytes

DOE PAGES

Han, Fudong; Zhu, Yizhou; He, Xingfeng; ...

2016-01-21

The electrochemical stability window of solid electrolyte is overestimated by the conventional experimental method using a Li/electrolyte/inert metal semiblocking electrode because of the limited contact area between solid electrolyte and inert metal. Since the battery is cycled in the overestimated stability window, the decomposition of the solid electrolyte at the interfaces occurs but has been ignored as a cause for high interfacial resistances in previous studies, limiting the performance improvement of the bulk-type solid-state battery despite the decades of research efforts. Thus, there is an urgent need to identify the intrinsic stability window of the solid electrolyte. The thermodynamic electrochemicalmore » stability window of solid electrolytes is calculated using first principles computation methods, and an experimental method is developed to measure the intrinsic electrochemical stability window of solid electrolytes using a Li/electrolyte/electrolyte-carbon cell. The most promising solid electrolytes, Li10GeP2S12 and cubic Li-garnet Li7La3Zr2O12, are chosen as the model materials for sulfide and oxide solid electrolytes, respectively. The results provide valuable insights to address the most challenging problems of the interfacial stability and resistance in high-performance solid-state batteries.« less

Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

PubMed

Ganapathy, Swapna; van Eck, Ernst R H; Kentgens, Arno P M; Mulder, Fokko M; Wagemaker, Marnix

2011-12-23

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extrusion of electrode material by liquid injection into extruder barrel

DOEpatents

Keller, D.G.; Giovannoni, R.T.; MacFadden, K.O.

1998-03-10

An electrode sheet product is formed using an extruder having a feed throat and a downstream section by separately mixing an active electrode material and a solid polymer electrolyte composition that contains lithium salt. The active electrode material is fed into the feed throat of the extruder, while a portion of at least one fluid component of the solid polymer electrolyte composition is introduced to the downstream section. The active electrode material and the solid polymer electrolyte composition are compounded in a downstream end of the extruder. The extruded sheets, adhered to current collectors, can be formed into battery cells. 1 fig.

Extrusion of electrode material by liquid injection into extruder barrel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keller, D.G.; Giovannoni, R.T.; MacFadden, K.O.

An electrode sheet product is formed using an extruder having a feed throat and a downstream section by separately mixing an active electrode material and a solid polymer electrolyte composition that contains lithium salt. The active electrode material is fed into the feed throat of the extruder, while a portion of at least one fluid component of the solid polymer electrolyte composition is introduced to the downstream section. The active electrode material and the solid polymer electrolyte composition are compounded in a downstream end of the extruder. The extruded sheets, adhered to current collectors, can be formed into battery cells.more » 1 fig.« less

MultiLayer solid electrolyte for lithium thin film batteries

DOEpatents

Lee, Se -Hee; Tracy, C. Edwin; Pitts, John Roland; Liu, Ping

2015-07-28

A lithium metal thin-film battery composite structure is provided that includes a combination of a thin, stable, solid electrolyte layer [18] such as Lipon, designed in use to be in contact with a lithium metal anode layer; and a rapid-deposit solid electrolyte layer [16] such as LiAlF.sub.4 in contact with the thin, stable, solid electrolyte layer [18]. Batteries made up of or containing these structures are more efficient to produce than other lithium metal batteries that use only a single solid electrolyte. They are also more resistant to stress and strain than batteries made using layers of only the stable, solid electrolyte materials. Furthermore, lithium anode batteries as disclosed herein are useful as rechargeable batteries.

Artificial solid electrolyte interphase to address the electrochemical degradation of silicon electrodes.

PubMed

Li, Juchuan; Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

2014-07-09

Electrochemical degradation on silicon (Si) anodes prevents them from being successfully used in lithium (Li)-ion battery full cells. Unlike the case of graphite anodes, the natural solid electrolyte interphase (SEI) films generated from carbonate electrolytes do not self-passivate on Si, causing continuous electrolyte decomposition and loss of Li ions. In this work, we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphorus oxynitride (Lipon), which conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, a significant effect is observed in suppressing electrolyte decomposition, while Lipon of thinner than 40 nm has a limited effect. Ionic and electronic conductivity measurements reveal that the artificial SEI is effective when it is a pure ionic conductor, but electrolyte decomposition is only partially suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40-50 nm. This work provides guidance for designing artificial SEI films for high-capacity Li-ion battery electrodes using solid electrolyte materials.

Artificial Solid Electrolyte Interphase to Address the Electrochemical Degradation of Silicon Electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

2014-01-01

Electrochemical degradation on Si anodes prevents them from being successfully used in lithium-ion full cells. Unlike the case of graphite anodes, natural solid electrolyte interphase (SEI) films generated from carbonate electrolyte do not self-passivate on Si and causes continuous electrolyte decomposition. In this work we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphor oxynitride (Lipon), that conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, significant effect is observed in suppressing the electrolyte decomposition, while Lipon of thinner than 40more » nm has little effect. Ionic and electronic conductivity measurement reveals that the artificial SEI is effective when it is a pure ionic conductor, and the electrolyte decomposition is not suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40~50 nm. This work provides guidance for designing artificial SEI for high capacity lithium-ion battery electrodes using solid electrolyte materials.« less

Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

NASA Astrophysics Data System (ADS)

Kartini, Evvy; Manawan, Maykel

2016-02-01

With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say "the most important emerging energy technology" is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner's cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes, promise the potential to replace organic liquid electrolytes and thereby improve the safety of next-generation high-energy batteries. Li3PO4 has been proved to be a good candidate for solid electrolyte, due to its easy in preparation, low cost, high melting temperature and good compatibility with the electrode materials. In the present work, Li3PO4 has been prepared by wet chemical reaction, a simple method with the advantage of recycling a waste product H3PO4. The crystal structure has been characterized by both neutron and x-ray diffraction. The use of neutron scattering plays important role on observing the light atoms such as lithium ion. The x-ray diffraction results showed the crystal structure of orthorhombic phase P m n 21 (31), that belongs to the β-Li3PO4, with the lattice parameters are a = 6.123872, b = 5.250211, c = 4.876378. The conductivity of β-Li3PO4 was around 10-8 S/cm. Furthermore, the future application of the solid electrolyte layer in lithium ion battery will also be considered. It is concluded that the used of local resources on producing the solid electrolyte Li3PO4 for lithium ion battery will give more added values to the researches and national industry.

Self-Passivating Lithium/Solid Electrolyte/Iodine Cells

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar; Whitcare, Jay; Narayanan, Sekharipuram; West, William

2006-01-01

Robust lithium/solid electrolyte/iodine electrochemical cells that offer significant advantages over commercial lithium/ iodine cells have been developed. At room temperature, these cells can be discharged at current densities 10 to 30 times those of commercial lithium/iodine cells. Moreover, from room temperature up to 80 C, the maximum discharge-current densities of these cells exceed those of all other solid-electrolyte-based cells. A cell of this type includes a metallic lithium anode in contact with a commercial flexible solid electrolyte film that, in turn, is in contact with an iodine/ graphite cathode. The solid electrolyte (the chemical composition of which has not been reported) offers the high ionic conductivity needed for high cell performance. However, the solid electrolyte exhibits an undesirable chemical reactivity to lithium that, if not mitigated, would render the solid electrolyte unsuitable for use in a lithium cell. In this cell, such mitigation is affected by the formation of a thin passivating layer of lithium iodide at the anode/electrolyte interface. Test cells of this type were fabricated from iodine/graphite cathode pellets, free-standing solid-electrolyte films, and lithium-foil anodes. The cathode mixtures were made by grinding together blends of nominally 10 weight percent graphite and 90 weight percent iodine. The cathode mixtures were then pressed into pellets at 36 kpsi (248 MPa) and inserted into coin-shaped stainless-steel cell cases that were coated with graphite paste to minimize corrosion. The solid-electrolyte film material was stamped to form circular pieces to fit in the coin cell cases, inserted in the cases, and pressed against the cathode pellets with polyethylene gaskets. Lithium-foil anodes were placed directly onto the electrolyte films. The layers described thus far were pressed and held together by stainless- steel shims, wave springs, and coin cell caps. The assembled cells were then crimped to form hermetic seals. It was found that the solid electrolyte films became discolored within seconds after they were placed in contact with the cathodes - a result of facile diffusion of iodine through the solid electrolyte material (see figure).

Structural and electrical properties of NASICON type solid electrolyte nanoscaled glass-ceramic powder by mechanical milling for thin film batteries.

PubMed

Patil, Vaishali; Patil, Arun; Yoon, Seok-Jin; Choi, Ji-Won

2013-05-01

During last two decades, lithium-based glasses have been studied extensively as electrolytes for solid-state secondary batteries. For practical use, solid electrolyte must have high ionic conductivity as well as chemical, thermal and electrochemical stability. Recent progresses have focused on glass electrolytes due to advantages over crystalline solid. Glass electrolytes are generally classified into two types oxide glass and sulfide glass. Oxide glasses do not react with electrode materials and this chemical inertness is advantageous for cycle performances of battery. In this study, major effort has been focused on the improvement of the ion conductivity of nanosized LiAlTi(PO4)3 oxide electrolyte prepared by mechanical milling (MM) method. After heating at 1000 degrees C the material shows good crystallinity and ionic conductivity with low electronic conductivity. In LiTi2(PO4)3, Ti4+ ions are partially substituted by Al3+ ions by heat-treatment of Li20-Al2O3-TiO2-P2O5 glasses at 1000 degrees C for 10 h. The conductivity of this material is 1.09 x 10(-3) S/cm at room temp. The glass-ceramics show fast ion conduction and low E(a) value. It is suggested that high conductivity, easy fabrication and low cost make this glass-ceramics promising to be used as inorganic solid electrolyte for all-solid-state Li rechargeable batteries.

Solid oxide fuel cells having porous cathodes infiltrated with oxygen-reducing catalysts

DOEpatents

Liu, Meilin; Liu, Ze; Liu, Mingfei; Nie, Lifang; Mebane, David Spencer; Wilson, Lane Curtis; Surdoval, Wayne

2014-08-12

Solid-oxide fuel cells include an electrolyte and an anode electrically coupled to a first surface of the electrolyte. A cathode is provided, which is electrically coupled to a second surface of the electrolyte. The cathode includes a porous backbone having a porosity in a range from about 20% to about 70%. The porous backbone contains a mixed ionic-electronic conductor (MIEC) of a first material infiltrated with an oxygen-reducing catalyst of a second material different from the first material.

Non-aqueous electrolytes for electrochemical cells

DOEpatents

Zhang, Zhengcheng; Dong, Jian; Amine, Khalil

2016-06-14

An electrolyte electrochemical device includes an anodic material and an electrolyte, the electrolyte including an organosilicon solvent, a salt, and a hybrid additiving having a first and a second compound, the hybrid additive configured to form a solid electrolyte interphase film on the anodic material upon application of a potential to the electrochemical device.

Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

DOEpatents

Jacobson, Allan J.; Wang, Shuangyan; Kim, Gun Tae

2016-01-12

Methods using novel cathode, electrolyte and oxygen separation materials operating at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes include oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

Cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

DOEpatents

Jacobson, Allan J; Wang, Shuangyan; Kim, Gun Tae

2014-01-28

Novel cathode, electrolyte and oxygen separation materials are disclosed that operate at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes based on oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

Method of fabricating a monolithic core for a solid oxide fuela cell

DOEpatents

Zwick, S.A.; Ackerman, J.P.

1983-10-12

A method is disclosed for forming a core for use in a solid oxide fuel cell that electrochemically combines fuel and oxidant for generating galvanic output. The core has an array of electrolyte and interconnect walls that are substantially devoid of any composite inert materials for support consisting instead only of the active anode, cathode, electrolyte and interconnect materials. Each electrolyte wall consists of cathode and anode materials sandwiching electrolyte material therebetween, and each interconnect wall consists of the cathode and anode materials sandwiching interconnect material therebetween. The electrolyte and interconnect walls define a plurality of substantially parallel core passageways alternately having respectively the inside faces thereof with only the anode material or with only the cathode material exposed. In the wall structure, the electrolyte and interconnect materials are only 0.002 to 0.01 cm thick; and the cathode and anode materials are only 0.002 to 0.05 cm thick. The method consists of building up the electrolyte and interconnect walls by depositing each material on individually and endwise of the wall itself, where each material deposit is sequentially applied for one cycle; and where the depositing cycle is repeated many times until the material buildup is sufficient to formulate the core. The core is heat cured to become dimensionally and structurally stable.

Method of fabricating a monolithic core for a solid oxide fuel cell

DOEpatents

Zwick, Stanley A.; Ackerman, John P.

1985-01-01

A method is disclosed for forming a core for use in a solid oxide fuel cell that electrochemically combines fuel and oxidant for generating galvanic output. The core has an array of electrolyte and interconnect walls that are substantially devoid of any composite inert materials for support consisting instead only of the active anode, cathode, electrolyte and interconnect materials. Each electrolyte wall consists of cathode and anode materials sandwiching electrolyte material therebetween, and each interconnect wall consists of the cathode and anode materials sandwiching interconnect material therebetween. The electrolyte and interconnect walls define a plurality of substantially parallel core passageways alternately having respectively the inside faces thereof with only the anode material or with only the cathode material exposed. In the wall structure, the electrolyte and interconnect materials are only 0.002-0.01 cm thick; and the cathode and anode materials are only 0.002-0.05 cm thick. The method consists of building up the electrolyte and interconnect walls by depositing each material on individually and endwise of the wall itself, where each material deposit is sequentially applied for one cycle; and where the depositing cycle is repeated many times until the material buildup is sufficient to formulate the core. The core is heat cured to become dimensionally and structurally stable.

Method for making an electrochemical cell

DOEpatents

Tuller, Harry L.; Kramer, Steve A.; Spears, Marlene A.; Pal, Uday B.

1996-01-01

An electrochemical device including a solid electrolyte and solid electrode composed of materials having different chemical compositions and characterized by different electrical properties but having the same crystalline phase is provided. A method for fabricating an electrochemical device having a solid electrode and solid electrolyte characterized by the same crystalline phase is provided.

Symmetric supercapacitors using urea-modified lignin derived N-doped porous carbon as electrode materials in liquid and solid electrolytes

NASA Astrophysics Data System (ADS)

Wang, Keliang; Xu, Ming; Gu, Yan; Gu, Zhengrong; Fan, Qi Hua

2016-11-01

N-doped porous carbon materials derived from urea-modified lignin were prepared via efficient KOH activation under carbonization. The synthesized N-doped carbon materials, which displayed a well-developed porous morphology with high specific surface area of 3130 m2 g-1, were used as electrode materials in symmetric supercapacitors with aqueous and solid electrolytes. In consistent with the observed physical structures and properties, the supercapacitors exhibited specific capacitances of 273 and 306 F g-1, small resistances of 2.6 and 7.7 Ω, stable charge/discharge at different current densities for over 5000 cycles and comparable energy and power density in 6 mol L-1 KOH liquid and KOH-PVA solid electrolytes, respectively.

Cell and current collector felt arrangement for solid oxide electrochemical cell combinations

DOEpatents

Reichner, Philip

1988-01-01

A solid electrolyte electrochemical cell combination 1 is made, comprising an annular, axially elongated, inner electrode 2 containing at least one interior gas feed conduit 3; annular solid electrolyte segments 4 around and covering portions of the inner electrode; annular outer electrode segments 6 around and covering portions of the electrolyte segments; electronically conducting, non-porous, interconnection material 5 disposed between electrolyte segments and in contact with the inner electrode, and electronically conducting, porous, metal fiber current collector felts 7 disposed on top of the non-porous interconnect material and outer electrode segments, where both the non-porous interconnect material and the porous metal felts are disposed circumferentially about the cell, transversely to the axial length of the cell and the inner electrode is continuous for the entire axial length of the cell combination.

Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kartini, Evvy; Manawan, Maykel

With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say “the most important emerging energy technology” is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is stillmore » the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner’s cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes, promise the potential to replace organic liquid electrolytes and thereby improve the safety of next-generation high-energy batteries. Li{sub 3}PO{sub 4} has been proved to be a good candidate for solid electrolyte, due to its easy in preparation, low cost, high melting temperature and good compatibility with the electrode materials. In the present work, Li{sub 3}PO{sub 4} has been prepared by wet chemical reaction, a simple method with the advantage of recycling a waste product H{sub 3}PO{sub 4}. The crystal structure has been characterized by both neutron and x-ray diffraction. The use of neutron scattering plays important role on observing the light atoms such as lithium ion. The x-ray diffraction results showed the crystal structure of orthorhombic phase P m n 21 (31), that belongs to the β-Li{sub 3}PO{sub 4}, with the lattice parameters are a = 6.123872, b = 5.250211, c = 4.876378. The conductivity of β-Li{sub 3}PO{sub 4} was around 10{sup −8} S/cm. Furthermore, the future application of the solid electrolyte layer in lithium ion battery will also be considered. It is concluded that the used of local resources on producing the solid electrolyte Li{sub 3}PO{sub 4} for lithium ion battery will give more added values to the researches and national industry.« less

Interfacial material for solid oxide fuel cell

DOEpatents

Baozhen, Li; Ruka, Roswell J.; Singhal, Subhash C.

1999-01-01

Solid oxide fuel cells having improved low-temperature operation are disclosed. In one embodiment, an interfacial layer of terbia-stabilized zirconia is located between the air electrode and electrolyte of the solid oxide fuel cell. The interfacial layer provides a barrier which controls interaction between the air electrode and electrolyte. The interfacial layer also reduces polarization loss through the reduction of the air electrode/electrolyte interfacial electrical resistance. In another embodiment, the solid oxide fuel cell comprises a scandia-stabilized zirconia electrolyte having high electrical conductivity. The scandia-stabilized zirconia electrolyte may be provided as a very thin layer in order to reduce resistance. The scandia-stabilized electrolyte is preferably used in combination with the terbia-stabilized interfacial layer. The solid oxide fuel cells are operable over wider temperature ranges and wider temperature gradients in comparison with conventional fuel cells.

Solid oxide MEMS-based fuel cells

DOEpatents

Jankowksi, Alan F.; Morse, Jeffrey D.

2007-03-13

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Solid polymer MEMS-based fuel cells

DOEpatents

Jankowski, Alan F [Livermore, CA; Morse, Jeffrey D [Pleasant Hill, CA

2008-04-22

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Three-dimensional ionic conduction in the strained electrolytes of solid oxide fuel cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Yupei; Zou, Minda; Lv, Weiqiang

2016-05-07

Flexible power sources including fuel cells and batteries are the key to realizing flexible electronic devices with pronounced foldability. To understand the bending effects in these devices, theoretical analysis on three-dimensional (3-D) lattice bending is necessary. In this report, we derive a 3-D analytical model to analyze the effects of electrolyte crystal bending on ionic conductivity in flexible solid-state batteries/fuel cells. By employing solid oxide fuel cells as a materials' platform, the intrinsic parameters of bent electrolyte materials, including lattice constant, Young's modulus, and Poisson ratio, are evaluated. Our work facilitates the rational design of highly efficient flexible electrolytes formore » high-performance flexible device applications.« less

Composite solid polymer electrolyte membranes

DOEpatents

Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

2001-06-19

The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

Composite solid polymer electrolyte membranes

DOEpatents

Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

2006-05-30

The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

An advanced model framework for solid electrolyte intercalation batteries.

PubMed

Landstorfer, Manuel; Funken, Stefan; Jacob, Timo

2011-07-28

Recent developments of solid electrolytes, especially lithium ion conductors, led to all solid state batteries for various applications. In addition, mathematical models sprout for different electrode materials and battery types, but are missing for solid electrolyte cells. We present a mathematical model for ion flux in solid electrolytes, based on non-equilibrium thermodynamics and functional derivatives. Intercalated ion diffusion within the electrodes is further considered, allowing the computation of the ion concentration at the electrode/electrolyte interface. A generalized Frumkin-Butler-Volmer equation describes the kinetics of (de-)intercalation reactions and is here extended to non-blocking electrodes. Using this approach, numerical simulations were carried out to investigate the space charge region at the interface. Finally, discharge simulations were performed to study different limitations of an all solid state battery cell. This journal is © the Owner Societies 2011

Fabrication of Semi-quasi Solid DSSC using Spiro Material as Hole Transport Material

NASA Astrophysics Data System (ADS)

Safriani, L.; Primawati, W. P.; Mulyana, C.; Susilawati, T.; Aprilia, A.

2017-05-01

Dye Sensitized Solar Cells (DSSC) has been emerging a promising development in recent years. DSSC is a low-cost solar cell belonging to the third generation of solar cells. However, the conversion efficiency of DSSC is still far behind compared to silicon based solar cells. To produce long stability of DSSC, the used of solid state electrolyte is recommended instead of liquid electrolyte, though solid state DSSC also has problem relating to a lack of pore-filling hole transport material into mesoporous TiO2. In this work an attempt to improve performance of DSSC has been done by adding hole transport material into mesoporous TiO2 layer and optimizing fabrication method. In the first part of the work, we used low Tg material spiro-TAD and spiro-TPD as hole transport material with mosalyte and hybrid polymer as gel electrolyte to obtain a semi-quasi solid DSSC. In the second part, we modified fabrication method by annealing process before spin-coated spiro material into dye-coated TiO2 substrate. Current-voltage measurement of semi-quasi solid DSSC was performed using halogen lamp. We found that the used of spiro-TPD as hole transport give the best power conversion efficiency η = 2.03% of semi-quasi solid DSSC.

Electrolyte materials containing highly dissociated metal ion salts

DOEpatents

Lee, H.S.; Geng, L.; Skotheim, T.A.

1996-07-23

The present invention relates to metal ion salts which can be used in electrolytes for producing electrochemical devices, including both primary and secondary batteries, photoelectrochemical cells and electrochromic displays. The salts have a low energy of dissociation and may be dissolved in a suitable polymer to produce a polymer solid electrolyte or in a polar aprotic liquid solvent to produce a liquid electrolyte. The anion of the salts may be covalently attached to polymer backbones to produce polymer solid electrolytes with exclusive cation conductivity. 2 figs.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tan, Guoqiang; Wu, Feng; Zhan, Chun

The development of safe, stable, and long-life Li-ion batteries is being intensively pursued to enable the electrification of transportation and intelligent grid applications. Here, we report a new solid-state Li-ion battery technology, using a solid nanocomposite electrolyte composed of porous silica matrices with in situ immobilizing Li+ conducting ionic liquid, anode material of MCMB, and cathode material of LiCoO 2, LiNi 1/3Co 1/3Mn 1/3O 2, or LiFePO 4. An injection printing method is used for the electrode/electrolyte preparation. Solid nanocomposite electrolytes exhibit superior performance to the conventional organic electrolytes with regard to safety and cycle-life. They also have a transparentmore » glassy structure with high ionic conductivity and good mechanical strength. Solid-state full cells tested with the various cathodes exhibited high specific capacities, long cycling stability, and excellent high temperature performance. This solid-state battery technology will provide new avenues for the rational engineering of advanced Li-ion batteries and other electrochemical devices.« less

Emerging applications of spark plasma sintering in all solid-state lithium-ion batteries and beyond

NASA Astrophysics Data System (ADS)

Zhu, Hongzheng; Liu, Jian

2018-07-01

Solid-state batteries have received increasing attention due to their high safety aspect and high energy and power densities. However, the development of solid-state batteries is hindered by inferior solid-solid interfaces between the solid-state electrolyte and electrode, which cause high interfacial resistance, reduced Li-ion and electron transfer rate, and limited battery performance. Recently, spark plasma sintering (SPS) is emerging as a promising technique for fabricating solid-state electrolyte and electrode pellets with clean and intimate solid-solid interfaces. During the SPS process, the unique reaction mechanism through the combination of current, pressure and high heating rate allow the formation of desirable solid-solid interfaces between active material particles. Herein, this work focuses on the overview of the application of SPS for fabricating solid-state electrolyte and electrode in all solid-state Li-ion batteries, and beyond, such as solid-state Li-S and Na-ion batteries. The correlations among SPS parameters, interfacial resistance, and electrochemical properties of solid-state electrolytes and electrodes are discussed for different material systems. In the end, we point out future opportunities and challenges associated with SPS application in the hot area of solid-state batteries. It is expected that this timely review will stimulate more fundamental and applied research in the development of solid-state batteries by SPS.

Elongated solid electrolyte cell configurations and flexible connections therefor

DOEpatents

Reichner, P.

1989-10-17

A flexible, high temperature, solid oxide electrolyte electrochemical cell stack configuration is made, comprising a plurality of flattened, elongated, connected cell combinations, each cell combination containing an interior electrode having a top surface and a plurality of interior gas feed conduits, through its axial length, electrolyte contacting the interior electrode and exterior electrode contacting electrolyte, where a major portion of the air electrode top surface is covered by interconnection material, and where each cell has at least one axially elongated, electronically conductive, flexible, porous, metal fiber felt material in electronic connection with the air electrode through contact with a major portion of the interconnection material, the metal fiber felt being effective as a shock absorbent body between the cells. 4 figs.

New Polymer Electrolyte Cell Systems

NASA Technical Reports Server (NTRS)

Smyrl, William H.; Owens, Boone B.; Mann, Kent; Pappenfus, T.; Henderson, W.

2004-01-01

PAPERS PUBLISHED: 1. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials. Journal of the Electrochemical Society (2004), 15 1 (2), A209-A2 15. 2. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Ionic-liquidlpolymer electrolyte composite materials for electrochemical device applications. Polymeric Materials Science and Engineering (2003), 88 302. 3. Pappenfus, Ted R.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; and Smyrl, William H. Ionic Conductivity of a poly(vinylpyridinium)/Silver Iodide Solid Polymer Electrolyte System. Solid State Ionics (in press 2004). 4. Pappenfus Ted M.; Mann, Kent R; Smyrl, William H. Polyelectrolyte Composite Materials with LiPFs and Tetraglyme. Electrochemical and Solid State Letters, (2004), 7(8), A254.

Ion conduction in crystalline superionic solids and its applications

NASA Astrophysics Data System (ADS)

Chandra, Angesh

2014-06-01

Superionic solids an area of multidisciplinary research activity, incorporates to study the physical, chemical and technological aspects of rapid ion movements within the bulk of the special class of ionic materials. It is an emerging area of materials science, as these solids show tremendous technological scopes to develop wide variety of solid state electrochemical devices such as batteries, fuel cells, supercapacitors, sensors, electrochromic displays (ECDs), memories, etc. These devices have wide range of applicabilities viz. power sources for IC microchips to transport vehicles, novel sensors for controlling atmospheric pollution, new kind of memories for computers, smart windows/display panels, etc. The field grew with a rapid pace since then, especially with regards to designing new materials as well as to explore their device potentialities. Amongst the known superionic solids, fast Ag+ ion conducting crystalline solid electrolytes are attracted special attention due to their relatively higher room temperature conductivity as well as ease of materials handling/synthesis. Ion conduction in these electrolytes is very much interesting part of today. In the present review article, the ion conducting phenomenon and some device applications of crystalline/polycrystalline superionic solid electrolytes have been reviewed in brief. Synthesis and characterization tools have also been discussed in the present review article.

Solid oxide fuel cell having monolithic core

DOEpatents

Ackerman, J.P.; Young, J.E.

1983-10-12

A solid oxide fuel cell is described for electrochemically combining fuel and oxidant for generating galvanic output, wherein the cell core has an array of electrolyte and interconnect walls that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween. The electrolyte walls are arranged and backfolded between adjacent interconnect walls operable to define a plurality of core passageways alternately arranged where the inside faces thereof have only the anode material or only the cathode material exposed. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageway; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte and interconnect materials is of the order of 0.002 to 0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002 to 0.05 cm thick.

Monolithic All-Phosphate Solid-State Lithium-Ion Battery with Improved Interfacial Compatibility.

PubMed

Yu, Shicheng; Mertens, Andreas; Tempel, Hermann; Schierholz, Roland; Kungl, Hans; Eichel, Rüdiger-A

2018-06-22

High interfacial resistance between solid electrolyte and electrode of ceramic all-solid-state batteries is a major reason for the reduced performance of these batteries. A solid-state battery using a monolithic all-phosphate concept based on screen printed thick LiTi 2 (PO 4 ) 3 anode and Li 3 V 2 (PO 4 ) 3 cathode composite layers on a densely sintered Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 solid electrolyte has been realized with competitive cycling performance. The choice of materials was primarily based on the (electro-)chemical and mechanical matching of the components instead of solely focusing on high-performance of individual components. Thus, the battery utilized a phosphate backbone in combination with tailored morphology of the electrode materials to ensure good interfacial matching for a durable mechanical stability. Moreover, the operating voltage range of the active materials matches with the intrinsic electrochemical window of the electrolyte which resulted in high electrochemical stability. A highly competitive discharge capacity of 63.5 mAh g -1 at 0.39 C after 500 cycles, corresponding to 84% of the initial discharge capacity, was achieved. The analysis of interfacial charge transfer kinetics confirmed the structural and electrical properties of the electrodes and their interfaces with the electrolyte, as evidenced by the excellent cycling performance of the all-phosphate solid-state battery. These interfaces have been studied via impedance analysis with subsequent distribution of relaxation times analysis. Moreover, the prepared solid-state battery could be processed and operated in air atmosphere owing to the low oxygen sensitivity of the phosphate materials. The analysis of electrolyte/electrode interfaces after cycling demonstrates that the interfaces remained stable during cycling.

Photoelectrochemical cells for conversion of solar energy to electricity and methods of their manufacture

DOEpatents

Skotheim, Terje

1984-04-10

A photoelectric device is disclosed which comprises first and second layers of semiconductive material, each of a different bandgap, with a layer of dry solid polymer electrolyte disposed between the two semiconductor layers. A layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte is further interposed between the dry solid polymer electrolyte and the first semiconductor layer. A method of manufacturing such devices is also disclosed.

Serially connected solid oxide fuel cells having monolithic cores

DOEpatents

Herceg, Joseph E.

1987-01-01

A solid oxide fuel cell for electrochemically combining fuel and oxidant for generating galvanic output, wherein the cell core has an array of cell segments electrically serially connected in the flow direction, each segment consisting of electrolyte walls and interconnect that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageways; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte composite materials is of the order of 0.002-0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002-0.05 cm thick. Between 2 and 50 cell segments may be connected in series.

NASICON-Structured Materials for Energy Storage.

PubMed

Jian, Zelang; Hu, Yong-Sheng; Ji, Xiulei; Chen, Wen

2017-05-01

The demand for electrical energy storage (EES) is ever increasing, which calls for better batteries. NASICON-structured materials represent a family of important electrodes due to its superior ionic conductivity and stable structures. A wide range of materials have been considered, where both vanadium-based and titanium-based materials are recommended as being of great interest. NASICON-structured materials are suitable for both the cathode and the anode, where the operation potential can be easily tuned by the choice of transition metal and/or polyanion group in the structure. NASICON-structured materials also represent a class of solid electrolytes, which are widely employed in all-solid-state ion batteries, all-solid-state air batteries, and hybrid batteries. NASICON-structured materials are reviewed with a focus on both electrode materials and solid-state electrolytes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fuel cells with doped lanthanum gallate electrolyte

NASA Astrophysics Data System (ADS)

Feng, Man; Goodenough, John B.; Huang, Keqin; Milliken, Christopher

Single cells with doped lanthanum gallate electrolyte material were constructed and tested from 600 to 800°C. Both ceria and the electrolyte material were mixed with NiO powder respectively to form composite anodes. Doped lanthanum cobaltite was used exclusively as the cathode material. While high power density from the solid oxide fuel cells at 800°C was achieved. our results clearly indicate that anode overpotential is the dominant factor in the power loss of the cells. Better anode materials and anode processing methods need to be found to fully utilize the high ionic conductivity of the doped lanthanum galiate and achieve higher power density at 800°C from solid oxide fuel cells.

A review of electrolyte materials and compositions for electrochemical supercapacitors.

PubMed

Zhong, Cheng; Deng, Yida; Hu, Wenbin; Qiao, Jinli; Zhang, Lei; Zhang, Jiujun

2015-11-07

Electrolytes have been identified as some of the most influential components in the performance of electrochemical supercapacitors (ESs), which include: electrical double-layer capacitors, pseudocapacitors and hybrid supercapacitors. This paper reviews recent progress in the research and development of ES electrolytes. The electrolytes are classified into several categories, including: aqueous, organic, ionic liquids, solid-state or quasi-solid-state, as well as redox-active electrolytes. Effects of electrolyte properties on ES performance are discussed in detail. The principles and methods of designing and optimizing electrolytes for ES performance and application are highlighted through a comprehensive analysis of the literature. Interaction among the electrolytes, electro-active materials and inactive components (current collectors, binders, and separators) is discussed. The challenges in producing high-performing electrolytes are analyzed. Several possible research directions to overcome these challenges are proposed for future efforts, with the main aim of improving ESs' energy density without sacrificing existing advantages (e.g., a high power density and a long cycle-life) (507 references).

Solid oxide fuel cell having compound cross flow gas patterns

DOEpatents

Fraioli, A.V.

1983-10-12

A core construction for a fuel cell is disclosed having both parallel and cross flow passageways for the fuel and the oxidant gases. Each core passageway is defined by electrolyte and interconnect walls. Each electrolyte wall consists of cathode and anode materials sandwiching an electrolyte material. Each interconnect wall is formed as a sheet of inert support material having therein spaced small plugs of interconnect material, where cathode and anode materials are formed as layers on opposite sides of each sheet and are electrically connected together by the interconnect material plugs. Each interconnect wall in a wavy shape is connected along spaced generally parallel line-like contact areas between corresponding spaced pairs of generally parallel electrolyte walls, operable to define one tier of generally parallel flow passageways for the fuel and oxidant gases. Alternate tiers are arranged to have the passageways disposed normal to one another. Solid mechanical connection of the interconnect walls of adjacent tiers to the opposite sides of the common electrolyte wall therebetween is only at spaced point-like contact areas, 90 where the previously mentioned line-like contact areas cross one another.

Solid oxide fuel cell having compound cross flow gas patterns

DOEpatents

Fraioli, Anthony V.

1985-01-01

A core construction for a fuel cell is disclosed having both parallel and cross flow passageways for the fuel and the oxidant gases. Each core passageway is defined by electrolyte and interconnect walls. Each electrolyte wall consists of cathode and anode materials sandwiching an electrolyte material. Each interconnect wall is formed as a sheet of inert support material having therein spaced small plugs of interconnect material, where cathode and anode materials are formed as layers on opposite sides of each sheet and are electrically connected together by the interconnect material plugs. Each interconnect wall in a wavy shape is connected along spaced generally parallel line-like contact areas between corresponding spaced pairs of generally parallel electrolyte walls, operable to define one tier of generally parallel flow passageways for the fuel and oxidant gases. Alternate tiers are arranged to have the passageways disposed normal to one another. Solid mechanical connection of the interconnect walls of adjacent tiers to the opposite sides of the common electrolyte wall therebetween is only at spaced point-like contact areas, 90 where the previously mentioned line-like contact areas cross one another.

Solid oxide fuel cell having monolithic core

DOEpatents

Ackerman, John P.; Young, John E.

1984-01-01

A solid oxide fuel cell for electrochemically combining fuel and oxidant for generating galvanic output, wherein the cell core has an array of electrolyte and interconnect walls that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween, and each interconnect wall consists of thin layers of the cathode and anode materials sandwiching a thin layer of interconnect material therebetween. The electrolyte walls are arranged and backfolded between adjacent interconnect walls operable to define a plurality of core passageways alternately arranged where the inside faces thereof have only the anode material or only the cathode material exposed. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageway; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte and interconnect materials is of the order of 0.002-0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002-0.05 cm thick.

Lithium Metal-Copper Vanadium Oxide Battery with a Block Copolymer Electrolyte

DOE PAGES

Devaux, Didier; Wang, Xiaoya; Thelen, Jacob L.; ...

2016-09-08

Lithium (Li) batteries comprising multivalent positive active materials such as copper vanadium oxide have high theoretical capacity. These batteries with a conventional liquid electrolyte exhibit limited cycle life because of copper dissolution into the electrolyte. In this paper, we report here on the characterization of solid-state Li metal batteries with a positive electrode based on α-Cu 6.9V 6O 18.9 (α-CuVO 3). We replaced the liquid electrolyte by a nanostructured solid block copolymer electrolyte comprising of a mixture of polystyrene-b-poly(ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. In situ X-ray diffraction was used to follow the Li insertion/de-insertion mechanism into themore » α-CuVO 3 host material and its reversibility. In situ X-ray scattering revealed that the multistep electrochemical reactions involved are similar in the presence of liquid or solid electrolyte. The capacity fade of the solid-state batteries is less rapid than that of α-CuVO 3–Li metal batteries with a conventional liquid electrolyte. Hard X-ray microtomography revealed that upon cycling, voids and Cu-rich agglomerates were formed at the interface between the Li metal and the SEO electrolyte. Finally, the void volume and the volume occupied by the Cu-rich agglomerates were independent of C-rate and cycle number.« less

Elongated solid electrolyte cell configurations and flexible connections therefor

DOEpatents

Reichner, Philip

1989-01-01

A flexible, high temperature, solid oxide electrolyte electrochemical cell stack configuration is made, comprising a plurality of flattened, elongated, connected cell combinations 1, each cell combination containing an interior electrode 2 having a top surface and a plurality of interior gas feed conduits 3, through its axial length, electrolyte 5 contacting the interior electrode and exterior electrode 8 contacting electrolyte, where a major portion of the air electrode top surface 7 is covered by interconnection material 6, and where each cell has at least one axially elongated, electronically conductive, flexible, porous, metal fiber felt material 9 in electronic connection with the air electrode 2 through contact with a major portion of the interconnection material 6, the metal fiber felt being effective as a shock absorbent body between the cells.

Basic investigation into the electrical performance of solid electrolyte membranes

NASA Technical Reports Server (NTRS)

Richter, R.

1982-01-01

The electrical performance of solid electrolyte membranes was investigated analytically and the results were compared with experimental data. It is concluded that in devices that are used for pumping oxygen the major power losses have to be attributed to the thin film electrodes. Relations were developed by which the effectiveness of tubular solid electrolyte membranes can be determined and the optimum length evaluated. The observed failure of solid electrolyte tube membranes in very localized areas is explained by the highly non-uniform current distribution in the membranes. The analysis points to a possible contact resistance between the electrodes and the solid electrolyte material. This possible contact resistance remains to be investigated experimentally. It is concluded that film electrodes are not appropriate for devices which operate with current flow, i.e., pumps though they can be employed without reservation in devices that measure oxygen pressures if a limited increase in the response time can be tolerated.

Recent Advances in Fast Ion Conducting Materials and Devices - Proceedings of the 2nd Asian Conference on Solid State Ionics

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Liu, Qingguo; Chen, Liquan

The Table of Contents for the book is as follows: * Preface * Invited Papers * Recent Trends in Solid State Ionics * Theoretical Aspects of Fast Ion Conduction in Solids * Chemical Bonding and Intercalation Processes in Framework Structures * Extra-Large Near-Electrode Regions and Diffusion Length on the Solid Electrolyte-Electrode Interface as Studied by Photo-EMF Method * Frequency Response of Glasses * XPS Studies on Ion Conducting Glasses * Characterization of New Ambient Temperature Lithium Polymer-Electrolyte * Recent Development of Polymer Electrolytes: Solid State Voltammetry in Polymer Electrolytes * Secondary Solid State Batteries: From Material Properties to Commercial Development * Silver Vanadium Oxide Bronze and its Applications for Electrochemical Devices * Study on β''-Alumina Solid Electrolyte and β Battery in SIC * Materials for Solid Oxide Fuel Cells * Processing for Super Superionic Ceramics * Hydrogen Production Using Oxide Ionic or Protonic Conductor * Ionically Conductive Sulfide-Based Lithium Glasses * Relation of Conductivity to Structure and Structural Relaxation in Ion-Conducting Glasses * The Mechanism of Ionic Conductivity in Glass * The Role of Synthesis and Structure in Solid State Ionics - Electrodes to Superconductors * Electrochromism in Spin-Coated Thin Films from Peroxo-Poly tungstate Solutions * Electrochemical Studies on High Tc Superconductors * Multivalence Fast Ionic Conductors - Montmorillonites * Contributed Papers * Volt-Ampere Characteristics and Interface Charge Transport in Solid Electrolytes * Internal Friction of Silver Chalcogenides * Thermal Expansion of Ionic and Superionic Solids * Improvement of PEO-LiCF3SO3 Complex Electrolytes Using Additives * Ionic Conductivity of Modified Poly (Methoxy Polyethylene Glycol Methacrylate) s-Lithium Salt Complexes * Solid Polymer Electrolytes of Crosslinked Polyethylene Glycol and Lithium Salts * Single Ionic Conductors Prepared by in Situ Polymerization of Methacrylic Acid Alkali Metal Salts in Polyethylene Oxide * Redox Behavior of Alkyl Viologens in Ion Conductive Polymer Solid * Ionic Conductivity of Interpenetrating Polymer Networks Containing LiClO4 * Electrochemical Behaviors of Porphyrins Incorporated into Solid Polymer Electrolytes * Lithium Ion Conducting Polymer Electrolytes * Electrochemical Synthesis of Polyaniline Thin Film * Electrochemical Aspect of Polyaniline Electrode in Aqueous Electrolyte * Mixed Cation Effect in Epoxy Resin - PEO-IPN Containing Perchlorate Salts * Conductivity, Raman and IR Studies on the Doped PEO-PPG Polymer Blends * Proton Conducting Polymeric Electrolytes from Poly (Ethyleneoxide) System * Surface Structure of Polymer Solid Ionic Conductors Based on Segmented Polyether Polyurethaneureas * Study on Addition Products of LiI and Diethylene Glycol etc. * Solid State Rechargeable Battery Using Paper Form Copper Ion Conductive Solid Electrolyte * Characterization of Electrode/Electrolyte Interfaces in Battery Li/PVAC-Li-Mont./Li1+xV3O8 by AC Impedance Method * Investigation on Reversibility of Vanadium Oxide Cathode Materials in Solid-State Battery * Preparation and Characterization of Silver Boromolybdate Solid State Batteries * The Electric Properties of the Trinary Cathode Material and its Application in Magnisium Solid State Cell * Electrical Properties and Phase Relation of Na2Mo0.1S0.9O4 Doped with Rare Earth Sulfate * New Electrochemical Probe for Rapid Determination of Silicon Concentration in Hot Metals * A New Theoretical EMF Expression for SOx(x = 2, 3) Sensors Based on Na2SO4 Solid Electrolyte * Evaluation of the Electrochemical SOx(x = 2, 3) Sensor with a Tubular Nasicon Electrolyte * The Response Time of a Modified Oxygen Sensor Using Zirconia Electrolyte * Preparation, Characteristics and Sintering Behavior of MgO-PSZ Powder * Reaction between La0.9MnO3 and Yttria Doped Zirconia * Development of the Extended-Life Oxygen Sensor of Caβ''-Al2O3 * Caβ''-Al2O3 Ultra-Low Oxygen Sensor * Measurement of Sulfur Concentration with Zirconia-Based Electrolyte Cell in Molten Iron * Influence of SO2 on the Conductivity of Calcia Stabilized Zirconia * Reactions between YSZ and La1-xCaxMnO3 as a Cathode for SOFC * Preparation and Electrical Properties of Lithium β''-Alumina * Influence of Lithia Content on Properties of β''-Alumina Ceramics * Electrical Conductivity of Solid Solutions of Na2SO4 with Na2SeO4 * Effect of Antagonist XO42- = MoO42- and WO42- Ion Substitution on the Electrical Conductivity of Li2SO4 : Li2CO3 Eutectic System * Study on the Electrical Properties and Structure of Multicrystal Materials Li5+xGe1-xCrxV3O12 * Preliminary Study on Synthesis of Silver Zirconium Silicophosphates by Sol - Gel Process * Sodium Ion Conduction in Iron(III) Exchanged Y Zeolite * Electrical Properties of V5O9+x (x = 0, 1) and CuxV5O9.1 * Electrical Properties of the Tetragonal ZrO2 Stabilized with CeO2, CeO2 + Gd2O3 * Study of Preparation and Ionic Conduction of Doped Barium Cerate Perovskite * Preparing Fine Alumina Powder by Homogeneous Precipitation Method for Fabricating β''-Al2O3 * Amorphous Lithium Ion Conductors in Li2S-SiS2-LiBO2 System * Mixed Alkali Effect of Glass Super Ionic Conductors * Electrical Property and Phase Separation, Crystallization Behavior of A Cu+-Conducting Glass * Investigation of Phase Separation and Crystallization for 0.4CuI-0.3 Cu2O-0.3P2O5 Glass by SEM and XRD * Study on the Lithium Solid Electrolytes of Li3N-LiX(X = F, Cl, Br, I)-B2O3 Ternary Systems * Synthesis and Characterization of the Li2O : P2O5 : WO3 Glasses * The Electrochromic Properties of Electrodeposited Ni-O Films in Nonaqueous Electrolytes * All Solid-State WO3-MnO2 Based Electrochromic Window * Electrochromism in Nickel Oxide Films * E S R of X-Irradiated Melt Quenched Li2SO4 * Mixed-Alkali Effect in the Li2O-Na2O-TeO2 Glass System * Electrical and Thermal Studies on Silver Tellurite Glasses * Late Entries (Invited Papers) * Proton Conducting Polymers * Light Scattering Studies on Superionic Conductor YSZ * Development of Thin Film Surface Modified Solid State Electrochemical Gas Sensors * Author Index * List of Participants

NiF2/NaF:CaF2/Ca Solid-State High-Temperature Battery Cells

NASA Technical Reports Server (NTRS)

West, William; Whitacre, Jay; DelCastillo, Linda

2009-01-01

Experiments and theoretical study have demonstrated the promise of all-solid-state, high-temperature electrochemical battery cells based on NiF2 as the active cathode material, CaF2 doped with NaF as the electrolyte material, and Ca as the active anode material. These and other all-solid-state cells have been investigated in a continuing effort to develop batteries for instruments that must operate in environments much hotter than can be withstood by ordinary commercially available batteries. Batteries of this type are needed for exploration of Venus (where the mean surface temperature is about 450 C), and could be used on Earth for such applications as measuring physical and chemical conditions in geothermal wells and oil wells. All-solid-state high-temperature power cells are sought as alternatives to other high-temperature power cells based, variously, on molten anodes and cathodes or molten eutectic salt electrolytes. Among the all-solid-state predecessors of the present NiF2/NaF:CaF2/Ca cells are those described in "Solid-State High-Temperature Power Cells" (NPO-44396), NASA Tech Briefs, Vol. 32, No. 5 (May 2008), page 40. In those cells, the active cathode material is FeS2, the electrolyte material is a crystalline solid solution of equimolar amounts of Li3PO4 and LiSiO4, and the active anode material is Li contained within an alloy that remains solid in the intended high operational temperature range.

Lithium sulfide compositions for battery electrolyte and battery electrode coatings

DOEpatents

Liang, Chengdu; Liu, Zengcai; Fu, Wujun; Lin, Zhan; Dudney, Nancy J; Howe, Jane Y; Rondinone, Adam J

2014-10-28

Method of forming lithium-containing electrolytes are provided using wet chemical synthesis. In some examples, the lithium containing electrolytes are composed of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7. The solid electrolyte may be a core shell material. In one embodiment, the core shell material includes a core of lithium sulfide (Li.sub.2S), a first shell of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7, and a second shell including one of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7 and carbon. The lithium containing electrolytes may be incorporated into wet cell batteries or solid state batteries.

Co9 S8 /Co as a High-Performance Anode for Sodium-Ion Batteries with an Ether-Based Electrolyte.

PubMed

Zhao, Yingying; Pang, Qiang; Wei, Yingjin; Wei, Luyao; Ju, Yanming; Zou, Bo; Gao, Yu; Chen, Gang

2017-12-08

Co 9 S 8 has been regarded as a desirable anode material for sodium-ion batteries because of its high theoretical capacity. In this study, a Co 9 S 8 anode material containing 5.5 wt % Co (Co 9 S 8 /Co) was prepared by a solid-state reaction. The electrochemical properties of the material were studied in carbonate and ether-based electrolytes (EBE). The results showed that the material had a longer cycle life and better rate capability in EBE. This excellent electrochemical performance was attributed to a low apparent activation energy and a low overpotential for Na deposition in EBE, which improved the electrode kinetic properties. Furthermore, EBE suppressed side reactions of the electrode and electrolyte, which avoided the formation of a solid electrolyte interphase film. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A high-conduction Ge substituted Li3AsS4 solid electrolyte with exceptional low activation energy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sahu, Gayatri; Rangasamy, Ezhiylmurugan; Li, Juchuan

2014-04-16

In lithium-ion conducting solid electrolytes the potential to enable high-energy-density secondary batteries and offer distinctive safety features as an advantage over traditional liquid electrolytes is shown. Achieving the combination of high ionic conductivity, low activation energy, and outstanding electrochemical stability in crystalline solid electrolytes is a challenge for the synthesis of novel solid electrolytes. We report an exceptionally low activation energy (Ea) and high room temperature superionic conductivity via facile aliovalent substitution of Li 3AsS 4 by Ge, which increased the conductivity by two orders of magnitude as compared to the parent compound. The composition Li 3.334Ge 0.334As 0.666S 4more » has a high ionic conductivity of 1.12 mScm -1 at 27°C. Local Li + hopping in this material is accompanied by distinctive low activation energy Ea of 0.17 eV being the lowest of Li + solid conductors. Finally, our study demonstrates the efficacy of surface passivation of solid electrolyte to achieve compatibility with metallic lithium electrodes.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hui; Chen, Yan; Hood, Zachary D.

All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na 3SbS 4, a novel Na superionic conductor that needs much lower processing temperature belowmore » 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm -1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.« less

Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

NASA Technical Reports Server (NTRS)

DeSilva, J .H. S. R.; Udinwe, V.; Sideris, P. J.; Smart, M. C.; Krause, F. C.; Hwang, C.; Smith, K. A.; Greenbaum, S. G.

2012-01-01

Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

Degradation Mechanisms at the Li10GeP2S12/LiCoO2 Cathode Interface in an All-Solid-State Lithium-Ion Battery.

PubMed

Zhang, Wenbo; Richter, Felix H; Culver, Sean P; Leichtweiss, Thomas; Lozano, Juan G; Dietrich, Christian; Bruce, Peter G; Zeier, Wolfgang G; Janek, Jürgen

2018-06-20

All-solid-state batteries (ASSBs) show great potential for providing high power and energy densities with enhanced battery safety. While new solid electrolytes (SEs) have been developed with high enough ionic conductivities, SSBs with long operational life are still rarely reported. Therefore, on the way to high-performance and long-life ASSBs, a better understanding of the complex degradation mechanisms, occurring at the electrode/electrolyte interfaces is pivotal. While the lithium metal/solid electrolyte interface is receiving considerable attention due to the quest for high energy density, the interface between the active material and solid electrolyte particles within the composite cathode is arguably the most difficult to solve and study. In this work, multiple characterization methods are combined to better understand the processes that occur at the LiCoO 2 cathode and the Li 10 GeP 2 S 12 solid electrolyte interface. Indium and Li 4 Ti 5 O 12 are used as anode materials to avoid the instability problems associated with Li-metal anodes. Capacity fading and increased impedances are observed during long-term cycling. Postmortem analysis with scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy show that electrochemically driven mechanical failure and degradation at the cathode/solid electrolyte interface contribute to the increase in internal resistance and the resulting capacity fading. These results suggest that the development of electrochemically more stable SEs and the engineering of cathode/SE interfaces are crucial for achieving reliable SSB performance.

Solid electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Isaacs, H. S.

Progress in the development of functioning solid electrolyte fuel cells is summarized. The solid electrolyte cells perform at 1000 C, a temperature elevated enough to indicate high efficiencies are available, especially if the cell is combined with a steam generator/turbine system. The system is noted to be sulfur tolerant, so coal containing significant amounts of sulfur is expected to yield satisfactory performances with low parasitic losses for gasification and purification. Solid oxide systems are electrically reversible, and are usable in both fuel cell and electrolysis modes. Employing zirconium and yttrium in the electrolyte provides component stability with time, a feature not present with other fuel cells. The chemical reactions producing the cell current are reviewed, along with materials choices for the cathodes, anodes, and interconnections.

Design and synthesis of the superionic conductor Na10SnP2S12

NASA Astrophysics Data System (ADS)

Richards, William D.; Tsujimura, Tomoyuki; Miara, Lincoln J.; Wang, Yan; Kim, Jae Chul; Ong, Shyue Ping; Uechi, Ichiro; Suzuki, Naoki; Ceder, Gerbrand

2016-03-01

Sodium-ion batteries are emerging as candidates for large-scale energy storage due to their low cost and the wide variety of cathode materials available. As battery size and adoption in critical applications increases, safety concerns are resurfacing due to the inherent flammability of organic electrolytes currently in use in both lithium and sodium battery chemistries. Development of solid-state batteries with ionic electrolytes eliminates this concern, while also allowing novel device architectures and potentially improving cycle life. Here we report the computation-assisted discovery and synthesis of a high-performance solid-state electrolyte material: Na10SnP2S12, with room temperature ionic conductivity of 0.4 mS cm-1 rivalling the conductivity of the best sodium sulfide solid electrolytes to date. We also computationally investigate the variants of this compound where tin is substituted by germanium or silicon and find that the latter may achieve even higher conductivity.

Design principles for solid-state lithium superionic conductors.

PubMed

Wang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J; Kim, Jae Chul; Mo, Yifei; Ceder, Gerbrand

2015-10-01

Lithium solid electrolytes can potentially address two key limitations of the organic electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochemical stability. However, achieving a Li(+) conductivity in the solid state comparable to existing liquid electrolytes (>1 mS cm(-1)) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centred cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic conductivity, and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.

Design and synthesis of the superionic conductor Na10SnP2S12.

PubMed

Richards, William D; Tsujimura, Tomoyuki; Miara, Lincoln J; Wang, Yan; Kim, Jae Chul; Ong, Shyue Ping; Uechi, Ichiro; Suzuki, Naoki; Ceder, Gerbrand

2016-03-17

Sodium-ion batteries are emerging as candidates for large-scale energy storage due to their low cost and the wide variety of cathode materials available. As battery size and adoption in critical applications increases, safety concerns are resurfacing due to the inherent flammability of organic electrolytes currently in use in both lithium and sodium battery chemistries. Development of solid-state batteries with ionic electrolytes eliminates this concern, while also allowing novel device architectures and potentially improving cycle life. Here we report the computation-assisted discovery and synthesis of a high-performance solid-state electrolyte material: Na10SnP2S12, with room temperature ionic conductivity of 0.4 mS cm(-1) rivalling the conductivity of the best sodium sulfide solid electrolytes to date. We also computationally investigate the variants of this compound where tin is substituted by germanium or silicon and find that the latter may achieve even higher conductivity.

A review of lithium and non-lithium based solid state batteries

NASA Astrophysics Data System (ADS)

Kim, Joo Gon; Son, Byungrak; Mukherjee, Santanu; Schuppert, Nicholas; Bates, Alex; Kwon, Osung; Choi, Moon Jong; Chung, Hyun Yeol; Park, Sam

2015-05-01

Conventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment such as laptop computers, cell phones, and electric vehicles; however, they have several drawbacks, including expensive sealing agents and inherent hazards of fire and leakages. All solid state batteries utilize solid state electrolytes to overcome the safety issues of liquid electrolytes. Drawbacks for all-solid state lithium-ion batteries include high resistance at ambient temperatures and design intricacies. This paper is a comprehensive review of all aspects of solid state batteries: their design, the materials used, and a detailed literature review of various important advances made in research. The paper exhaustively studies lithium based solid state batteries, as they are the most prevalent, but also considers non-lithium based systems. Non-lithium based solid state batteries are attaining widespread commercial applications, as are also lithium based polymeric solid state electrolytes. Tabular representations and schematic diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity to occupy a niche in the alternative energy sector.

Solid state electrolyte composites based on complex hydrides and metal doped fullerenes/fulleranes for batteries and electrochemical applications

DOEpatents

Zidan, Ragaiy; Teprovich, Jr., Joseph A.; Colon-Mercado, Hector R.; Greenway, Scott D.

2018-05-01

A LiBH₄--C₆₀ nanocomposite that displays fast lithium ionic conduction in the solid state is provided. The material is a homogenous nanocomposite that contains both LiBH₄ and a hydrogenated fullerene species. In the presence of C₆₀, the lithium ion mobility of LiBH₄ is significantly enhanced in the as prepared state when compared to pure LiBH₄. After the material is annealed the lithium ion mobility is further enhanced. Constant current cycling demonstrated that the material is stable in the presence of metallic lithium electrodes. The material can serve as a solid state electrolyte in a solid-state lithium ion battery.

Serially connected solid oxide fuel cells having monolithic cores

DOEpatents

Herceg, J.E.

1985-05-20

Disclosed is a solid oxide fuel cell for electrochemically combining fuel and oxidant for generating galvanic output. The cell core has an array of cell segments electrically serially connected in the flow direction, each segment consisting of electrolyte walls and interconnect that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageways; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte composite materials is of the order of 0.002 to 0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002 to 0.05 cm thick. Between 2 and 50 cell segments may be connected in series.

Electrochemical cell method

DOEpatents

Kaun, T.D.; Eshman, P.F.

1980-05-09

A secondary electrochemical cell is prepared by providing positive and negative electrodes having outer enclosures of rigid perforated electrically conductive material defining an internal compartment containing the electrode material in porous solid form. The electrodes are each immersed in molten electrolyte salt prior to cell assembly to incorporate the cell electrolyte. Following solidification of the electrolyte substantially throughout the porous volume of the electrode material, the electrodes are arranged in an alternating positive-negative array with interelectrode separators of porous frangible electrically insulative material. The completed array is assembled into the cell housing and sealed such that on heating the solidified electrolyte flows into the interelectrode separator.

Study of ceria-carbonate nanocomposite electrolytes for low-temperature solid oxide fuel cells.

PubMed

Fan, L; Wang, C; Di, J; Chen, M; Zheng, J; Zhu, B

2012-06-01

Composite and nanocomposite samarium doped ceria-carbonates powders were prepared by solid-state reaction, citric acid-nitrate combustion and modified nanocomposite approaches and used as electrolytes for low temperature solid oxide fuel cells. X-ray Diffraction, Scanning Electron Microscope, low-temperature Nitrogen Adsorption/desorption Experiments, Electrochemical Impedance Spectroscopy and fuel cell performance test were employed in characterization of these materials. All powders are nano-size particles with slight aggregation and carbonates are amorphous in composites. Nanocomposite electrolyte exhibits much lower impedance resistance and higher ionic conductivity than those of the other electrolytes at lower temperature. Fuel cell using the electrolyte prepared by modified nanocomposite approach exhibits the best performance in the whole operation temperature range and achieves a maximum power density of 839 mW cm(-2) at 600 degrees C with H2 as fuel. The excellent physical and electrochemical performances of nanocomposite electrolyte make it a promising candidate for low-temperature solid oxide fuel cells.

Method of making sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

DOEpatents

Isenberg, Arnold O.

1989-01-01

An electrochemical apparatus is made containing an exterior electorde bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

DOEpatents

Isenberg, Arnold O.

1987-01-01

An electrochemical apparatus is made containing an exterior electrode bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

Multi-layered proton-conducting electrolyte

DOEpatents

Lee, Tae H.; Dorris, Stephen E.; Balachandran, Uthamalingam

2017-06-27

The present invention provides a multilayer anode/electrolyte assembly comprising a porous anode substrate and a layered solid electrolyte in contact therewith. The layered solid electrolyte includes a first dense layer of yttrium-doped barium zirconate (BZY), optionally including another metal besides Y, Ba, and Zr (e.g., a lanthanide metal such as Pr) on one surface thereof, a second dense layer of yttrium-doped barium cerate (BCY), and an interfacial layer between and contacting the BZY and BCY layers. The interfacial layer comprises a solid solution of the BZY and BCY electrolytes. The porous anode substrate comprises at least one porous ceramic material that is stable to carbon dioxide and water (e.g., porous BZY), as well as an electrically conductive metal and/or metal oxide (e.g., Ni, NiO, and the like).

Solid oxide fuel cell with single material for electrodes and interconnect

DOEpatents

McPheeters, Charles C.; Nelson, Paul A.; Dees, Dennis W.

1994-01-01

A solid oxide fuel cell having a plurality of individual cells. A solid oxide fuel cell has an anode and a cathode with electrolyte disposed therebetween, and the anode, cathode and interconnect elements are comprised of substantially one material.

Screening possible solid electrolytes by calculating the conduction pathways using Bond Valence method

NASA Astrophysics Data System (ADS)

Gao, Jian; Chu, Geng; He, Meng; Zhang, Shu; Xiao, RuiJuan; Li, Hong; Chen, LiQuan

2014-08-01

Inorganic solid electrolytes have distinguished advantages in terms of safety and stability, and are promising to substitute for conventional organic liquid electrolytes. However, low ionic conductivity of typical candidates is the key problem. As connective diffusion path is the prerequisite for high performance, we screen for possible solid electrolytes from the 2004 International Centre for Diffraction Data (ICDD) database by calculating conduction pathways using Bond Valence (BV) method. There are 109846 inorganic crystals in the 2004 ICDD database, and 5295 of them contain lithium. Except for those with toxic, radioactive, rare, or variable valence elements, 1380 materials are candidates for solid electrolytes. The rationality of the BV method is approved by comparing the existing solid electrolytes' conduction pathways we had calculated with those from experiments or first principle calculations. The implication for doping and substitution, two important ways to improve the conductivity, is also discussed. Among them Li2CO3 is selected for a detailed comparison, and the pathway is reproduced well with that based on the density functional studies. To reveal the correlation between connectivity of pathways and conductivity, α/ γ-LiAlO2 and Li2CO3 are investigated by the impedance spectrum as an example, and many experimental and theoretical studies are in process to indicate the relationship between property and structure. The BV method can calculate one material within a few minutes, providing an efficient way to lock onto targets from abundant data, and to investigate the structure-property relationship systematically.

Gradient isolator for flow field of fuel cell assembly

DOEpatents

Ernst, W.D.

1999-06-15

Isolator(s) include isolating material and optionally gasketing material strategically positioned within a fuel cell assembly. The isolating material is disposed between a solid electrolyte and a metal flow field plate. Reactant fluid carried by flow field plate channel(s) forms a generally transverse electrochemical gradient. The isolator(s) serve to isolate electrochemically a portion of the flow field plate, for example, transversely outward from the channel(s), from the electrochemical gradient. Further, the isolator(s) serve to protect a portion of the solid electrolyte from metallic ions. 4 figs.

Gradient isolator for flow field of fuel cell assembly

DOEpatents

Ernst, William D.

1999-01-01

Isolator(s) include isolating material and optionally gasketing material strategically positioned within a fuel cell assembly. The isolating material is disposed between a solid electrolyte and a metal flow field plate. Reactant fluid carried by flow field plate channel(s) forms a generally transverse electrochemical gradient. The isolator(s) serve to isolate electrochemically a portion of the flow field plate, for example, transversely outward from the channel(s), from the electrochemical gradient. Further, the isolator(s) serve to protect a portion of the solid electrolyte from metallic ions.

Performance of intermediate temperature (600-800 °C) solid oxide fuel cell based on Sr and Mg doped lanthanum-gallate electrolyte

NASA Astrophysics Data System (ADS)

Gong, Wenquan; Gopalan, Srikanth; Pal, Uday B.

The solid electrolyte chosen for this investigation was La 0.9Sr 0.1Ga 0.8Mg 0.2O 3 (LSGM). To select appropriate electrode materials from a group of possible candidate materials, AC complex impedance spectroscopy studies were conducted between 600 and 800 °C on symmetrical cells that employed the LSGM electrolyte. Based on the results of the investigation, LSGM electrolyte supported solid oxide fuel cells (SOFCs) were fabricated with La 0.6Sr 0.4Co 0.8Fe 0.2O 3-La 0.9Sr 0.1Ga 0.8Mg 0.2O 3 (LSCF-LSGM) composite cathode and nickel-Ce 0.6La 0.4O 2 (Ni-LDC) composite anode having a barrier layer of Ce 0.6La 0.4O 2 (LDC) between the LSGM electrolyte and the Ni-LDC anode. Electrical performances of these cells were determined and the electrode polarization behavior as a function of cell current was modeled between 600 and 800 °C.

An air-stable Na 3SbS 4 superionic conductor prepared by a rapid and economic synthetic procedure

DOE PAGES

Wang, Hui; Chen, Yan; Hood, Zachary D.; ...

2016-01-01

All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na 3SbS 4, a novel Na superionic conductor that needs much lower processing temperature belowmore » 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm -1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.« less

Spin coating of electrolytes

DOEpatents

Stetter, Joseph R.; Maclay, G. Jordan

1989-01-01

Methods for spin coating electrolytic materials onto substrates are disclosed. More particularly, methods for depositing solid coatings of ion-conducting material onto planar substrates and onto electrodes are disclosed. These spin coating methods are employed to fabricate electrochemical sensors for use in measuring, detecting and quantifying gases and liquids.

Solid electrolytes strengthened by metal dispersions

DOEpatents

Lauf, Robert J.; Morgan, Chester S.

1983-01-01

An improvement in solid electrolytes of advanced secondary batteries of the sodium-sulfur, sodium-halogen, and like combinations is achieved by providing said battery with a cermet electrolyte containing a metal dispersion ranging from 0.1 to 10.0 vol. % of a substantially nonreactive metal selected from the group consisting essentially of Pt, Cr, Fe, Co, Ni, Nb, their alloys, and their physical mixtures in the elemental or uncombined state, the remainder of said cermet being an ion-conductive ceramic material.

Solid electrolytes strengthened by metal dispersions

DOEpatents

Lauf, R.J.; Morgan, C.S.

1981-10-05

An improvement in solid electrolytes of advanced secondary batteries of the sodium-sulfur, sodium-halogen, and like combinations is achieved by providing said battery with a cermet electrolyte containing a metal dispersion ranging from 0.1 to 10.0 vol. % of a substantially nonreactive metal selected from the group consisting essentially of Pt, Cr, Fe, Co, Ni, Nb, their alloys, and their physical mixtures in the elemental or uncombined state, the remainder of said cermet being an ion-conductive ceramic material.

Lithium sulfide compositions for battery electrolyte and battery electrode coatings

DOEpatents

Liang, Chengdu; Liu, Zengcai; Fu, Wunjun; Lin, Zhan; Dudney, Nancy J; Howe, Jane Y; Rondinone, Adam J

2013-12-03

Methods of forming lithium-containing electrolytes are provided using wet chemical synthesis. In some examples, the lithium containing electroytes are composed of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7. The solid electrolyte may be a core shell material. In one embodiment, the core shell material includes a core of lithium sulfide (Li.sub.2S), a first shell of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7, and a second shell including one or .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7 and carbon. The lithium containing electrolytes may be incorporated into wet cell batteries or solid state batteries.

Trace water sensor

NASA Technical Reports Server (NTRS)

Stephens, James B. (Inventor); Yang, Mary M. (Inventor); Laue, Eric G. (Inventor)

1985-01-01

A solid electrolytic type hygrometer is described, which operates with high reliability while providing rapid and sensitive response. A gold foil electrode (16) is wrapped about a hollow glass cylinder (18), a sheet (12) of hygroscopic-electrolytic material is wrapped about the foil, and a wire (14) is wound around the outside of the electrolytic sheet. Moisture passing between wire turns can be absorbed by the electrolytic material (12), and then dissociated by current passed by the electrodes (14, 16) through the electrolytic material. The cylinder has a slit (20) extending along its length, to allow resilient expansion to press the sheet of electrolytic material firmly against the electrodes. The wire turns lie against one another to cause rapid dissociation of moisture throughout the electrolytic material. Additional guard wires (42,44, FIG. 2) lie at opposite ends of the electrolytic sheet, and currents pass through them to avoid moisture buildup at the ends of the main wire coil. The electrical current through the sheet or membrane is proportional to the partial pressure of the water-vapor.

Method for manufacturing an electrochemical cell

DOEpatents

Kaun, Thomas D.; Eshman, Paul F.

1982-01-01

A secondary electrochemical cell is prepared by providing positive and negative electrodes having outer enclosures of rigid perforated electrically conductive material defining an internal compartment containing the electrode material in porous solid form. The electrodes are each immersed in molten electrolyte salt prior to cell assembly to incorporate the cell electrolyte. Following solidification of the electrolyte substantially throughout the porous volume of the electrode material, the electrodes are arranged in an alternating positive-negative array with interelectrode separators of porous frangible electrically insulative material. The completed array is assembled into the cell housing and sealed such that on heating the solidified electrolyte flows into the interelectrode separator.

Design and synthesis of the superionic conductor Na10SnP2S12

PubMed Central

Richards, William D.; Tsujimura, Tomoyuki; Miara, Lincoln J.; Wang, Yan; Kim, Jae Chul; Ong, Shyue Ping; Uechi, Ichiro; Suzuki, Naoki; Ceder, Gerbrand

2016-01-01

Sodium-ion batteries are emerging as candidates for large-scale energy storage due to their low cost and the wide variety of cathode materials available. As battery size and adoption in critical applications increases, safety concerns are resurfacing due to the inherent flammability of organic electrolytes currently in use in both lithium and sodium battery chemistries. Development of solid-state batteries with ionic electrolytes eliminates this concern, while also allowing novel device architectures and potentially improving cycle life. Here we report the computation-assisted discovery and synthesis of a high-performance solid-state electrolyte material: Na10SnP2S12, with room temperature ionic conductivity of 0.4 mS cm−1 rivalling the conductivity of the best sodium sulfide solid electrolytes to date. We also computationally investigate the variants of this compound where tin is substituted by germanium or silicon and find that the latter may achieve even higher conductivity. PMID:26984102

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

DOEpatents

Eberhart, James G.; Battles, James E.

1980-01-01

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

Solid oxide fuel cell with single material for electrodes and interconnect

DOEpatents

McPheeters, C.C.; Nelson, P.A.; Dees, D.W.

1994-07-19

A solid oxide fuel cell is described having a plurality of individual cells. A solid oxide fuel cell has an anode and a cathode with electrolyte disposed there between, and the anode, cathode and interconnect elements are comprised of substantially one material. 9 figs.

Deliberate modification of the solid electrolyte interphase (SEI) during lithiation of magnetite, Fe 3O 4: impact on electrochemistry

DOE PAGES

Bock, David C.; Marschilok, Amy C.; Takeuchi, Kenneth J.; ...

2017-11-20

Here, magnetite is a conversion anode material displaying multi-electron transfer during lithiation and delithiation. The solid electrolyte interphase (SEI) on magnetite, Fe 3O 4, electrodes for lithium ion batteries was deliberately modified through the use of fluoroethylene carbonate (FEC) electrolyte additive, improving both capacity retention and rate capability. Analysis showed reduction of FEC at higher voltage compared to non-fluorinated solvents with formation of a modified lithium flouride containing electrode surface.

Cobalt doped lanthanum chromite material suitable for high temperature use

DOEpatents

Ruka, Roswell J.

1986-01-01

A high temperature, solid electrolyte electrochemical cell, subject to thermal cycling temperatures of between about 25.degree. C. and about 1200.degree. C., capable of electronic interconnection to at least one other electrochemical cell and capable of operating in an environment containing oxygen and a fuel, is made; where the cell has a first and second electrode with solid electrolyte between them, where an improved interconnect material is applied along a portion of a supporting electrode; where the interconnect is made of a chemically modified lanthanum chromite, containing cobalt as the important additive, which interconnect allows for adjustment of the thermal expansion of the interconnect material to more nearly match that of other cell components, such as zirconia electrolyte, and is stable in oxygen containing atmospheres such as air and in fuel environments.

Evaluation of Ca3Co2O6 as cathode material for high-performance solid-oxide fuel cell

PubMed Central

Wei, Tao; Huang, Yun-Hui; Zeng, Rui; Yuan, Li-Xia; Hu, Xian-Luo; Zhang, Wu-Xing; Jiang, Long; Yang, Jun-You; Zhang, Zhao-Liang

2013-01-01

A cobalt-based thermoelectric compound Ca3Co2O6 (CCO) has been developed as new cathode material with superior performance for intermediate-temperature (IT) solid-oxide fuel cell (SOFC). Systematic evaluation has been carried out. Measurement of thermal expansion coefficient (TEC), thermal-stress (σ) and interfacial shearing stress (τ) with the electrolyte show that CCO matches well with several commonly-used IT electrolytes. Maximum power density as high as 1.47 W cm−2 is attained at 800°C, and an additional thermoelectric voltage of 11.7 mV is detected. The superior electrochemical performance, thermoelectric effect, and comparable thermal and mechanical behaviors with the electrolytes make CCO to be a promising cathode material for SOFC. PMID:23350032

Glassy materials for lithium batteries: electrochemical properties and devices performances

NASA Astrophysics Data System (ADS)

Duclot, Michel; Souquet, Jean-Louis

Amorphous or glassy materials may be used as electrolyte or electrode materials for lithium primary or secondary batteries. A first generation proceeded from classical coin cells in which the organic electrolyte was replaced by a high lithium conductive glassy electrolyte. The solid components were assembled under isostatic pressure. The main advantages of such cells are a good storage stability and ability to operate until 200°C. Nevertheless, the high resistivity of the glassy electrolyte below room temperature and a limited depth for charge and discharge cycles makes these cells not competitive compared to conventional lithium-ion batteries. More promising, are the thin films solid state microbatteries realised by successive depositions of electrodes and electrolyte. The low resistance of the electrolyte amorphous layer allows cycling at temperatures as low as -10°C. The total thickness of thin film batteries, including packaging is less than 100 μm. A capacity of about 100 μAh cm -2 with over 10 4 charge-discharge cycles at 90% in depth of discharge is well suited for energy independent smart cards or intelligent labels, which represent for these devices a large and unrivalled market.

Method of doping a semiconductor

DOEpatents

Yang, Chiang Y.; Rapp, Robert A.

1983-01-01

A method for doping semiconductor material. An interface is established between a solid electrolyte and a semiconductor to be doped. The electrolyte is chosen to be an ionic conductor of the selected impurity and the semiconductor material and electrolyte are jointly chosen so that any compound formed from the impurity and the semiconductor will have a free energy no lower than the electrolyte. A potential is then established across the interface so as to allow the impurity ions to diffuse into the semiconductor. In one embodiment the semiconductor and electrolyte may be heated so as to increase the diffusion coefficient.

Solid-state proton conductors

NASA Astrophysics Data System (ADS)

Jewulski, J. R.; Osif, T. L.; Remick, R. J.

1990-12-01

The purpose of this program was to survey the field of solid-state proton conductors (SSPC), identify conductors that could be used to develop solid-state fuel cells suitable for use with coal derived fuel gases, and begin the experimental research required for the development of these fuel cells. This document covers the following topics: the history of developments and current status of the SSPC, including a review of proton conducting electrolyte structures, the current status of the medium temperature SSPC development, electrodes for moderate temperature (SSPC) fuel cell, basic material and measurement techniques applicable for SSPC development, modeling, and optimization studies. Correlation and optimization studies are described which include correlation studies on proton conduction and oxide cathode optimization for the SSPC fuel cell. Experiments with the SSPC fuel cells are presented which include the fabrication of the electrolyte disks, apparatus for conducting measurements, the strontium-cerium based electrolyte, the barium-cerium based electrolyte with solid foil electrodes, the barium-cerium based electrolyte with porous electrodes, and conduction mechanisms.

Ionic Borate-Based Covalent Organic Frameworks: Lightweight Porous Materials for Lithium-Stable Solid State Electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Black, Hayden T.; Harrison, Katharine Lee

2016-10-01

The synthesis and characterization of the first polyelectrolyte of intrinsic microporosity (PEIM) is described. The novel material was synthesized via reaction between the nitrile group in the polymer backbone and n-butyl lithium, effectively anchoring an imine anion to the porous framework while introducing a mobile lithium counterion. The PEIM was characterized by 13C, 1H, and 7Li NMR experiments, revealing quantitative conversion of the nitrile functionality to the anionic imine. Variable temperature 7Li NMR analysis of the dry PEIM and the electrolyteswollen PEIM revealed that lithium ion transport within the dry PEIM was largely due to interchain hopping of the Limore » + ions, and that the mobility of polymer associated Li + was reduced after swelling in electrolyte solution. Meanwhile, the swollen PEIM supported efficient transport of dissolved Li + within the expanded pores. These results are discussed in the context of developing novel solid or solid-like lithium ion electrolytes using the new PEIM material.« less

Electrochemical micro sensor

DOEpatents

Setter, Joseph R.; Maclay, G. Jordan

1989-09-12

A micro-amperometric electrochemical sensor for detecting the presence of a pre-determined species in a fluid material is disclosed. The sensor includes a smooth substrate having a thin coating of solid electrolytic material deposited thereon. The working and counter electrodes are deposited on the surface of the solid electrolytic material and adhere thereto. Electrical leads connect the working and counter electrodes to a potential source and an apparatus for measuring the change in an electrical signal caused by the electrochemical oxidation or reduction of the species. Alternatively, the sensor may be fabricated in a sandwich structure and also may be cylindrical, spherical or other shapes.

First-Principles Investigation of Electronic Properties in Sodium-Ion Electrolytes for Solid-State Battery Materials

NASA Astrophysics Data System (ADS)

Rush, Larry E., Jr.

This thesis mainly focuses on characterizing and understanding the electronic properties of sodium-ion electrolytes using first-principles calculations. The core of these calculations is built upon a functional understanding of the relationship between quantum mechanics and the crystalline geometries that contribute to unique properties of materials such as diffusion mechanisms of ions within solid-state materials, conductivity, and ground state structures. The goal of this body of work is to understand how this relationship can give us insight into materials that might have use in an emerging field within battery technology. Sodium-ion solid-state batteries are an auspicious technology because nature has provided us with widely distributed precursor materials in such a way that removes geopolitical constraints in its construction and distribution. This is extremely important to individuals (and a collection of individuals) who want to expedite the wide use of clean and renewable energy from a societal perspective. An example is Morocco's initiative to generate 52% of its total energy consumption from clean and renewable energy sources to eliminate dependencies on foreign countries to supply energy resources. Sodium-ion solid-state batteries are an inexpensive option for large-scale grid storage, so this could play a role in providing a cost-effective option for Morocco. The challenging part is to sift through the large chemical space of sodium-ion solid-state electrolytes to find optimal materials for battery technology, and that is what motivates this body of work.

Electrode electrolyte interlayers containing cerium oxide for electrochemical fuel cells

DOEpatents

Borglum, Brian P.; Bessette, Norman F.

2000-01-01

An electrochemical cell is made having a porous fuel electrode (16) and a porous air electrode (13), with solid oxide electrolyte (15) therebetween, where the air electrode surface opposing the electrolyte has a separate, attached, dense, continuous layer (14) of a material containing cerium oxide, and where electrolyte (16) contacts the continuous oxide layer (14), without contacting the air electrode (13).

Oxygen separation from air using zirconia solid electrolyte membranes

NASA Technical Reports Server (NTRS)

Suitor, J. W.; Marner, W. J.; Schroeder, J. E.; Losey, R. W.; Ferrall, J. F.

1988-01-01

Air separation using a zirconia solid electrolyte membrane is a possible alternative source of oxygen. The process of zirconia oxygen separation is reviewed, and an oxygen plant concept using such separation is described. Potential cell designs, stack designs, and testing procedures are examined. Fabrication of the materials used in a zirconia module as well as distribution plate design and fabrication are examined.

Nonstoichiometric fluorides—Solid electrolytes for electrochemical devices: A review

NASA Astrophysics Data System (ADS)

Sorokin, N. I.; Sobolev, B. P.

2007-09-01

The solid electrolytes with fluorine-ion conductivity that were revealed during the analysis of the phase diagrams of the MF m - RF n systems within the program of search for new multicomponent fluoride crystalline materials carried out at the Shubnikov Institute of Crystallography, Russian Academy of Sciences, are described. The most widespread and promising materials are the nonstoichiometric phases with fluorite (CaF2) and tysonite (LaF3) structures, which are formed in the MF2- RF3 systems ( M = Ca, Sr, Ba, Cd, or Pb; R = Sc, Y, or La-Lu). These phases have superionic fluorine conductivity due to the anion sublattice disorder. The ionic conductivity of crystals of both structure types has been studied and the limits of its change with composition and temperature are determined. Nonstoichiometric fluorides are used as solid electrolytes in chemical sensors, fluorine sources, and batteries. The prospects of the use of fluorine-ion conductors in solid-state electrochemical devices, principles of their operation, and the problems of optimization of their composition are discussed.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, A.F.; Makowiecki, D.M.; Rambach, G.D.; Randich, E.

1998-05-19

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated. 8 figs.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, Alan F.; Makowiecki, Daniel M.; Rambach, Glenn D.; Randich, Erik

1999-01-01

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, Alan F.; Makowiecki, Daniel M.; Rambach, Glenn D.; Randich, Erik

1998-01-01

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated.

Novel electrolytes for use in new and improved batteries: An NMR study

NASA Astrophysics Data System (ADS)

Berman, Marc B.

This thesis focuses on the use of nuclear magnetic resonance (NMR) spectroscopy in order to study materials for use as electrolytes in batteries. The details of four projects are described in this thesis as well as a brief theoretical background of NMR. Structural and dynamics properties were determined using several NMR techniques such as static, MAS, PFG diffusion, and relaxation to understand microscopic and macroscopic properties of the materials described within. Nuclei investigate were 1H, 2H, 7Li, 13C, 19F, 23Na, and 27Al. The first project focuses on an exciting new material to be used as a solid electrolyte membrane. T. The second project focuses on the dynamics of ionic liquid-solvent mixtures and their comparison to molecular dynamics computer simulations. The third project involves a solvent-free film containing NaTFSI salt mixed in to PEO for use in sodium-ion batteries. This final project focuses on a composite electrolyte consisting of a ceramic and solid: LiI:PEO:LiAlO2.

Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

2002-01-01

Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

Cobalt doped lanthanum chromite material suitable for high temperature use

DOEpatents

Ruka, R.J.

1986-12-23

A high temperature, solid electrolyte electrochemical cell, subject to thermal cycling temperatures of between about 25 C and about 1,200 C, capable of electronic interconnection to at least one other electrochemical cell and capable of operating in an environment containing oxygen and a fuel, is made; where the cell has a first and second electrode with solid electrolyte between them, where an improved interconnect material is applied along a portion of a supporting electrode; where the interconnect is made of a chemically modified lanthanum chromite, containing cobalt as the important additive, which interconnect allows for adjustment of the thermal expansion of the interconnect material to more nearly match that of other cell components, such as zirconia electrolyte, and is stable in oxygen containing atmospheres such as air and in fuel environments. 2 figs.

Solid State Ionic Materials - Proceedings of the 4th Asian Conference on Solid State Ionics

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Yahaya, M.; Talib, I. A.; Salleh, M. M.

1994-07-01

The Table of Contents for the full book PDF is as follows: * Preface * I. INVITED PAPERS * Diffusion of Cations and Anions in Solid Electrolytes * Silver Ion Conductors in the Crystalline State * NMR Studies of Superionic Conductors * Hall Effect and Thermoelectric Power in High Tc Hg-Ba-Ca-Cu-O Ceramics * Solid Electrolyte Materials Prepared by Sol-Gel Chemistry * Preparation of Proton-Conducting Gel Films and their Application to Electrochromic Devices * Thin Film Fuel Cells * Zirconia based Solid Oxide Ion Conductors in Solid Oxide Fuel Cells * The Influence of Anion Substitution on Some Phosphate-based Ion Conducting Glasses * Lithium Intercalation in Carbon Electrodes and its Relevance in Rocking Chair Batteries * Chemical Sensors using Proton Conducting Ceramics * NMR/NQR Studies of Y-Ba-Cu-O Superconductors * Silver Molybdate Glasses and Battery Systems * New Highly Conducting Polymer Ionics and their Application in Electrochemical Devices * Study of Li Electrokinetics on Oligomeric Electrolytes using Microelectrodes * Calculation of Conductivity for Mixed-Phase Electrolytes PEO-MX-Immiscible Additive by Means of Effective Medium Theory * II. CONTRIBUTED PAPERS * Phase Relationship and Electrical Conductivity of Sr-V-O System with Vanadium Suboxide * Amorphous Li+ Ionic Conductors in Li2SO4-Li2O-P2O5 System * Fast Ion Transport in KCl-Al2O3 Composites * The Effect of the Second Phase Precipitation on the Ionic Conductivity of Zr0.85Mg0.15O1.85 * Conductivity Measurements and Phase Relationships in CaCl2-CaHCl Solid Electrolyte * Relationships Between Crystal Structure and Sodium Ion Conductivity in Na7Fe4(AsO4)6 and Na3Al2(AsO4)3 * Electrical Conductivity and Solubility Limit of Ti4+ Ion in Na1+x TiyZr2-ySixP3-xO12 System * Study on Sodium Fast Ion Conductors of Na1+3xAlxTi2-xSi2xP3-2xO12 System * Influences of Zirconia on the Properties of β''-Alumina Ceramics * Decay of Luminescence from Cr3+ Ions in β-Alumina * Lithium Ion Conductivity in the Li4XO4-Li2SO4 (X=Si, Ge, Ti) Systems * A DSC and Conductivity Study of the Influence of Cesium Ion on the Beta-Alpha Transition in Silver Iodide * Phase Diagrams, Stoichiometries and Properties of Bi4V2O11:M2+ Solid Electrolytes * Physical Properties of Electrodeposited Silver Chromotungstate * Pseudopotential Study of Bonding in the Superionic Material AgI: The Effect of Statistical Distribution of Mobile Ions * Cubic Phase Dominant Region in Submicron BaTiO3 Particles * The Crystallization of CoZr Amorphous Alloys via Electrical Resistivity * Cation Ratio Related Properties of Synthetic Mg/Al Layered Double Hydroxide and it's Nanocomposite * DC Conductivity of Nano-Particles of Silver Iodide * Effect of Anomalous Diffusion on Quasielastic Scattering in Superionic Conductors * Computer Simulation Study of Conductivity Enhancement in Superionic-Insulator Composites * Dynamics of Superionic Silver and Copper Iodide Salt Melts * Influence of Dopant Salt AgI, Glass Modifier Ag2O and Glass Formers (SeO3 + MoO3) on Electrical Conductivity in Quaternary Glassy System * Fast Ion Conductivity in the Presence of Competitive Network Formers * Role of Alkali Ions in Borate Glasses * Inelastic Light Scattering in Cadmium Borate Glasses * Investigation on Transport Properties of Mixed Glass System 0.75 [0.75AgI:0.25AgCl]. 0.25[Ag2O:CrO3] * Conduction Mechanism in Lithium Tellurite Glasses * Optimized Silver Tungstoarsenate Glass Electrolyte * Stabilized Superfine Zirconia Powder Prepared by Sol-Gel Process * Study of New PAN-based Electrolytes * Electrical and Thermal Characterization of PVA based Polymer Electrolytes * Conductive Electroactive Polymers: Versatile Solid State Ionic Materials * The Role of Ag2O Addition on the Superconducting Properties of Y-124 Compound * Absorption Spectra Studies of the C60 Films on Transition Metal Film Substrates * Effect of Alumina Dispersal on the Conductivity and Crystallite Size of Polymer Electrolyte * New Mixed Galss-Polymer Solid Electrolytes * The Sputtered La0.5Sr0.5MnO3-Yttria Stabilized Zirconia Composite Electrode in Solid Oxide Fuel Cells * A Solid Electrochemical Ferro Sensor for Molten Matte * SnO2-based Sensor for H2S Monitoring-Electrical Conductivity Measurements and Device Testing * Humidity Sensor using Potassium Tungsten Bronze Synthesized from Peroxo-Polytungstic Acid * Study on Li/LiClO4/V6O13 Test Cells * Fabrication and Characterisation of Some Solid Electrolyte Cells Containing CuI and Silver Oxysalts * Solid State Battery of Proton Conducting Sodium Thiosulphate Pentahydrate * Low Temperature Synthesis of LiMn2O4 for Secondary Lithium Batteries * Effect of Different Cathode Active Materials on Battery Performance with Silver Molybdate Electrolyte Partially Substituted with Zinc Oxide * Fabrication and Characterization of Electrochemical Cells based on Silver Molybdoarsenate and Silver Tungstoarsenate Glass Electrolytes * Lorentz Force Dependence of Dissipation in a Granular Superconductor * Late Entry (Invited paper) * Simultaneous Voltammetry and Spectroscopy of Polyaniline in Propylene Carbonate * Author Index * Tentative List of Participants

Towards the next generation of solid oxide fuel cells operating below 600 °c with chemically stable proton-conducting electrolytes.

PubMed

Fabbri, Emiliana; Bi, Lei; Pergolesi, Daniele; Traversa, Enrico

2012-01-10

The need for reducing the solid oxide fuel cell (SOFC) operating temperature below 600 °C is imposed by cost reduction, which is essential for widespread SOFC use, but might also disclose new applications. To this aim, high-temperature proton-conducting (HTPC) oxides have gained widespread interest as electrolyte materials alternative to oxygen-ion conductors. This Progress Report describes recent developments in electrolyte, anode, and cathode materials for protonic SOFCs, addressing the issue of chemical stability, processability, and good power performance below 600 °C. Different fabrication methods are reported for anode-supported SOFCs, obtained using state-of-the-art, chemically stable proton-conducting electrolyte films. Recent findings show significant improvements in the power density output of cells based on doped barium zirconate electrolytes, pointing out towards the feasibility of the next generation of protonic SOFCs, including a good potential for the development of miniaturized SOFCs as portable power supplies. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on Zinc Oxide-Based Electrolytes in Low-Temperature Solid Oxide Fuel Cells.

PubMed

Xia, Chen; Qiao, Zheng; Feng, Chu; Kim, Jung-Sik; Wang, Baoyuan; Zhu, Bin

2017-12-28

Semiconducting-ionic conductors have been recently described as excellent electrolyte membranes for low-temperature operation solid oxide fuel cells (LT-SOFCs). In the present work, two new functional materials based on zinc oxide (ZnO)-a legacy material in semiconductors but exceptionally novel to solid state ionics-are developed as membranes in SOFCs for the first time. The proposed ZnO and ZnO-LCP (La/Pr doped CeO₂) electrolytes are respectively sandwiched between two Ni 0.8 Co 0.15 Al 0.05 Li-oxide (NCAL) electrodes to construct fuel cell devices. The assembled ZnO fuel cell demonstrates encouraging power outputs of 158-482 mW cm -2 and high open circuit voltages (OCVs) of 1-1.06 V at 450-550 °C, while the ZnO-LCP cell delivers significantly enhanced performance with maximum power density of 864 mW cm -2 and OCV of 1.07 V at 550 °C. The conductive properties of the materials are investigated. As a consequence, the ZnO electrolyte and ZnO-LCP composite exhibit extraordinary ionic conductivities of 0.09 and 0.156 S cm -1 at 550 °C, respectively, and the proton conductive behavior of ZnO is verified. Furthermore, performance enhancement of the ZnO-LCP cell is studied by electrochemical impedance spectroscopy (EIS), which is found to be as a result of the significantly reduced grain boundary and electrode polarization resistances. These findings indicate that ZnO is a highly promising alternative semiconducting-ionic membrane to replace the electrolyte materials for advanced LT-SOFCs, which in turn provides a new strategic pathway for the future development of electrolytes.

Study on Zinc Oxide-Based Electrolytes in Low-Temperature Solid Oxide Fuel Cells

PubMed Central

Qiao, Zheng; Feng, Chu; Wang, Baoyuan; Zhu, Bin

2017-01-01

Semiconducting-ionic conductors have been recently described as excellent electrolyte membranes for low-temperature operation solid oxide fuel cells (LT-SOFCs). In the present work, two new functional materials based on zinc oxide (ZnO)—a legacy material in semiconductors but exceptionally novel to solid state ionics—are developed as membranes in SOFCs for the first time. The proposed ZnO and ZnO-LCP (La/Pr doped CeO2) electrolytes are respectively sandwiched between two Ni0.8Co0.15Al0.05Li-oxide (NCAL) electrodes to construct fuel cell devices. The assembled ZnO fuel cell demonstrates encouraging power outputs of 158–482 mW cm−2 and high open circuit voltages (OCVs) of 1–1.06 V at 450–550 °C, while the ZnO-LCP cell delivers significantly enhanced performance with maximum power density of 864 mW cm−2 and OCV of 1.07 V at 550 °C. The conductive properties of the materials are investigated. As a consequence, the ZnO electrolyte and ZnO-LCP composite exhibit extraordinary ionic conductivities of 0.09 and 0.156 S cm−1 at 550 °C, respectively, and the proton conductive behavior of ZnO is verified. Furthermore, performance enhancement of the ZnO-LCP cell is studied by electrochemical impedance spectroscopy (EIS), which is found to be as a result of the significantly reduced grain boundary and electrode polarization resistances. These findings indicate that ZnO is a highly promising alternative semiconducting-ionic membrane to replace the electrolyte materials for advanced LT-SOFCs, which in turn provides a new strategic pathway for the future development of electrolytes. PMID:29283395

Microstructural Control and Characterization of Bi2V0.9Cu0.1O5.35 (BICUVOX) Ceramics

NASA Astrophysics Data System (ADS)

Razmyar, Soheil

2011-12-01

The widespread commercialization of solid-oxide fuel cells (SOFCs) and solid-oxide electrolyte cells (SOECs) is primarily limited by material degradation issues related to the required high temperature operation (>800°C). Applications of stabilized zirconia based electrolytes, which are the most commonly used oxide ion conductors, have been limited to this high temperature regime due to its low oxygen ion conductivity below 800°C. Solid electrolytes made of the BIMEVOX compositional family of materials (Bi2MexV 1-xO5.5-delta where Me=Cu, Co, Mg, Ni, Fe...) exhibit high oxide ionic conductivity similar to YSZ at a low temperature (300--600°C). Among these materials copper-substituted bismuth vanadate (Bi2V0.9Cu0.1O5.35, BICUVOX), was reported to have the highest ionic conductivity at 400°C (0.02 S/cm). It's one of the most important drawbacks of using BICUVOX, as a SOFC electrolyte is the low mechanical strength, which makes it unusable for most electrolyte supported applications. This research aims at improving mechanical strength by careful control of synthesis processing and sintering processes, thus making BICUVOX a viable material option for intermediate temperature SOFC. A co-precipitation method was used to synthesize submicron BICUVOX powder. The powder was utilized to fabricate a thin (< 250 microm) BICUVOX electrolyte membrane, with 2.5 cm2 active area and high mechanical strength. The fabricated BICUVOX membranes were densified to 97% theoretical density at lower sintering temperature and shorter time (675°C/1 h), and shows fine grain size (<1.5microm) and high mechanical strength (159 MPa).

Solid electrolytes for fluoride ion batteries: ionic conductivity in polycrystalline tysonite-type fluorides.

PubMed

Rongeat, Carine; Reddy, M Anji; Witter, Raiker; Fichtner, Maximilian

2014-02-12

Batteries based on a fluoride shuttle (fluoride ion battery, FIB) can theoretically provide high energy densities and can thus be considered as an interesting alternative to Li-ion batteries. Large improvements are still needed regarding their actual performance, in particular for the ionic conductivity of the solid electrolyte. At the current state of the art, two types of fluoride families can be considered for electrolyte applications: alkaline-earth fluorides having a fluorite-type structure and rare-earth fluorides having a tysonite-type structure. As regard to the latter, high ionic conductivities have been reported for doped LaF3 single crystals. However, polycrystalline materials would be easier to implement in a FIB due to practical reasons in the cell manufacturing. Hence, we have analyzed in detail the ionic conductivity of La(1-y)Ba(y)F(3-y) (0 ≤ y ≤ 0.15) solid solutions prepared by ball milling. The combination of DC and AC conductivity analyses provides a better understanding of the conduction mechanism in tysonite-type fluorides with a blocking effect of the grain boundaries. Heat treatment of the electrolyte material was performed and leads to an improvement of the ionic conductivity. This confirms the detrimental effect of grain boundaries and opens new route for the development of solid electrolytes for FIB with high ionic conductivities.

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

PubMed Central

Fu, Kun (Kelvin); Gong, Yunhui; Liu, Boyang; Zhu, Yizhou; Xu, Shaomao; Yao, Yonggang; Luo, Wei; Wang, Chengwei; Lacey, Steven D.; Dai, Jiaqi; Chen, Yanan; Mo, Yifei; Wachsman, Eric; Hu, Liangbing

2017-01-01

Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li7La3Zr2O12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10−3 to 10−4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnet solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm2 for the surface-engineered garnet/Li. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries. PMID:28435874

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Kun; Gong, Yunhui; Liu, Boyang

Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li 7La 3Zr 2O 12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10 -3 to 10 -4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnetmore » solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm 2 for the surface-engineered garnet/Li. Li 7La 2.75Ca 0.25Zr 1.75Nb 0.25O 12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.« less

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

DOE PAGES

Fu, Kun; Gong, Yunhui; Liu, Boyang; ...

2017-04-07

Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li 7La 3Zr 2O 12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10 -3 to 10 -4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnetmore » solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm 2 for the surface-engineered garnet/Li. Li 7La 2.75Ca 0.25Zr 1.75Nb 0.25O 12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.« less

Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crowe, Adam J.; Bartlett, Bart M., E-mail: bartmb@umich.edu

2016-10-15

With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg{sup 2+}), relative to lithium-ion (Li{sup +}) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg{sup 2+}, improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recentmore » advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes. - Graphical abstract: In this short review, we present candidate materials for reversible Mg-battery cathodes that are compatible with magnesium metal in water-free electrolytes. The data suggest that soft, polarizable anions are required for reversible cycling.« less

High performance of SDC and GDC core shell type composite electrolytes using methane as a fuel for low temperature SOFC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Irshad, Muneeb; Siraj, Khurram, E-mail: razahussaini786@gmail.com, E-mail: khurram.uet@gmail.com; Javed, Fayyaz

Nanocomposites Samarium doped Ceria (SDC), Gadolinium doped Ceria (GDC), core shell SDC amorphous Na{sub 2}CO{sub 3} (SDCC) and GDC amorphous Na{sub 2}CO{sub 3} (GDCC) were synthesized using co-precipitation method and then compared to obtain better solid oxide electrolytes materials for low temperature Solid Oxide Fuel Cell (SOFCs). The comparison is done in terms of structure, crystallanity, thermal stability, conductivity and cell performance. In present work, XRD analysis confirmed proper doping of Sm and Gd in both single phase (SDC, GDC) and dual phase core shell (SDCC, GDCC) electrolyte materials. EDX analysis validated the presence of Sm and Gd in bothmore » single and dual phase electrolyte materials; also confirming the presence of amorphous Na{sub 2}CO{sub 3} in SDCC and GDCC. From TGA analysis a steep weight loss is observed in case of SDCC and GDCC when temperature rises above 725 °C while SDC and GDC do not show any loss. The ionic conductivity and cell performance of single phase SDC and GDC nanocomposite were compared with core shell GDC/amorphous Na{sub 2}CO{sub 3} and SDC/ amorphous Na{sub 2}CO{sub 3} nanocomposites using methane fuel. It is observed that dual phase core shell electrolytes materials (SDCC, GDCC) show better performance in low temperature range than their corresponding single phase electrolyte materials (SDC, GDC) with methane fuel.« less

The Role of Sub- and Supercritical CO2 as "Processing Solvent" for the Recycling and Sample Preparation of Lithium Ion Battery Electrolytes.

PubMed

Nowak, Sascha; Winter, Martin

2017-03-06

Quantitative electrolyte extraction from lithium ion batteries (LIB) is of great interest for recycling processes. Following the generally valid EU legal guidelines for the recycling of batteries, 50 wt % of a LIB cell has to be recovered, which cannot be achieved without the electrolyte; hence, the electrolyte represents a target component for the recycling of LIBs. Additionally, fluoride or fluorinated compounds, as inevitably present in LIB electrolytes, can hamper or even damage recycling processes in industry and have to be removed from the solid LIB parts, as well. Finally, extraction is a necessary tool for LIB electrolyte aging analysis as well as for post-mortem investigations in general, because a qualitative overview can already be achieved after a few minutes of extraction for well-aged, apparently "dry" LIB cells, where the electrolyte is deeply penetrated or even gellified in the solid battery materials.

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes.

PubMed

Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

2012-02-17

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf(2)]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g(-1) at a current density of 2 A g(-1), when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg(-1) and 41 Wh kg(-1), respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes

NASA Astrophysics Data System (ADS)

Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

2012-02-01

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf2]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g-1 at a current density of 2 A g-1, when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg-1 and 41 Wh kg-1, respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

Conductivity studies of PEG based polymer electrolyte for applications as electrolyte in ion batteries

NASA Astrophysics Data System (ADS)

Patil, Ravikumar V.; Praveen, D.; Damle, R.

2018-05-01

Development of lithium ion batteries employing solid polymer electrolytes as electrolyte material has led to efficient energy storage and usage in many portable devices. However, due to a few drawbacks like lower ionic conductivity of solid polymer electrolytes (SPEs), studies on SPEs for improvement in conductivity still have a good scope. In the present paper, we report the conductivity studies of a new SPE with low molecular weight poly ethylene glycol (PEG) as host polymer in which a salt with larger anion Lithium trifluro methane sulphonate (LTMS). XRD studies have revealed that the salt completely dissociates in the polymer giving a good stable electrolyte at lower salt concentration. Conductivity of the SPEs has been studied as a function of temperature and we reiterate that the conductivity is a thermally activated process and follows Arrhenius type behavior.

Tailored Organic Electrode Material Compatible with Sulfide Electrolyte for Stable All-Solid-State Sodium Batteries.

PubMed

Chi, Xiaowei; Liang, Yanliang; Hao, Fang; Zhang, Ye; Whiteley, Justin; Dong, Hui; Hu, Pu; Lee, Sehee; Yao, Yan

2018-03-01

All-solid-state sodium batteries (ASSSBs) with nonflammable electrolytes and ubiquitous sodium resource are a promising solution to the safety and cost concerns for lithium-ion batteries. However, the intrinsic mismatch between low anodic decomposition potential of superionic sulfide electrolytes and high operating potentials of sodium-ion cathodes leads to a volatile cathode-electrolyte interface and undesirable cell performance. Here we report a high-capacity organic cathode, Na 4 C 6 O 6 , that is chemically and electrochemically compatible with sulfide electrolytes. A bulk-type ASSSB shows high specific capacity (184 mAh g -1 ) and one of the highest specific energies (395 Wh kg -1 ) among intercalation compound-based ASSSBs. The capacity retentions of 76 % after 100 cycles at 0.1 C and 70 % after 400 cycles at 0.2 C represent the record stability for ASSSBs. Additionally, Na 4 C 6 O 6 functions as a capable anode material, enabling a symmetric all-organic ASSSB with Na 4 C 6 O 6 as both cathode and anode materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct liquid-feed fuel cell with membrane electrolyte and manufacturing thereof

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram (Inventor); Surampudi, Subbarao (Inventor); Halpert, Gerald (Inventor)

1999-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Improvements in interfacing of the catalyst layer and the membrane and activating catalyst materials are disclosed.

Computational understanding of Li-ion batteries

NASA Astrophysics Data System (ADS)

Urban, Alexander; Seo, Dong-Hwa; Ceder, Gerbrand

2016-03-01

Over the last two decades, computational methods have made tremendous advances, and today many key properties of lithium-ion batteries can be accurately predicted by first principles calculations. For this reason, computations have become a cornerstone of battery-related research by providing insight into fundamental processes that are not otherwise accessible, such as ionic diffusion mechanisms and electronic structure effects, as well as a quantitative comparison with experimental results. The aim of this review is to provide an overview of state-of-the-art ab initio approaches for the modelling of battery materials. We consider techniques for the computation of equilibrium cell voltages, 0-Kelvin and finite-temperature voltage profiles, ionic mobility and thermal and electrolyte stability. The strengths and weaknesses of different electronic structure methods, such as DFT+U and hybrid functionals, are discussed in the context of voltage and phase diagram predictions, and we review the merits of lattice models for the evaluation of finite-temperature thermodynamics and kinetics. With such a complete set of methods at hand, first principles calculations of ordered, crystalline solids, i.e., of most electrode materials and solid electrolytes, have become reliable and quantitative. However, the description of molecular materials and disordered or amorphous phases remains an important challenge. We highlight recent exciting progress in this area, especially regarding the modelling of organic electrolytes and solid-electrolyte interfaces.

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

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

Electrode assembly for use in a solid polymer electrolyte fuel cell

DOEpatents

Raistrick, Ian D.

1989-01-01

A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

Rational coating of Li7P3S11 solid electrolyte on MoS2 electrode for all-solid-state lithium ion batteries

NASA Astrophysics Data System (ADS)

Xu, R. C.; Wang, X. L.; Zhang, S. Z.; Xia, Y.; Xia, X. H.; Wu, J. B.; Tu, J. P.

2018-01-01

Large interfacial resistance between electrode and electrolyte limits the development of high-performance all-solid-state batteries. Herein we report a uniform coating of Li7P3S11 solid electrolyte on MoS2 to form a MoS2/Li7P3S11 composite electrode for all-solid-state lithium ion batteries. The as-synthesized Li7P3S11 processes a high ionic of 2.0 mS cm-1 at room temperature. Due to homogeneous union and reduced interfacial resistance, the assembled all-solid-state batteries with the MoS2/Li7P3S11 composite electrode exhibit higher reversible capacity of 547.1 mAh g-1 at 0.1 C and better cycling stability than the counterpart based on untreated MoS2. Our study provides a new reference for design/fabrication of advanced electrode materials for high-performance all-solid-state batteries.

Materiais a base de oxidos com estrutura do tipo perovskite e compositos como anodos de PCES: Propriedades Funcionais e Comportamento Eletroquimico em Celulas com Eletrolitos Solidos a Base de Galatos e Silicatos

NASA Astrophysics Data System (ADS)

Kolotygin, Vladislav

This work was focused on the analysis of transport, thermomechanical and electrochemical properties of a series of perovskite-like oxide materials and composites for potential applications as anodes of intermediate-temperature solid oxide fuel cells (SOFCs) with lanthanum gallate and silicate solid electrolytes. The primary attention was centered on A(Mn,Nb)O3-delta (A = Sr, Ca) and (La,Sr)(Mn,Ti)O3-based systems, lanthanum chromite substituted with acceptor-type and variable-valence cations, and various Ni-containing cermets. Emphasis was given to phase stability of the materials, their crystal structure, microstructure of porous electrode layers and dense ceramics, electronic conductivity, Seebeck coefficient, oxygen permeability, thermal and chemical induced expansion, and anodic overpotentials of the electrodes deposited onto (La,Sr)(Ga,Mg)O3- and La10(Si,Al)6O27-based electrolyte membranes. In selected cases, roles of oxygen diffusivity, states of the transition metal cations relevant for the electronic transport, catalytically active additives and doped ceria protective interlayers introduced in the model electrochemical cells were assessed. The correlations between transport properties of the electrode materials and electrochemical behavior of porous electrodes showed that the principal factors governing anode performance include, in particular, electronic conduction of the anode compositions and cation interdiffusion between the electrodes and solid electrolytes. The latter is critically important for the silicatebased electrolyte membranes, leading to substantially worse anode properties compared to the electrochemical cells with lanthanum gallate solid electrolyte. The results made it possible to select several anode compositions exhibiting lower area-specific electrode resistivity compared to known analogues, such as (La,Sr)(Cr,Mn)O3-delta.

Role of Dynamically Frustrated Bond Disorder in a Li + Superionic Solid Electrolyte

DOE PAGES

Adelstein, Nicole; Wood, Brandon C.

2016-09-16

Inorganic lithium solid electrolytes are critical components in next-generation solid-state batteries, yet the fundamental nature of the cation-anion interactions and their relevance for ionic conductivity in these materials remains enigmatic. Here, we employ first-principles molecular dynamics simulations to explore the interplay between chemistry, structure, and functionality of a highly conductive Li + solid electrolyte, Li3InBr6. Using local-orbital projections to dynamically track the evolution of the electronic charge density, the simulations reveal rapid, correlated fluctuations between cation-anion interactions with different degrees of directional covalent character. These chemical bond dynamics are shown to correlate with Li + mobility, and are enabled thermallymore » by intrinsic frustration between the preferred geometries of chemical bonding and lattice symmetry. We suggest that the fluctuating chemical environment from the polarizable anions functions similar to a solvent, contributing to the superionic behavior of Li 3InBr 6 by temporarily stabilizing configurations favorable for migrating Li +. The generality of these conclusions for understanding solid electrolytes and key factors governing the superionic phase transition is discussed.« less

Current status of environmental, health, and safety issues of lithium ion electric vehicle batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vimmerstedt, L.J.; Ring, S.; Hammel, C.J.

The lithium ion system considered in this report uses lithium intercalation compounds as both positive and negative electrodes and has an organic liquid electrolyte. Oxides of nickel, cobalt, and manganese are used in the positive electrode, and carbon is used in the negative electrode. This report presents health and safety issues, environmental issues, and shipping requirements for lithium ion electric vehicle (EV) batteries. A lithium-based electrochemical system can, in theory, achieve higher energy density than systems using other elements. The lithium ion system is less reactive and more reliable than present lithium metal systems and has possible performance advantages overmore » some lithium solid polymer electrolyte batteries. However, the possibility of electrolyte spills could be a disadvantage of a liquid electrolyte system compared to a solid electrolyte. The lithium ion system is a developing technology, so there is some uncertainty regarding which materials will be used in an EV-sized battery. This report reviews the materials presented in the open literature within the context of health and safety issues, considering intrinsic material hazards, mitigation of material hazards, and safety testing. Some possible lithium ion battery materials are toxic, carcinogenic, or could undergo chemical reactions that produce hazardous heat or gases. Toxic materials include lithium compounds, nickel compounds, arsenic compounds, and dimethoxyethane. Carcinogenic materials include nickel compounds, arsenic compounds, and (possibly) cobalt compounds, copper, and polypropylene. Lithiated negative electrode materials could be reactive. However, because information about the exact compounds that will be used in future batteries is proprietary, ongoing research will determine which specific hazards will apply.« less

Aggregate-mediated charge transport in ionomeric electrolytes

NASA Astrophysics Data System (ADS)

Lu, Keran; Maranas, Janna; Milner, Scott

Polymers such PEO can conduct ions, and have been studied as possible replacements for organic liquid electrolytes in rechargeable metal-ion batteries. More generally, fast room-temperature ionic conduction has been reported for a variety of materials, from liquids to crystalline solids. Unfortunately, polymer electrolytes generally have limited conductivity; these polymers are too viscous to have fast ion diffusion like liquids, and too unstructured to promote cooperative transport like crystalline solids. Ionomers are polymer electrolytes in which ionic groups are covalently bound to the polymer backbone, neutralized by free counterions. These materials also conduct ions, and can exhibit strong ionic aggregation. Using coarse-grained molecular dynamics, we explore the forces driving ionic aggregation, and describe the role ion aggregates have in mediating charge transport. The aggregates are string-like such that ions typically have two neighbors. We find ion aggregates self-assemble like worm-like micelles. Excess charge, or free ions, occasionally coordinate with aggregates and are transported along the chain in a Grotthuss-like mechanism. We propose that controlling ionomer aggregate structure through materials design can enhance cooperative ion transport.

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications

PubMed Central

Lochala, Joshua A.; Kwok, Alexander; Deng, Zhiqun Daniel

2017-01-01

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices with batteries being a prime example. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode, and electrolyte are optimized, it is the interface between the solid electrode and the liquid electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1–1.2 m based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (>1.0 m) have received intensive attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally distinct from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanisms are discussed. New insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges. PMID:28852621

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications

DOE PAGES

Zheng, Jianming; Lochala, Joshua A.; Kwok, Alexander; ...

2017-03-31

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices, for example, batteries. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode and electrolyte are optimized, it is the interface between the solid electrode and the liquidmore » electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1-1.2 M based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (> 1.0 M) have received additional attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally different from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanism are discussed. As a result, new insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges.« less

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications.

PubMed

Zheng, Jianming; Lochala, Joshua A; Kwok, Alexander; Deng, Zhiqun Daniel; Xiao, Jie

2017-08-01

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices with batteries being a prime example. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode, and electrolyte are optimized, it is the interface between the solid electrode and the liquid electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1-1.2 m based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (>1.0 m) have received intensive attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally distinct from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanisms are discussed. New insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges.

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Jianming; Lochala, Joshua A.; Kwok, Alexander

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices, for example, batteries. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode and electrolyte are optimized, it is the interface between the solid electrode and the liquidmore » electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1-1.2 M based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (> 1.0 M) have received additional attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally different from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanism are discussed. As a result, new insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges.« less

High capacity and stable all-solid-state Li ion battery using SnO2-embedded nanoporous carbon.

PubMed

Notohara, Hiroo; Urita, Koki; Yamamura, Hideyuki; Moriguchi, Isamu

2018-06-08

Extensive research efforts are devoted to development of high performance all-solid-state lithium ion batteries owing to their potential in not only improving safety but also achieving high stability and high capacity. However, conventional approaches based on a fabrication of highly dense electrode and solid electrolyte layers and their close contact interface is not always applicable to high capacity alloy- and/or conversion-based active materials such as SnO 2 accompanied with large volume change in charging-discharging. The present work demonstrates that SnO 2 -embedded nanoporous carbons without solid electrolyte inside the nanopores are a promising candidate for high capacity and stable anode material of all-solid-state battery, in which the volume change reactions are restricted in the nanopores to keep the constant electrode volume. A prototype all-solid-state full cell consisting of the SnO 2 -based anode and a LiNi 1/3 Co 1 / 3 Mn 1/3 O 2 -based cathode shows a good performance of 2040 Wh/kg at 268.6 W/kg based on the anode material weight.

Electrochemical testing of suspension plasma sprayed solid oxide fuel cell electrolytes

NASA Astrophysics Data System (ADS)

Waldbillig, D.; Kesler, O.

Electrochemical performance of metal-supported plasma sprayed (PS) solid oxide fuel cells (SOFCs) was tested for three nominal electrolyte thicknesses and three electrolyte fabrication conditions to determine the effects of electrolyte thickness and microstructure on open circuit voltage (OCV) and series resistance (R s). The measured OCV values were approximately 90% of the Nernst voltages, and electrolyte area specific resistances below 0.1 Ω cm 2 were obtained at 750 °C for electrolyte thicknesses below 20 μm. Least-squares fitting was used to estimate the contributions to R s of the YSZ bulk material, its microstructure, and the contact resistance between the current collectors and the cells. It was found that the 96% dense electrolyte layers produced from high plasma gas flow rate conditions had the lowest permeation rates, the highest OCV values, and the smallest electrolyte-related voltage losses. Optimal electrolyte thicknesses were determined for each electrolyte microstructure that would result in the lowest combination of OCV loss and voltage loss due to series resistance for operating voltages of 0.8 V and 0.7 V.

Cured composite materials for reactive metal battery electrolytes

DOEpatents

Harrup, Mason K.; Stewart, Frederick F.; Peterson, Eric S.

2006-03-07

A solid molecular composite polymer-based electrolyte is made for batteries, wherein silicate compositing produces a electrolytic polymer with a semi-rigid silicate condensate framework, and then mechanical-stabilization by radiation of the outer surface of the composited material is done to form a durable and non-tacky texture on the electrolyte. The preferred ultraviolet radiation produces this desirable outer surface by creating a thin, shallow skin of crosslinked polymer on the composite material. Preferably, a short-duration of low-medium range ultraviolet radiation is used to crosslink the polymers only a short distance into the polymer, so that the properties of the bulk of the polymer and the bulk of the molecular composite material remain unchanged, but the tough and stable skin formed on the outer surface lends durability and processability to the entire composite material product.

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

Broad Funding Opportunity Announcement Project: Led by MIT professor Donald Sadoway, the Electroville project team is creating a community-scale electricity storage device using new materials and a battery design inspired by the aluminum production process known as smelting. A conventional battery includes a liquid electrolyte and a solid separator between its 2 solid electrodes. MIT’s battery contains liquid metal electrodes and a molten salt electrolyte. Because metals and salt don’t mix, these 3 liquids of different densities naturally separate into layers, eliminating the need for a solid separator. This efficient design significantly reduces packaging materials, which reduces cost and allowsmore » more space for storing energy than conventional batteries offer. MIT’s battery also uses cheap, earth-abundant, domestically available materials and is more scalable. By using all liquids, the design can also easily be resized according to the changing needs of local communities.« less

Holistic computational structure screening of more than 12,000 candidates for solid lithium-ion conductor materials

NASA Astrophysics Data System (ADS)

Sendek, Austin D.; Yang, Qian; Cubuk, Ekin D.; Duerloo, Karel-Alexander N.; Cui, Yi; Reed, Evan J.

We present a new type of large-scale computational screening approach for identifying promising candidate materials for solid state electrolytes for lithium ion batteries that is capable of screening all known lithium containing solids. To predict the likelihood of a candidate material exhibiting high lithium ion conductivity, we leverage machine learning techniques to train an ionic conductivity classification model using logistic regression based on experimental measurements reported in the literature. This model, which is built on easily calculable atomistic descriptors, provides new insight into the structure-property relationship for superionic behavior in solids and is approximately one million times faster to evaluate than DFT-based approaches to calculating diffusion coefficients or migration barriers. We couple this model with several other technologically motivated heuristics to reduce the list of candidate materials from the more than 12,000 known lithium containing solids to 21 structures that show promise as electrolytes, few of which have been examined experimentally. Our screening utilizes structures and electronic information contained in the Materials Project database. This work is supported by an Office of Technology Licensing Fellowship through the Stanford Graduate Fellowship Program and a seed Grant from the TomKat Center for Sustainable Energy at Stanford.

Investigation on the interface between Li10GeP2S12 electrolyte and carbon conductive agents in all-solid-state lithium battery.

PubMed

Yoon, Kyungho; Kim, Jung-Joon; Seong, Won Mo; Lee, Myeong Hwan; Kang, Kisuk

2018-05-23

All-solid-state batteries are considered as one of the attractive alternatives to conventional lithium-ion batteries, due to their intrinsic safe properties benefiting from the use of non-flammable solid electrolytes in ASSBs. However, one of the issues in employing the solid-state electrolyte is the sluggish ion transport kinetics arising from the chemical and physical instability of the interfaces among solid components including electrode material, electrolyte and additive agents. In this work, we investigate the stability of the interface between carbon conductive agents and Li 10 GeP 2 S 12 in a composite cathode and its effect on the electrochemical performance of ASSBs. It is found that the inclusion of various carbon conductive agents in composite cathode leads to inferior kinetic performance of the cathode despite expectedly enhanced electrical conductivity of the composite. We observe that the poor kinetic performance is attributed to a large interfacial impedance which is gradually developed upon the inclusions of the various carbon conductive agents regardless of their physical differences. The analysis through X-ray Photoelectron Spectroscopy suggests that the carbon additives in the composite cathode stimulate the electrochemical decomposition of LGPS electrolyte degrading its surface during cycling, indicating the large interfacial resistance stems from the undesirable decomposition of the electrolyte at the interface.

Role of salt concentration in blend polymer for energy storage conversion devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arya, Anil; Sharma, A. L., E-mail: alsharmaiitkgp@gmail.com; Sadiq, M.

2016-05-06

Solid Polymer Electrolytes (SPE) are materials of considerable interest worldwide, which serves dual purpose of electrolyte and separator between electrode compartments in renewable energy conversion/storage devices such as; high energy density batteries, electrochromic display devices, and supercapacitors. Polymer blend electrolytes are prepared for various concentration of salt (Ö/Li) with the constant ratio (0.5 gm) of each PEO and PAN polymers (blend polymer) using solution casting technique. Solid polymeric ionic conductor as a separator is the ultimate substitute to eliminate the drawback related to liquid and gel polymer ionic conductors. In the present work, solid polymer electrolyte film consisting of PEO,more » PAN and LiPF{sub 6} are examined for various concentration of lithium salt by keeping PEO/PAN blend ratio as a constant with a view to optimize the dominant salt concentration which could give the maximum conductivity at ambient temperature.« less

Preparation of redox polymer cathodes for thin film rechargeable batteries

DOEpatents

Skotheim, T.A.; Lee, H.S.; Okamoto, Yoshiyuki.

1994-11-08

The present invention relates to the manufacture of thin film solid state electrochemical devices using composite cathodes comprising a redox polymer capable of undergoing oxidation and reduction, a polymer solid electrolyte and conducting carbon. The polymeric cathode material is formed as a composite of radiation crosslinked polymer electrolytes and radiation crosslinked redox polymers based on polysiloxane backbones with attached organosulfur side groups capable of forming sulfur-sulfur bonds during electrochemical oxidation.

Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions

DOE PAGES

Tang, Wan Si; Unemoto, Atsushi; Zhou, Wei; ...

2015-10-08

Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na 2B 12H 12, which contains large, icosahedral, divalent B 12H 12 2– anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li 2B 12H 12, possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB 11H 12 and NaCB 11H 12 salts, which contain icosahedral, monovalent CB 11H 12–more » anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, and truly stellar ionic conductivities (>0.1 S cm –1) unmatched by any other known polycrystalline materials at these temperatures. Furthermore with proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.« less

Effect of proton-conduction in electrolyte on electric efficiency of multi-stage solid oxide fuel cells

PubMed Central

Matsuzaki, Yoshio; Tachikawa, Yuya; Somekawa, Takaaki; Hatae, Toru; Matsumoto, Hiroshige; Taniguchi, Shunsuke; Sasaki, Kazunari

2015-01-01

Solid oxide fuel cells (SOFCs) are promising electrochemical devices that enable the highest fuel-to-electricity conversion efficiencies under high operating temperatures. The concept of multi-stage electrochemical oxidation using SOFCs has been proposed and studied over the past several decades for further improving the electrical efficiency. However, the improvement is limited by fuel dilution downstream of the fuel flow. Therefore, evolved technologies are required to achieve considerably higher electrical efficiencies. Here we present an innovative concept for a critically-high fuel-to-electricity conversion efficiency of up to 85% based on the lower heating value (LHV), in which a high-temperature multi-stage electrochemical oxidation is combined with a proton-conducting solid electrolyte. Switching a solid electrolyte material from a conventional oxide-ion conducting material to a proton-conducting material under the high-temperature multi-stage electrochemical oxidation mechanism has proven to be highly advantageous for the electrical efficiency. The DC efficiency of 85% (LHV) corresponds to a net AC efficiency of approximately 76% (LHV), where the net AC efficiency refers to the transmission-end AC efficiency. This evolved concept will yield a considerably higher efficiency with a much smaller generation capacity than the state-of-the-art several tens-of-MW-class most advanced combined cycle (MACC). PMID:26218470

Effect of proton-conduction in electrolyte on electric efficiency of multi-stage solid oxide fuel cells.

PubMed

Matsuzaki, Yoshio; Tachikawa, Yuya; Somekawa, Takaaki; Hatae, Toru; Matsumoto, Hiroshige; Taniguchi, Shunsuke; Sasaki, Kazunari

2015-07-28

Solid oxide fuel cells (SOFCs) are promising electrochemical devices that enable the highest fuel-to-electricity conversion efficiencies under high operating temperatures. The concept of multi-stage electrochemical oxidation using SOFCs has been proposed and studied over the past several decades for further improving the electrical efficiency. However, the improvement is limited by fuel dilution downstream of the fuel flow. Therefore, evolved technologies are required to achieve considerably higher electrical efficiencies. Here we present an innovative concept for a critically-high fuel-to-electricity conversion efficiency of up to 85% based on the lower heating value (LHV), in which a high-temperature multi-stage electrochemical oxidation is combined with a proton-conducting solid electrolyte. Switching a solid electrolyte material from a conventional oxide-ion conducting material to a proton-conducting material under the high-temperature multi-stage electrochemical oxidation mechanism has proven to be highly advantageous for the electrical efficiency. The DC efficiency of 85% (LHV) corresponds to a net AC efficiency of approximately 76% (LHV), where the net AC efficiency refers to the transmission-end AC efficiency. This evolved concept will yield a considerably higher efficiency with a much smaller generation capacity than the state-of-the-art several tens-of-MW-class most advanced combined cycle (MACC).

Process for desulfurizing petroleum feedstocks

DOEpatents

Gordon, John Howard; Alvare, Javier

2014-06-10

A process for upgrading an oil feedstock includes reacting the oil feedstock with a quantity of an alkali metal, wherein the reaction produces solid materials and liquid materials. The solid materials are separated from the liquid materials. The solid materials may be washed and heat treated by heating the materials to a temperature above 400.degree. C. The heat treating occurs in an atmosphere that has low oxygen and water content. Once heat treated, the solid materials are added to a solution comprising a polar solvent, where sulfide, hydrogen sulfide or polysulfide anions dissolve. The solution comprising polar solvent is then added to an electrolytic cell, which during operation, produces alkali metal and sulfur.

Strongly correlated perovskite fuel cells

NASA Astrophysics Data System (ADS)

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

2016-06-01

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Strongly correlated perovskite fuel cells

DOE PAGES

Zhou, You; Guan, Xiaofei; Zhou, Hua; ...

2016-05-16

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes.more » Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.« less

Strongly correlated perovskite fuel cells.

PubMed

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

2016-06-09

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Realisation of an all solid state lithium battery using solid high temperature plastic crystal electrolytes exhibiting liquid like conductivity.

PubMed

Shekibi, Youssof; Rüther, Thomas; Huang, Junhua; Hollenkamp, Anthony F

2012-04-07

Replacement of volatile and combustible electrolytes in conventional lithium batteries is desirable for two reasons: safety concerns and increase in specific energy. In this work we consider the use of an ionic organic plastic crystal material (IOPC), N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF(4)], as a solid-state electrolyte for lithium battery applications. The effect of inclusion of 1 to 33 mol% lithium tetrafluoroborate, LiBF(4), into [C2mpyr][BF(4)] has been investigated over a wide temperature range by differential scanning calorimetry (DSC), impedance spectroscopy, cyclic voltammetry and cycling of full Li|LiFePO(4) batteries. The increases in ionic conductivity by orders of magnitude observed at higher temperature are most likely associated with an increase in Li ion mobility in the highest plastic phase. At concentrations >5 mol% LiBF(4) the ionic conductivity of these solid-state composites is comparable to the ionic conductivity of room temperature ionic liquids. Galvanostatic cycling of Li|Li symmetrical cells showed that the reversibility of the lithium metal redox reaction at the interface of this plastic crystal electrolyte is sufficient for lithium battery applications. For the first time we demonstrate an all solid state lithium battery incorporating solid electrolytes based on IOPC as opposed to conventional flammable organic solvents.

Ultracapacitor separator

DOEpatents

Wei, Chang; Jerabek, Elihu Calvin; LeBlanc, Jr., Oliver Harris

2001-03-06

An ultracapacitor includes two solid, nonporous current collectors, two porous electrodes separating the collectors, a porous separator between the electrodes and an electrolyte occupying the pores in the electrodes and separator. The electrolyte is a polar aprotic organic solvent and a salt. The porous separator comprises a wet laid cellulosic material.

Bioinspired Ultrastrong Solid Electrolytes with Fast Proton Conduction along 2D Channels.

PubMed

He, Guangwei; Xu, Mingzhao; Zhao, Jing; Jiang, Shengtao; Wang, Shaofei; Li, Zhen; He, Xueyi; Huang, Tong; Cao, Moyuan; Wu, Hong; Guiver, Michael D; Jiang, Zhongyi

2017-07-01

Solid electrolytes have attracted much attention due to their great prospects in a number of energy- and environment-related applications including fuel cells. Fast ion transport and superior mechanical properties of solid electrolytes are both of critical significance for these devices to operate with high efficiency and long-term stability. To address a common tradeoff relationship between ionic conductivity and mechanical properties, electrolyte membranes with proton-conducting 2D channels and nacre-inspired architecture are reported. An unprecedented combination of high proton conductivity (326 mS cm -1 at 80 °C) and superior mechanical properties (tensile strength of 250 MPa) are achieved due to the integration of exceptionally continuous 2D channels and nacre-inspired brick-and-mortar architecture into one materials system. Moreover, the membrane exhibits higher power density than Nafion 212 membrane, but with a comparative weight of only ≈0.1, indicating potential savings in system weight and cost. Considering the extraordinary properties and independent tunability of ion conduction and mechanical properties, this bioinspired approach may pave the way for the design of next-generation high-performance solid electrolytes with nacre-like architecture. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dendrite Suppression by Synergistic Combination of Solid Polymer Electrolyte Crosslinked with Natural Terpenes and Lithium-Powder Anode for Lithium-Metal Batteries.

PubMed

Shim, Jimin; Lee, Jae Won; Bae, Ki Yoon; Kim, Hee Joong; Yoon, Woo Young; Lee, Jong-Chan

2017-05-22

Lithium-metal anode has fundamental problems concerning formation and growth of lithium dendrites, which prevents practical applications of next generation of high-capacity lithium-metal batteries. The synergistic combination of solid polymer electrolyte (SPE) crosslinked with naturally occurring terpenes and lithium-powder anode is promising solution to resolve the dendrite issues by substituting conventional liquid electrolyte/separator and lithium-foil anode system. A series of SPEs based on polysiloxane crosslinked with natural terpenes are prepared by facile thiol-ene click reaction under mild condition and the structural effect of terpene crosslinkers on electrochemical properties is studied. Lithium powder with large surface area is prepared by droplet emulsion technique (DET) and used as anode material. The effect of the physical state of electrolyte (solid/liquid) and morphology of lithium-metal anode (powder/foil) on dendrite growth behavior is systematically studied. The synergistic combination of SPE and lithium-powder anode suggests an effective solution to suppress the dendrite growth owing to the formation of a stable solid-electrolyte interface (SEI) layer and delocalized current density. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The electrochemical reduction processes of solid compounds in high temperature molten salts.

PubMed

Xiao, Wei; Wang, Dihua

2014-05-21

Solid electrode processes fall in the central focus of electrochemistry due to their broad-based applications in electrochemical energy storage/conversion devices, sensors and electrochemical preparation. The electrolytic production of metals, alloys, semiconductors and oxides via the electrochemical reduction of solid compounds (especially solid oxides) in high temperature molten salts has been well demonstrated to be an effective and environmentally friendly process for refractory metal extraction, functional materials preparation as well as spent fuel reprocessing. The (electro)chemical reduction of solid compounds under cathodic polarizations generally accompanies a variety of changes at the cathode/melt electrochemical interface which result in diverse electrolytic products with different compositions, morphologies and microstructures. This report summarizes various (electro)chemical reactions taking place at the compound cathode/melt interface during the electrochemical reduction of solid compounds in molten salts, which mainly include: (1) the direct electro-deoxidation of solid oxides; (2) the deposition of the active metal together with the electrochemical reduction of solid oxides; (3) the electro-inclusion of cations from molten salts; (4) the dissolution-electrodeposition process, and (5) the electron hopping process and carbon deposition with the utilization of carbon-based anodes. The implications of the forenamed cathodic reactions on the energy efficiency, chemical compositions and microstructures of the electrolytic products are also discussed. We hope that a comprehensive understanding of the cathodic processes during the electrochemical reduction of solid compounds in molten salts could form a basis for developing a clean, energy efficient and affordable production process for advanced/engineering materials.

A high performance flexible all solid state supercapacitor based on the MnO2 sphere coated macro/mesoporous Ni/C electrode and ionic conducting electrolyte

NASA Astrophysics Data System (ADS)

Zhi, Jian; Reiser, Oliver; Wang, Youfu; Hu, Aiguo

2016-06-01

A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices.A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr02215d

Li14P2O3N6 and Li7PN4: Computational study of two nitrogen rich crystalline LiPON electrolyte materials

NASA Astrophysics Data System (ADS)

Al-Qawasmeh, Ahmad; Holzwarth, N. A. W.

2017-10-01

Two lithium oxonitridophosphate materials are computationally examined and found to be promising solid electrolytes for possible use in all solid-state batteries having metallic Li anodes - Li14P2O3N6 and Li7PN4. The first principles simulations are in good agreement with the structural analyses reported in the literature for these materials and the computed total energies indicate that both materials are stable with respect to decomposition into binary and ternary products. The computational results suggest that both materials are likely to form metastable interfaces with Li metal. The simulations also find both materials to have Li ion migration activation energies comparable or smaller than those of related Li ion electrolyte materials. Specifically, for Li7PN4, the experimentally measured activation energy can be explained by the migration of a Li ion vacancy stabilized by a small number of O2- ions substituting for N3- ions. For Li14P2O3N6, the activation energy for Li ion migration has not yet been experimentally measured, but simulations predict it to be smaller than that measured for Li7PN4.

Fabrication of advanced electrochemical energy materials using sol-gel processing techniques

NASA Technical Reports Server (NTRS)

Chu, C. T.; Chu, Jay; Zheng, Haixing

1995-01-01

Advanced materials play an important role in electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. They are being used as both electrodes and electrolytes. Sol-gel processing is a versatile solution technique used in fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. The application of sol-gel processing in the fabrication of advanced electrochemical energy materials will be presented. The potentials of sol-gel derived materials for electrochemical energy applications will be discussed along with some examples of successful applications. Sol-gel derived metal oxide electrode materials such as V2O5 cathodes have been demonstrated in solid-slate thin film batteries; solid electrolytes materials such as beta-alumina for advanced secondary batteries had been prepared by the sol-gel technique long time ago; and high surface area transition metal compounds for capacitive energy storage applications can also be synthesized with this method.

Solid oxide fuel cell having monolithic cross flow core and manifolding

DOEpatents

Poeppel, Roger B.; Dusek, Joseph T.

1984-01-01

This invention discloses a monolithic core construction having the flow passageways for the fuel and for the oxidant gases extended transverse to one another, whereby full face core manifolding can be achieved for these gases and their reaction products. The core construction provides that only anode material surround each fuel passageway and only cathode material surround each oxidant passageway, each anode and each cathode further sandwiching at spaced opposing sides electrolyte and interconnect materials to define electrolyte and interconnect walls. Webs of the cathode and anode material hold the electrolyte and interconnect walls spaced apart to define the flow passages. The composite anode and cathode wall structures are further alternately stacked on one another (with the separating electrolyte or interconnect material typically being a single common layer) whereby the fuel passageway and the oxidant passageways are disposed transverse to one another.

Solid oxide fuel cell having monolithic cross flow core and manifolding

DOEpatents

Poeppel, R.B.; Dusek, J.T.

1983-10-12

This invention discloses a monolithic core construction having the flow passageways for the fuel and for the oxidant gases extended transverse to one another, whereby full face core manifolding can be achieved for these gases and their reaction products. The core construction provides that only anode material surround each fuel passageway and only cathode material surround each oxidant passageway, each anode and each cathode further sandwiching at spaced opposing sides electrolyte and interconnect materials to define electrolyte and interconnect walls. Webs of the cathode and anode material hold the electrolyte and interconnect walls spaced apart to define the flow passages. The composite anode and cathode wall structures are further alternately stacked on one another (with the separating electrolyte or interconnect material typically being a single common layer) whereby the fuel passageways and the oxidant passageways are disposed transverse to one another.

The Use of Solid States Ionic Materials and Devices in Medical Applications

NASA Astrophysics Data System (ADS)

Linford, R. G.

2006-06-01

Electrolyte materials used in solid state polymer batteries can also be utilised in a special type of drug delivery system called an iontophoretic device. This review will describe the history, applications and limitations of iontophoretic and related systems and also the use of batteries and biofuel cells in medicine.

Materials Development for All-Solid-State Battery Electrolytes

NASA Astrophysics Data System (ADS)

Wang, Weimin

Solid electrolytes in all solid-state batteries, provide higher attainable energy density and improved safety. Ideal solid electrolytes require high ionic conductivity, a high elastic modulus to prevent dendrite growth, chemical compatibility with electrodes, and ease of fabrication into thin films. Although various materials types, including polymers, ceramics, and composites, are under intense investigation, unifying design principles have not been identified. In this thesis, we study the key ion transport mechanisms in relation to the structural characteristics of polymers and glassy solids, and apply derived material design strategies to develop polymer-silica hybrid materials with improved electrolyte performance characteristics. Poly(ethylene) oxide-based solid electrolytes containing ceramic nanoparticles are attractive alternatives to liquid electrolytes for high-energy density Li batteries. We compare the effect of Li1.3Al0.3Ti 1.7(PO4)3 active nanoparticles, passive TiO 2 nanoparticles and fumed silica. Up to two orders of magnitude enhancement in ionic conductivity is observed for composites with active nanoparticles, attributed to cation migration through a percolating interphase region that develops around the active nanoparticles, even at low nanoparticle loading. We investigate the structural origin of elastic properties and ionic migration mechanisms in sodium borosilicate and sodium borogermanate glass electrolyte system. A new statistical thermodynamic reaction equilibrium model is used in combination with data from nuclear magnetic resonance and Brillouin light scattering measurements to determine network structural unit fractions. The highly coordinated structural units are found to be predominantly responsible for effective mechanical load transmission, by establishing three-dimensional covalent connectivity. A strong correlation exists between bulk modulus and the activation energy for ion conduction. We describe the activated process in glasses as involving a jump by the migrating cation and transient reversible isotropic displacement of atoms in the immediate vicinity, and express the activation energy as a sum of Coulomb and elastic terms. By fitting our experimental data to this model, we find that the number of affected atoms in the vicinity ranges between 20 and 30. Furthermore, elastic deformations in ion jumping are almost purely hydrostatic and hardly shear. Considering that the energy required for the cation jump is made available by concentrating thermal phonons at the jump site, we establish a relationship between structural stiffness and activation energy. Moreover, the more atoms that partake in the cation jump, the more degrees of freedom for atomic motion can be relied upon to achieve the required net outward expansion to facilitate the passage of the jumping cation, lowering the activation energy. To combine the flexibility of polymers and the good mechanical and electrochemical properties of silica, we use sol-gel methods for fabricating silica-based hybrid organic-inorganic electrolytes. Polyethylene glycol is covalently grafted onto the silica backbone as the organic filler that provides the environment for ion conduction. We developed synthesis methods in which grafting and polycondensation occur concurrently, or the grafting occurs after the silica backbone has formed. Small angle x-ray scattering measurements reveal that different structures are achieved depending on the method used. The two-step procedure allows for a larger amount of conducting polymer to be embedded into network pores than in the one-pot method. This greatly enhances the ionic conductivity without sacrificing mechanical stability afforded by the continuous silica backbone. Here we provide a cumulative account of a systematic materials design efforts, in which we sequentially implement several important design aspects to identify their respective importance and influence on the materials performance characteristics.

Ultra-thin solid oxide fuel cells: Materials and devices

NASA Astrophysics Data System (ADS)

Kerman, Kian

Solid oxide fuel cells are electrochemical energy conversion devices utilizing solid electrolytes transporting O2- that typically operate in the 800 -- 1000 °C temperature range due to the large activation barrier for ionic transport. Reducing electrolyte thickness or increasing ionic conductivity can enable lower temperature operation for both stationary and portable applications. This thesis is focused on the fabrication of free standing ultrathin (<100 nm) oxide membranes of prototypical O 2- conducting electrolytes, namely Y2O3-doped ZrO2 and Gd2O3-doped CeO2. Fabrication of such membranes requires an understanding of thin plate mechanics coupled with controllable thin film deposition processes. Integration of free standing membranes into proof-of-concept fuel cell devices necessitates ideal electrode assemblies as well as creative processing schemes to experimentally test devices in a high temperature dual environment chamber. We present a simple elastic model to determine stable buckling configurations for free standing oxide membranes. This guides the experimental methodology for Y 2O3-doped ZrO2 film processing, which enables tunable internal stress in the films. Using these criteria, we fabricate robust Y2O3-doped ZrO2 membranes on Si and composite polymeric substrates by semiconductor and micro-machining processes, respectively. Fuel cell devices integrating these membranes with metallic electrodes are demonstrated to operate in the 300 -- 500 °C range, exhibiting record performance at such temperatures. A model combining physical transport of electronic carriers in an insulating film and electrochemical aspects of transport is developed to determine the limits of performance enhancement expected via electrolyte thickness reduction. Free standing oxide heterostructures, i.e. electrolyte membrane and oxide electrodes, are demonstrated. Lastly, using Y2O3-doped ZrO2 and Gd2O 3-doped CeO2, novel electrolyte fabrication schemes are explored to develop oxide alloys and nanoscale compositionally graded membranes that are thermomechanically robust and provide added interfacial functionality. The work in this thesis advances experimental state-of-the-art with respect to solid oxide fuel cell operation temperature, provides fundamental boundaries expected for ultrathin electrolytes, develops the ability to integrate highly dissimilar material (such as oxide-polymer) heterostructures, and introduces nanoscale compositionally graded electrolyte membranes that can lead to monolithic materials having multiple functionalities.

Electrode materials: a challenge for the exploitation of protonic solid oxide fuel cells

PubMed Central

Fabbri, Emiliana; Pergolesi, Daniele; Traversa, Enrico

2010-01-01

High temperature proton conductor (HTPC) oxides are attracting extensive attention as electrolyte materials alternative to oxygen-ion conductors for use in solid oxide fuel cells (SOFCs) operating at intermediate temperatures (400–700 °C). The need to lower the operating temperature is dictated by cost reduction for SOFC pervasive use. The major stake for the deployment of this technology is the availability of electrodes able to limit polarization losses at the reduced operation temperature. This review aims to comprehensively describe the state-of-the-art anode and cathode materials that have so far been tested with HTPC oxide electrolytes, offering guidelines and possible strategies to speed up the development of protonic SOFCs. PMID:27877342

Self-doped molecular composite battery electrolytes

DOEpatents

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

2003-04-08

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

Atomistic Simulation of Interfaces in Materials of Solid State Ionics

NASA Astrophysics Data System (ADS)

Ivanov-Schitz, A. K.; Mazo, G. N.

2018-01-01

The possibilities of describing correctly interfaces of different types in solids within a computer experiment using molecular statics simulation, molecular dynamics simulation, and quantum chemical calculations are discussed. Heterophase boundaries of various types, including grain boundaries and solid electrolyte‒solid electrolyte and ionic conductor‒electrode material interfaces, are considered. Specific microstructural features and mechanisms of the ion transport in real heterophase structures (cationic conductor‒metal anode and anionic conductor‒cathode) existing in solid state ionics devices (such as solid-state batteries and fuel cells) are discussed.

Performance of strontium- and magnesium-doped lanthanum gallate electrolyte with lanthanum-doped ceria as a buffer layer for IT-SOFCs

NASA Astrophysics Data System (ADS)

Lee, Dokyol; Han, Ju-Hyeong; Kim, Eun-Gu; Song, Rak-Hyun; Shin, Dong-Ryul

La 0.8Sr 0.2Ga 0.8Mg 0.2O 2.8 (LSGM8080) powder, showing the highest electrical conductivity among LSGMs of various compositions, is synthesized using the glycine nitrate process (GNP) and used as the electrolyte for an intermediate-temperature solid oxide fuel cell (IT-SOFC). The LDC (Ce 0.55La 0.45O 1.775) powder is synthesized by a solid-state reaction and employed as the material for a buffer layer to prevent the reaction between the anode and electrolyte materials. The LDC also serves as the skeleton material for the anode. An anode-supported single cell with an active area of 1 cm 2 is constructed for performance evaluation. A single-cell test is performed at 750 and 800 °C. The maximum power density of the cell 459 and 664 mW cm -2 at 750 and 800 °C, respectively.

The mechanics of pressed-pellet separators in molten salt batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, Kevin Nicholas; Roberts, Christine Cardinal; Roberts, Scott Alan

2014-06-01

We present a phenomenological constitutive model that describes the macroscopic behavior of pressed-pellet materials used in molten salt batteries. Such materials include separators, cathodes, and anodes. The purpose of this model is to describe the inelastic deformation associated with the melting of a key constituent, the electrolyte. At room temperature, all constituents of these materials are solid and do not transport cations so that the battery is inert. As the battery is heated, the electrolyte, a constituent typically present in the separator and cathode, melts and conducts charge by flowing through the solid skeletons of the anode, cathode, and separator.more » The electrochemical circuit is closed in this hot state of the battery. The focus of this report is on the thermal-mechanical behavior of the separator, which typically exhibits the most deformation of the three pellets during the process of activating a molten salt battery. Separator materials are composed of a compressed mixture of a powdered electrolyte, an inert binder phase, and void space. When the electrolyte melts, macroscopically one observes both a change in volume and shape of the separator that depends on the applied boundary conditions during the melt transition. Although porous flow plays a critical role in the battery mechanics and electrochemistry, the focus of this report is on separator behavior under flow-free conditions in which the total mass of electrolyte is static within the pellet. Specific poromechanics effects such as capillary pressure, pressure-saturation, and electrolyte transport between layers are not considered. Instead, a phenomenological model is presented to describe all such behaviors including the melting transition of the electrolyte, loss of void space, and isochoric plasticity associated with the binder phase rearrangement. The model is appropriate for use finite element analysis under finite deformation and finite temperature change conditions. The model reasonably describes the stress dependent volume and shape change associated with dead load compression and spring-type boundary conditions; the latter is relevant in molten salt batteries. Future work will transition the model towards describing the solid skeleton of the separator in the traditional poromechanics context.« less

Electrochemical slurry compositions and methods for preparing the same

DOEpatents

Doherty, Tristan; Limthongkul, Pimpa; Butros, Asli; Duduta, Mihai; Cross, III, James C.

2016-11-01

Embodiments described herein generally relate to semi-solid suspensions, and more particularly to systems and methods for preparing semi-solid suspensions for use as electrodes in electrochemical devices such as, for example batteries. In some embodiments, a method for preparing a semi-solid electrode includes combining a quantity of an active material with a quantity of an electrolyte to form an intermediate material. The intermediate material is then combined with a conductive additive to form an electrode material. The electrode material is mixed to form a suspension having a mixing index of at least about 0.80 and is then formed into a semi-solid electrode.

Semi-solid electrode cell having a porous current collector and methods of manufacture

DOEpatents

Chiang, Yet-Ming; Carter, William Craig; Cross, III, James C.; Bazzarella, Ricardo; Ota, Naoki

2017-11-21

An electrochemical cell includes an anode, a semi-solid cathode, and a separator disposed therebetween. The semi-solid cathode includes a porous current collector and a suspension of an active material and a conductive material disposed in a non-aqueous liquid electrolyte. The porous current collector is at least partially disposed within the suspension such that the suspension substantially encapsulates the porous current collector.

Method of making an air electrode material having controlled sinterability

DOEpatents

Vasilow, Theodore R.; Kuo, Lewis J. H.; Ruka, Roswell J.

1994-01-01

A tubular, porous ceramic electrode structure (3) is made from the sintered admixture of doped lanthanum manganite and an additive containing cerium where a solid electrolyte (4), substantially surrounds the air electrode, and a porous outer fuel electrode (7) substantially surrounds the electrolyte, to form a fuel cell (1).

Method of making an air electrode material having controlled sinterability

DOEpatents

Vasilow, T.R.; Kuo, L.J.H.; Ruka, R.J.

1994-08-30

A tubular, porous ceramic electrode structure is made from the sintered admixture of doped lanthanum manganite and an additive containing cerium where a solid electrolyte, substantially surrounds the air electrode, and a porous outer fuel electrode substantially surrounds the electrolyte, to form a fuel cell. 2 figs.

Single- and double-ion type cross-linked polysiloxane solid electrolytes for lithium cells

NASA Astrophysics Data System (ADS)

Tsutsumi, Hiromori; Yamamoto, Masahiro; Morita, Masayuki; Matsuda, Yoshiharu; Nakamura, Takashi; Asai, Hiroyuki

Polymeric solid electrolytes, that have poly(dimethylsiloxane) (PMS) backbone and cross-linked network, were applied to a rechargeable lithium battery system. Single- (PMS-Li) and double-ion type (PMS-LiClO 4) electrolytes were prepared from the same prepolymers. Lithium electrode in the both electrolytes showed reversible stripping and deposition of lithium. Intercalation and deintercalation processes of lithium ion between lithium-manganese composite oxide (Li xMnO 2) electrode and the electrolytes were also confirmed by cyclic voltammetry, however, peak current decreased with several cycles in both cases. The model cell, Li/PMS-Li/Li xMnO 2 cell had 1.4 mA h g -1 (per 1 g of active material, current density: 3.77 μA cm -2), and the Li/PMS-LiClO 4/Li xMnO 2 cell had 1.6 mA h g -1 (current density: 75.3 μA cm -2).

Water-gel for gating graphene transistors.

PubMed

Kim, Beom Joon; Um, Soong Ho; Song, Woo Chul; Kim, Yong Ho; Kang, Moon Sung; Cho, Jeong Ho

2014-05-14

Water, the primary electrolyte in biology, attracts significant interest as an electrolyte-type dielectric material for transistors compatible with biological systems. Unfortunately, the fluidic nature and low ionic conductivity of water prevents its practical usage in such applications. Here, we describe the development of a solid state, megahertz-operating, water-based gate dielectric system for operating graphene transistors. The new electrolyte systems were prepared by dissolving metal-substituted DNA polyelectrolytes into water. The addition of these biocompatible polyelectrolytes induced hydrogelation to provide solid-state integrity to the system. They also enhanced the ionic conductivities of the electrolytes, which in turn led to the quick formation of an electric double layer at the graphene/electrolyte interface that is beneficial for modulating currents in graphene transistors at high frequencies. At the optimized conditions, the Na-DNA water-gel-gated flexible transistors and inverters were operated at frequencies above 1 MHz and 100 kHz, respectively.

A high performance flexible all solid state supercapacitor based on the MnO2 sphere coated macro/mesoporous Ni/C electrode and ionic conducting electrolyte.

PubMed

Zhi, Jian; Reiser, Oliver; Wang, Youfu; Hu, Aiguo

2016-06-09

A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm(-3), which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L(-1) and 549 W L(-1), based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices.

Demonstration of an electrochemical liquid cell for operando transmission electron microscopy observation of the lithiation/delithiation behavior of Si nanowire battery anodes.

PubMed

Gu, Meng; Parent, Lucas R; Mehdi, B Layla; Unocic, Raymond R; McDowell, Matthew T; Sacci, Robert L; Xu, Wu; Connell, Justin Grant; Xu, Pinghong; Abellan, Patricia; Chen, Xilin; Zhang, Yaohui; Perea, Daniel E; Evans, James E; Lauhon, Lincoln J; Zhang, Ji-Guang; Liu, Jun; Browning, Nigel D; Cui, Yi; Arslan, Ilke; Wang, Chong-Min

2013-01-01

Over the past few years, in situ transmission electron microscopy (TEM) studies of lithium ion batteries using an open-cell configuration have helped us to gain fundamental insights into the structural and chemical evolution of the electrode materials in real time. In the standard open-cell configuration, the electrolyte is either solid lithium oxide or an ionic liquid, which is point-contacted with the electrode. This cell design is inherently different from a real battery, where liquid electrolyte forms conformal contact with electrode materials. The knowledge learnt from open cells can deviate significantly from the real battery, calling for operando TEM technique with conformal liquid electrolyte contact. In this paper, we developed an operando TEM electrochemical liquid cell to meet this need, providing the configuration of a real battery and in a relevant liquid electrolyte. To demonstrate this novel technique, we studied the lithiation/delithiation behavior of single Si nanowires. Some of lithiation/delithation behaviors of Si obtained using the liquid cell are consistent with the results from the open-cell studies. However, we also discovered new insights different from the open cell configuration-the dynamics of the electrolyte and, potentially, a future quantitative characterization of the solid electrolyte interphase layer formation and structural and chemical evolution.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rangasamy, Ezhiylmurugan; Li, Juchuan; Sahu, Gayatri

2014-01-01

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

Solid State Ionics: from Michael Faraday to green energy-the European dimension.

PubMed

Funke, Klaus

2013-08-01

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag 2 S and PbF 2 and coined terms such as cation and anion , electrode and electrolyte . In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an 'evolving scheme of materials science', point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987.

Solid State Ionics: from Michael Faraday to green energy—the European dimension

PubMed Central

Funke, Klaus

2013-01-01

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag2S and PbF2 and coined terms such as cation and anion, electrode and electrolyte. In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an ‘evolving scheme of materials science’, point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987. PMID:27877585

Development of all-solid lithium-ion battery using Li-ion conducting glass-ceramics

NASA Astrophysics Data System (ADS)

Inda, Yasushi; Katoh, Takashi; Baba, Mamoru

We have developed a high performance lithium-ion conducting glass-ceramics. This glass-ceramics has the crystalline form of Li 1+ x+ yAl xTi 2- xSi yP 3- yO 12 with a NASICON-type structure, and it exhibits a high lithium-ion conductivity of 10 -3 S cm -1 or above at room temperature. Moreover, since this material is stable in the open atmosphere and even to exposure to moist air, it is expected to be applied for various uses. One of applications of this material is as a solid electrolyte for a lithium-ion battery. Batteries were developed by combining a LiCoO 2 positive electrode, a Li 4Ti 5O 12 negative electrode, and a composite electrolyte. The battery using the composite electrolyte with a higher conductivity exhibited a good charge-discharge characteristic.

Fast Lithium-Ion Transportation in Crystalline Polymer Electrolytes.

PubMed

Fu, Xiao-Bin; Yang, Guang; Wu, Jin-Ze; Wang, Jia-Chen; Chen, Qun; Yao, Ye-Feng

2018-01-05

Fast lithium-ion transportation is found in the crystalline polymer electrolytes, α-CD-PEO n /Li + (n=12, 40), prepared by self-assembly of α-cyclodextrin (CD), polyethylene oxide (PEO) and Li + salts. A detailed solid-state NMR study combined with the X-ray diffraction technique reveals the unique structural features of the samples, that is, a) the tunnel structure formed by the assembled CDs, providing the ordered long-range pathway for Li + ion transportation; b) the all-trans conformational sequence of the PEO chains in the tunnels, attenuating significantly the coordination between Li + and the EO segments. The origin of the fast lithium-ion transportation has been attributed to these unique structural features. This work demonstrates the first example in solid polymer electrolytes (SPEs) for "creating" fast ion transportation through material design and will find potential applications in the design of new ionconducting SPE materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design, fabrication and characterization of a double layer solid oxide fuel cell (DLFC)

NASA Astrophysics Data System (ADS)

Wang, Guangjun; Wu, Xiangying; Cai, Yixiao; Ji, Yuan; Yaqub, Azra; Zhu, Bin

2016-11-01

A double layer solid oxide fuel cell (DLSOFC) without using the electrolyte (layer) has been designed by integrating advantages of positive electrode material of lithium ion battery(LiNi0.8Co0.15Al0.05O2) and oxygen-permeable membranes material (trace amount cobalt incorporated terbium doped ceria, TDC + Co) based on the semiconductor physics principle. Instead of using an electrolyte layer, the depletion layer between the anode and cathode served as an electronic insulator to block the electrons but to maintain the electrolyte function for ionic transport. Thus the device with two layers can realize the function of SOFC and at the same time avoids the electronic short circuiting problem. Such novel DLFC showed good performance at low temperatures, for instance, a maximum power density of 230 mWcm-2 was achieved at 500 °C. The working principle of the new device is presented.

Materials system for intermediate temperature solid oxide fuel cells based on doped lanthanum-gallate electrolyte

NASA Astrophysics Data System (ADS)

Gong, Wenquan

2005-07-01

The objective of this work was to identify a materials system for intermediate temperature solid oxide fuel cells (IT-SOFCs). Towards this goal, alternating current complex impedance spectroscopy was employed as a tool to study electrode polarization effects in symmetrical cells employing strontium and magnesium doped lanthanum gallate (LSGM) electrolyte. Several cathode materials were investigated including strontium doped lanthanum manganite (LSM), Strontium and iron doped lanthanum cobaltate (LSCF), LSM-LSGM, and LSCF-LSGM composites. Investigated Anode materials included nickel-gadolinium or lanthanum doped cerium oxide (Ni-GDC, or Ni-LDC) composites. The ohmic and the polarization resistances of the symmetrical cells were obtained as a function of temperature, time, thickness, and the composition of the electrodes. Based on these studies, the single phase LSM electrode had the highest polarization resistance among the cathode materials. The mixed-conducting LSCF electrode had polarization resistance orders of magnitude lower than that of the LSM-LSGM composite electrodes. Although incorporating LSGM in the LSCF electrode did not reduce the cell polarization resistance significantly, it could reduce the thermal expansion coefficient mismatch between the LSCF electrodes and LSGM electrolyte. Moreover, the polarization resistance of the LSCF electrode decreased asymptotically as the electrode thickness was increased thus suggesting that the electrode thickness needed not be thicker than this asymptotic limit. On the anode side of the IT-SOFC, Ni reacted with LSGM electrolyte, and lanthanum diffusion occurred from the LSGM electrolyte to the GDC barrier layer, which was between the LSGM electrolyte and the Ni-composite anode. However, LDC served as an effective barrier layer. Ni-LDC (70 v% Ni) anode had the largest polarization resistance, while all other anode materials, i.e. Ni-LDC (50 v% Ni), Ni-GDC (70 v% NO, and Ni-GDC (50 v% Ni), had similar polarization resistances. Ni-LDC (50 v% NO was selected to be the anode for the LSGM electrolyte with a thin LDC barrier layer. Finally, the performance of complete LSGM electrolyte-supported IT-SOFCs with the selected cathode (LSCF-LSGM) and anode (Ni-LDC) materials coupled with the LDC barrier layer was evaluated at 600--800°C. The simulated cell performance of the anode-supported cell based on LSGM electrolyte was promising.

Mixed Conducting Electrodes for Better AMTEC Cells

NASA Technical Reports Server (NTRS)

Ryan, Margaret; Williams, Roger; Homer, Margie; Lara. Liana

2003-01-01

Electrode materials that exhibit mixed conductivity (that is, both electronic and ionic conductivity) have been investigated in a continuing effort to improve the performance of the alkali metal thermal-to-electric converter (AMTEC). These electrode materials are intended primarily for use on the cathode side of the sodium-ion-conducting solid electrolyte of a sodium-based AMTEC cell. They may also prove useful in sodium-sulfur batteries, which are under study for use in electric vehicles. An understanding of the roles played by the two types of conduction in the cathode of a sodium-based AMTEC cell is prerequisite to understanding the advantages afforded by these materials. In a sodium-based AMTEC cell, the anode face of an anode/solid-electrolyte/cathode sandwich is exposed to Na vapor at a suitable pressure. Upon making contact with the solid electrolyte on the anode side, Na atoms oxidize to form Na+ ions and electrons. Na+ ions then travel through the electrolyte to the cathode. Na+ ions leave the electrolyte at the cathode/electrolyte interface and are reduced by electrons that have been conducted through an external electrical load from the anode to the cathode. Once the Na+ ions have been reduced to Na atoms, they travel through the cathode to vaporize into a volume where the Na vapor pressure is much lower than it is on the anode side. Thus, the cathode design is subject to competing requirements to be thin enough to allow transport of sodium to the low-pressure side, yet thick enough to afford adequate electronic conductivity. The concept underlying the development of the present mixed conducting electrode materials is the following: The constraint on the thickness of the cathode can be eased by incorporating Na+ -ionconducting material to facilitate transport of sodium through the cathode in ionic form. At the same time, by virtue of the electronically conducting material mixed with the ionically conducting material, reduction of Na+ ions to Na atoms can take place throughout the thickness of the cathode. The net effect is to reduce the diffusion and flow resistance to sodium through the electrode while reducing the electronic resistance by providing shorter conduction paths for electrons. Reduced resistance to both sodium transport and electronic conductivity results in an increase in electric power output.

Neutron scattering study on cathode LiMn{sub 2}O{sub 4} and solid electrolyte 5(Li{sub 2}O)(P{sub 2}O{sub 5})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kartini, E., E-mail: kartini@batan.go.id; Putra, Teguh P., E-mail: kartini@batan.go.id; Jahya, A. K., E-mail: kartini@batan.go.id

2014-09-30

Neutron scattering is very important technique in order to investigate the energy storage materials such as lithium-ion battery. The unique advantages, neutron can see the light atoms such as Hydrogen, Lithium, and Oxygen, where those elements are negligible by other corresponding X-ray method. On the other hand, the energy storage materials, such as lithium ion battery is very important for the application in the electric vehicles, electronic devices or home appliances. The battery contains electrodes (anode and cathode), and the electrolyte materials. There are many challenging to improve the existing lithium ion battery materials, in order to increase their lifemore » time, cyclic ability and also its stability. One of the most scientific challenging is to investigate the crystal structure of both electrode and electrolyte, such as cathodes LiCoO{sub 2}, LiMn{sub 2}O{sub 4} and LiFePO{sub 4}, and solid electrolyte Li{sub 3}PO{sub 4}. Since all those battery materials contain Lithium ions and Oxygen, the used of neutron scattering techniques to study their structure and related properties are very important and indispensable. This article will review some works of investigating electrodes and electrolytes, LiMn{sub 2}O{sub 4} and 5(Li{sub 2}O)(P{sub 2}O{sub 5}), by using a high resolution powder diffraction (HRPD) at the multipurpose research reactor, RSG-Sywabessy of the National Nuclear Energy Agency (BATAN), Indonesia.« less

Solid Electrolyte Materials for use in Lithium-water Primary Batteries And the Synthesis and Characterization of Lanthanide Orthoferrite Magnetic Nanomaterials

NASA Astrophysics Data System (ADS)

Cook, Clifford Corlin

This thesis was developed in two parts with the overall goals of this work being (1) synthesize and develop solid electrolyte materials for use in a lithium-water battery and (2) synthesize and characterize ternary magnetic nanomaterials. Lithium metal in combination with water is a highly attractive power source due to its high specific energy. Because of the vigorous nature of the reaction between lithium and water, many obstacles must be overcome in order to harness the energy that this system is capable of producing. Parasitic reactions must be controlled so as not to passivate the lithium or consume it totally. In addition, production of hydrogen gas that accompanies both the electrochemical and parasitic reactions can present a serious challenge. As a result it is difficult to maintain high voltage and control the current density in these systems. In order to overcome these obstacles we have developed composite membranes of various lithium-ion conducting solid electrolytes and polymers. Lithium-ion conducting solid electrolytes are known to achieve ionic conductance as high as 10-3 S/cm2. Utilizing these materials in conjunction with polymers, we have created hydrophobic membranes that allow us to limit the parasitic reactions and maintain low cell impedance. Lanthanide orthoferrite materials are technologically important classes of magnetic materials. They have found application in magneto-optical devices as well as in magnetic recording devices. We have explored the syntheses and magnetic properties of nanocrystalline materials. The synthesis of the nanomaterials was done by co-reduction of lanthanide, Ln3+, and iron, Fe 3+, cations with alkalide solution producing the Ln-Fe alloy of the desired stoichiometry. Removal of the byproducts and oxidization of the alloy was accomplished by washing the product with aerated water. Presented herein, several nanoscale lanthanide orthoferrite materials (LnFeO3, Ln = Gd, Tb, Er, Tm, Sm, Dy, Ho, and La) have been prepared. The products have been characterized by X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and magnetic properties characterized by use of a Superconducting Quantum Interference Device (SQUID).

Jumping liquid metal droplet in electrolyte triggered by solid metal particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Jianbo; University of Chinese Academy of Sciences, Beijing 100049; Wang, Junjie

2016-05-30

We report the electron discharge effect due to point contact between liquid metal and solid metal particles in electrolyte. Adding nickel particles induces drastic hydrogen generating and intermittent jumping of a sub-millimeter EGaIn droplet in NaOH solution. Observations from different orientations disclose that such jumping behavior is triggered by pressurized bubbles under the assistance of interfacial interactions. Hydrogen evolution around particles provides clear evidence that such electric instability originates from the varied electric potential and morphology between the two metallic materials. The point-contact-induced charge concentration significantly enhances the near-surface electric field intensity at the particle tips and thus causes electricmore » breakdown of the electrolyte.« less

Multi-layer coatings for bipolar rechargeable batteries with enhanced terminal voltage

DOEpatents

Farmer, Joseph C.; Kaschmitter, James; Pierce, Steve

2017-06-06

A method for producing a multi-layer bipolar coated cell according to one embodiment includes applying a first active cathode material above a substrate to form a first cathode; applying a first solid-phase ionically-conductive electrolyte material above the first cathode to form a first electrode separation layer; applying a first active anode material above the first electrode separation layer to form a first anode; applying an electrically conductive barrier layer above the first anode; applying a second active cathode material above the anode material to form a second cathode; applying a second solid-phase ionically-conductive electrolyte material above the second cathode to form a second electrode separation layer; applying a second active anode material above the second electrode separation layer to form a second anode; and applying a metal material above the second anode to form a metal coating section. In another embodiment, the anode is formed prior to the cathode. Cells are also disclosed.

Method of making a cermet fuel electrode containing an inert additive

DOEpatents

Jensen, R.R.

1992-08-25

An electrode is attached to a solid electrolyte material by: (1) mixing a metallic nickel component and 1 wt% to 10 wt% of yttria stabilized zirconia having particle diameters up to 3 micrometers with an organic binder solution to form a slurry, (2) applying the slurry to a solid zirconia electrolyte material, (3) heating the slurry to drive off the organic binder and form a porous layer of metallic nickel substantially surrounded and separated by the zirconia particles, and (4) electro-chemical vapor depositing a skeletal structure between and around the metallic nickel and the zirconia particles where the metallic nickel components do not substantially sinter to each other, yet the layer remains porous. 4 figs.

Method of making a cermet fuel electrode containing an inert additive

DOEpatents

Jensen, Russel R.

1992-01-01

An electrode is attached to a solid electrolyte material by: (1) mixing a metallic nickel component and 1 wt% to 10 wt% of yttria stabilized zirconia having particle diameters up to 3 micrometers with an organic binder solution to form a slurry, (2) applying the slurry to a solid zirconia electrolyte material, (3) heating the slurry to drive off the organic binder and form a porous layer of metallic nickel substantially surrounded and separated by the zirconia particles, and (4) electro-chemical vapor depositing a skeletal structure between and around the metallic nickel and the zirconia particles where the metallic nickel components do not substantially sinter to each other, yet the layer remains porous.

Solid electroytes for CNT-based actuators

NASA Astrophysics Data System (ADS)

Riemenschneider, Johannes; Geier, Sebastian; Mahrholz, Thorsten; Mosch, Jürgen; Monner, Hans Peter; Sinapius, Michael

2009-03-01

Actuators based on carbon nanotubes (CNT) have the potential to generate high forces at very low voltages. The density of the raw material is just 1330 kg/m3, which makes them well applicable for lightweight applications. Moreover, active strains of up to 1% can be achieved - due to the CNTs dimensional changes on charge injection. Therefore the nanotubes have to be arranged and electrically wired like electrodes of a capacitor. In previous works the system's response of the Nanotubes comprising a liquid electrolyte was studied in detail. The major challenge is to repeat such experiments with solid electrolytes, which is a prerequisite for structural integration. In this paper a method is proposed which makes sure the expansion is not based on thermal expansion. This is done by analysing the electrical system response. As thermal expansion is dominated by ohmic resistance the CNT based actuators show a strong capacitive behavior. This behavior is referable to the constitution of the electrochemical double layer around the nanotubes, which causes the tubes to expand. Also a novel test setup is described, which guarantees that the displacement which is measured will not be caused by bending of a bimorph but due to expansion of a single layer of nanotubes. This paper also presents experimental results demonstrating both, the method of electrical characterization of CNT based actuators with implemented solid electrolytes and the novel test setup which is used to measure the needed data. The actuators which were characterized are hybrids of CNT and the solid electrolyte NAFION which is supplying the ions needed to constitute the electrochemical double layer. The manufacturing, processing of these actuators and also some first experimental results are shown. Unfortunately, the results are not as clear as those for liquid electrolytes, which depend on the hybrid character of the analyzed devices. In the liquid electrolyte based case the CNTs are the only source of stiffness, whereas in the solid electrolyte case electrodes and electrolyte contribute to the overall stiffness and damping as well. Since the introduction of solid electrolytes is a major stumbling block in the development of such actuators, this work is of particular importance.

A comparative study of quasi-solid nanoclay gel electrolyte and liquid electrolyte dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Main, Laura

Dye sensitized solar cells (DSSCs) are currently being explored as a cheaper alternative to the more common silicon (Si) solar cell technology. In addition to the cost advantages, DSSCs show good performance in low light conditions and are not sensitive to varying angles of incident light like traditional Si cells. One of the major challenges facing DSSCs is loss of the liquid electrolyte, through evaporation or leakage, which lowers stability and leads to increased degradation. Current research with solid-state and quasi-solid DSSCs has shown success regarding a reduction of electrolyte loss, but at a cost of lower conversion efficiency output. The research work presented in this paper focuses on the effects of using nanoclay material as a gelator in the electrolyte of the DSSC. The data showed that the quasi-solid cells are more stable than their liquid electrolyte counterparts, and achieved equal or better I-V characteristics. The quasi-solid cells were fabricated with a gel electrolyte that was prepared by adding 7 wt% of Nanoclay, Nanomer® (1.31PS, montmorillonite clay surface modified with 15-35% octadecylamine and 0.5-5 wt% aminopropyltriethoxysilane, Aldrich) to the iodide/triiodide liquid electrolyte, (Iodolyte AN-50, Solaronix). Various gel concentrations were tested in order to find the optimal ratio of nanoclay to liquid. The gel electrolyte made with 7 wt% nanoclay was more viscous, but still thin enough to allow injection with a standard syringe. Batches of cells were fabricated with both liquid and gel electrolyte and were evaluated at STC conditions (25°C, 100 mW/cm2) over time. The gel cells achieved efficiencies as high as 9.18% compared to the 9.65% achieved by the liquid cells. After 10 days, the liquid cell decreased to 1.75%, less than 20% of its maximum efficiency. By contrast, the gel cell's efficiency increased for two weeks, and did not decrease to 20% of maximum efficiency until 45 days. After several measurements, the liquid cells showed visible signs of leakage through the sealant, whereas the gel cells did not. This resistance to leakage likely contributed to the improved performance of the quasi-solid cells over time, and is a significant advantage over liquid electrolyte DSSCs.

Study, selection, and preparation of solid cationic conductors. [characteristics of solid electrolytes for rechargeable high energy and high power density batteries

NASA Technical Reports Server (NTRS)

Roth, W. L.; Muller, O.

1974-01-01

Crystal chemical principles and transport theory have been used to predict structures and specific compounds which might find application as solid electrolytes in rechargeable high energy and high power density batteries operating at temperatures less than 200 C. Structures with 1-, 2-, and 3-dimensional channels were synthesized and screened by nuclear magnetic resonance, dielectric loss, and conductivity. There is significant conductivity at room temperature in some of the materials but none attain a level that is comparable to beta-alumina. Microwave and fast pulse methods were developed to measure conductivity in powders and in small crystals.

Vertically-aligned Co(OH)2 Nanosheet Films for Flexible All-solid-state Electrochemical Supercapacitor

NASA Astrophysics Data System (ADS)

Tian, Yazhou; Gong, Jiangfeng; Zhu, Weihua

2017-11-01

Vertically-aligned Co(OH)2 nanosheets were cathodically electrodeposited on a piece of gold coated polyethylene terephthalate (Au-PET) as an electrode material for supercapacitor. The Co(OH)2 electrode showed a high capacitance of 2695 F g-1 at 8 A g-1 in 1 M KOH aqueous electrolyte. Besides, the films were employed to assemble symmetric all-solid-state supercapacitors with PVA/LiCl gel served as solid electrolyte. The device exhibits an areal capacitance of 50.5 μF cm-2 at the current density of 2 μA cm-2 accompanied by excellent cycle stability.

Fluorescent material concentration dependency: Förster resonance energy transfer in quasi-solid state DSSCs

NASA Astrophysics Data System (ADS)

Kim, Dong Woo; Jo, Hyun-Jun; Thogiti, Suresh; Yang, Weon Ki; Cheruku, Rajesh; Kim, Jae Hong

2017-05-01

Förster resonance energy transfer (FRET) is critical for wide spectral absorption, an increased dye loading, and photocurrent generation of dye-sensitized solar cells (DSSCs). This process consists of organic fluorescent materials (as an energy donor), and an organic dye (as an energy acceptor on TiO2 surfaces) with quasi-solid electrolyte. The judicious choice of the energy donor and acceptor facilitates a strong spectral overlap between the emission and absorption regions of the fluorescent materials and dye. This FRET process enhances the light-harvesting characteristics of quasi-solid state DSSCs. In this study, DSSCs containing different concentrations (0, 1, and 1.5 wt%) of a fluorescent material (FM) as the energy donor are investigated using FRET. The power conversion efficiency of DSSCs containing FMs in a quasi-solid electrolyte increased by 33% over a pristine cell. The optimized cell fabricated with the quasi-solid state DSSC containing 1.0 wt% FM shows a maximum efficiency of 3.38%, with a short-circuit current density ( J SC ) of 4.32 mA/cm-2, and an open-circuit voltage ( V OC ) of 0.68 V under illumination of simulated solar light (AM 1.5G, 100 mW/cm-2). [Figure not available: see fulltext.

A rationally designed self-standing V2O5 electrode for high voltage non-aqueous all-solid-state symmetric (2.0 V) and asymmetric (2.8 V) supercapacitors.

PubMed

Ghosh, Meena; Vijayakumar, Vidyanand; Soni, Roby; Kurungot, Sreekumar

2018-05-10

The maximum capacitive potential window of certain pseudocapacitive materials cannot be accessed in aqueous electrolytes owing to the low dissociation potential of 1.2 V possessed by water molecules. However, the inferior pseudocapacitance exhibited by the commonly used electrode materials when integrated with non-aqueous electrolytes still remains a challenge in the development of supercapacitors (SC). Proper selection of materials for the electrode and a rational design process are indeed important to overcome these practical intricacies so that such systems can perform well with non-aqueous electrolytes. We address this challenge by fabricating a prototype all-solid-state device designed with high-capacitive V2O5 as the electrode material along with a Li-ion conducting organic electrolyte. V2O5 is synthesized on a pre-treated carbon-fibre paper by adopting an electrochemical deposition technique that effects an improved contact resistance. A judicious electrode preparation strategy makes it possible to overcome the constraints of the low ionic and electrical conductivities imposed by the electrolyte and electrode material, respectively. The device, assembled in a symmetrical fashion, achieves a high specific capacitance of 406 F g-1 (at 1 A g-1). The profitable aspect of using an organic electrolyte is also demonstrated with an asymmetric configuration by using activated carbon as the positive and V2O5 as the negative electrode materials, respectively. The asymmetric device displays a wide working-voltage window of 2.8 V and delivers a high energy density of 102.68 W h kg-1 at a power density of 1.49 kW kg-1. Moreover, the low equivalent series resistance of 9.9 Ω and negligible charge transfer resistance are observed in the impedance spectra, which is a key factor that accounts for such an exemplary performance.

Molecular interactions in high conductive gel electrolytes based on low molecular weight gelator.

PubMed

Bielejewski, Michał; Łapiński, Andrzej; Demchuk, Oleg

2017-03-15

Organic ionic gel (OIG) electrolytes, also known as gel electrolytes or ionogels are one example of modern functional materials with the potential to use in wide range of electrochemical applications. The functionality of OIGs arises from the thermally reversible solidification of electrolytes or ionic liquids and their superior ionic conductivity. To understand and to predict the properties of these systems it is important to get the knowledge about the interactions on molecular level between the solid gelator matrix and the electrolyte solution. This paper reports the spectroscopic studies (FT-IR, UV-Vis and Raman) of the gel electrolyte based on low molecular weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside and solution of quaternary ammonium salt, tetramethylammonium bromide. The solidification process was based on sol-gel technique. Below characteristic temperature, defined as gel to sol phase transition temperature, T gs , the samples were solid-like and showed high conductivity values of the same order as observed for pure liquid electrolytes. The investigations were performed for a OIGs in a wide range of molar concentrations of the electrolyte solution. Copyright © 2016 Elsevier Inc. All rights reserved.

Electrolytic decontamination of conductive materials

NASA Astrophysics Data System (ADS)

Campbell, George M.; Nelson, Timothy O.; Parker, John L.; Getty, Richard H.; Hergert, Tom R.; Lindahl, Kirk A.; Peppers, Larry G.

1994-10-01

Using the electrolytic method, we have demonstrated removal of Pu and Am from contaminated conductive material. At EG and G /Rocky Flats, we electrolytically decontaminated stainless steel. Results from this work show removal of fixed contamination, including the following geometries: planar, large radius, bolt holes, glove ports, and protruding studs. More specifically, fixed contamination was reduced from levels ranging from greater than 1 000 000 counts per minute (cpm) down to levels ranging from 1500 to 250 cpm using the electrolytic method. More recently, the electrolytic work has continued at Los Alamos National Laboratory as a joint project with EG and G/Rocky Flats. Impressively, electrolytic decontamination of Pu /Am from U surfaces (10 sq cm per side) shows decreases in swipable contamination from 500 000-1 500 000 disintegrations per minute (dpm) down to 0-2 dpm. Moreover, the solid waste product of the electrolytic method is reduced in volume by more than 50 times compared with the liquid waste produced by the previous U decontamination method -- a hot concentrated acid spray leach process.

Process Developed for Generating Ceramic Interconnects With Low Sintering Temperatures for Solid Oxide Fuel Cells

NASA Technical Reports Server (NTRS)

Zhong, Zhi-Min; Goldsby, Jon C.

2005-01-01

Solid oxide fuel cells (SOFCs) have been considered as premium future power generation devices because they have demonstrated high energy-conversion efficiency, high power density, and extremely low pollution, and have the flexibility of using hydrocarbon fuel. The Solid-State Energy Conversion Alliance (SECA) initiative, supported by the U.S. Department of Energy and private industries, is leading the development and commercialization of SOFCs for low-cost stationary and automotive markets. The targeted power density for the initiative is rather low, so that the SECA SOFC can be operated at a relatively low temperature (approx. 700 C) and inexpensive metallic interconnects can be utilized in the SOFC stack. As only NASA can, the agency is investigating SOFCs for aerospace applications. Considerable high power density is required for the applications. As a result, the NASA SOFC will be operated at a high temperature (approx. 900 C) and ceramic interconnects will be employed. Lanthanum chromite-based materials have emerged as a leading candidate for the ceramic interconnects. The interconnects are expected to co-sinter with zirconia electrolyte to mitigate the interface electric resistance and to simplify the processing procedure. Lanthanum chromites made by the traditional method are sintered at 1500 C or above. They react with zirconia electrolytes (which typically sinter between 1300 and 1400 C) at the sintering temperature of lanthanum chromites. It has been envisioned that lanthanum chromites with lower sintering temperatures can be co-fired with zirconia electrolyte. Nonstoichiometric lanthanum chromites can be sintered at lower temperatures, but they are unstable and react with zirconia electrolyte during co-sintering. NASA Glenn Research Center s Ceramics Branch investigated a glycine nitrate process to generate fine powder of the lanthanum-chromite-based materials. By simultaneously doping calcium on the lanthanum site, and cobalt and aluminum on the chromium site, we could sinter the materials below 1400 C. The doping concentrations were adjusted so that the thermal expansion coefficient matched that of the zirconia electrolyte. Also, the investigation was focused on stoichiometric compositions so that the materials would have better stability. Co-sintering and chemical compatibility with zirconia electrolyte were examined by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy (line scanning and dot map). The results showed that the materials bond well, but do not react, with zirconia electrolyte. The electric conductivity of the materials measured at 900 C in air was about 20 S/cm.

Interfacial behaviours between lithium ion conductors and electrode materials in various battery systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Bingbin; Wang, Shanyu; Evans IV, Willie J.

In recent years room temperature Li+ ion conductors have been intensively revisited in order to develop safe lithium ion (Li-ion) batteries and beyond that can be deployed in the electrical vehicles. Through careful modification on materials synthesis, promising solid Li+ conductors with high ionic conductivity, competitve with liquid electrolytes, have been demonstrated. However, the integration of those highly conductive solid electrolytes into the whole system is still very challenging mainly due to the high impedance existing in the different interfaces throughout the entire battery structure. Herein , this review paper focuses on the overview of the interfacial behaviors between Li+more » conductors and cathode/anode materials. The origin, evolution and potential solutions to reuce these interfacial impedances are reviewed for various battery systems spanning from Li-ion, lithium sulfur (Li-S), lithium oxygen (Li-O2) batteries to lithium metal protection. The predicted gravimetric and volumetric energy densities at different scenarios are also discussed along with the prospectives for further development of solid state batteries.« less

High power density proton exchange membrane fuel cells

NASA Technical Reports Server (NTRS)

Murphy, Oliver J.; Hitchens, G. Duncan; Manko, David J.

1993-01-01

Proton exchange membrane (PEM) fuel cells use a perfluorosulfonic acid solid polymer film as an electrolyte which simplifies water and electrolyte management. Their thin electrolyte layers give efficient systems of low weight, and their materials of construction show extremely long laboratory lifetimes. Their high reliability and their suitability for use in a microgravity environment makes them particularly attractive as a substitute for batteries in satellites utilizing high-power, high energy-density electrochemical energy storage systems. In this investigation, the Dow experimental PEM (XUS-13204.10) and unsupported high platinum loading electrodes yielded very high power densities, of the order of 2.5 W cm(exp -2). A platinum black loading of 5 mg per cm(exp 2) was found to be optimum. On extending the three-dimensional reaction zone of fuel cell electrodes by impregnating solid polymer electrolyte into the electrode structures, Nafion was found to give better performance than the Dow experimental PEM. The depth of penetration of the solid polymer electrolyte into electrode structures was 50-70 percent of the thickness of the platinum-catalyzed active layer. However, the degree of platinum utilization was only 16.6 percent and the roughness factor of a typical electrode was 274.

High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory

NASA Astrophysics Data System (ADS)

Xiao, Ruijuan; Li, Hong; Chen, Liquan

2015-09-01

Looking for solid state electrolytes with fast lithium ion conduction is an important prerequisite for developing all-solid-state lithium secondary batteries. By combining the simulation techniques in different levels of accuracy, e.g. the bond-valence (BV) method and the density functional theory (DFT), a high-throughput design and optimization scheme is proposed for searching fast lithium ion conductors as candidate solid state electrolytes for lithium rechargeable batteries. The screening from more than 1000 compounds is performed through BV-based method, and the ability to predict reliable tendency of the Li+ migration energy barriers is confirmed by comparing with the results from DFT calculations. β-Li3PS4 is taken as a model system to demonstrate the application of this combination method in optimizing properties of solid electrolytes. By employing the high-throughput DFT simulations to more than 200 structures of the doping derivatives of β-Li3PS4, the effects of doping on the ionic conductivities in this material are predicted by the BV calculations. The O-doping scheme is proposed as a promising way to improve the kinetic properties of this materials, and the validity of the optimization is proved by the first-principles molecular dynamics (FPMD) simulations.

Combustibles sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pebler, A.R.

1980-02-26

A gaseous mixture of oxygen and fuel (Combustibles) is supplied to first and second electrodes disposed on opposite surfaces of an oxygen ion conductive solid electrolyte member wherein the electrodes are composed of different materials each exhibiting a different catalytic action on the gaseous mixture at a given temperature. The difference in oxygen potentials established at the respective electrodes as a result of the dissimilar catalytic action produces oxygen ion conductivity in the solid electrolyte cell which produces an electrical signal the magnitude of which is indicative of the combustible present in the mixture, I.E., methane, hydrogen, carbon monoxide, etc.

Strength and Fracture Toughness of Solid Oxide Fuel Cell Electrolyte Material Improved

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Choi, Sung R.

2002-01-01

Solid oxide fuel cells (SOFC) are being developed for various applications in the automobile, power-generation, and aeronautics industries. Recently, the NASA Glenn Research Center has been exploring the possibility of using SOFC's for aeropropulsion under its Zero Carbon Dioxide Emission Technology (ZCET) Program. 10-mol% yttriastabilized zirconia (10YSZ) is a very good anionic conductor at high temperatures and is, therefore, used as an oxygen solid electrolyte in SOFC. However, it has a high thermal expansion coefficient, low thermal shock resistance, low fracture toughness, and poor mechanical strength. For aeronautic applications, the thin ceramic electrolyte membrane of the SOFC needs to be strong and tough. Therefore, we have been investigating the possibility of enhancing the strength and fracture toughness of the 10YSZ electrolyte without degrading its electrical conductivity to an appreciable extent. We recently demonstrated that the addition of alumina to zirconia electrolyte increases its strength as well as its fracture toughness. Zirconia-alumina composites containing 0 to 30 mol% of alumina were fabricated by hot pressing. The hot pressing procedure was developed and various hot pressing parameters were optimized, resulting in dense, crackfree panels of composite materials. Cubic zirconia and a-alumina were the only phases detected, indicating that there was no chemical reaction between the constituents during hot pressing at elevated temperatures. Flexure strength sf and fracture toughness K(sub IC) of the various zirconia-alumina composites were measured at room temperature as well as at 1000 C in air. Both properties showed systematic improvement with increased alumina addition at room temperature and at 1000 C. Use of these modified electrolytes with improved strength and fracture toughness should prolong the life and enhance the performance of SOFC in aeronautics and other applications.

Interfacial reactions in lithium batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Zonghai; Amine, Rachid; Ma, Zi-Feng

The lithium-ion battery was first commercially introduced by Sony Corporation on 1991 using LiCoO 2 as the cathode material and mesocarbon microbeads as the anode material. After continuous research and development for 25 years, lithium-ion batteries have been the dominant energy storage devices for modern portable electronics, as well as for the emerging application for electric vehicles and smart grids. It has been a common sense that the success of lithium-ion technologies is rooted to the existence of a solid electrolyte interphase (SEI) that kinetically suppresses the parasitic reactions between the lithiated 2 graphitic anodes and the carbonate-based non-aqueous electrolytes.more » Recently, major attention has been paid to the importance of a similar passivation/protection layer on the surface of cathode materials, aiming for rational design of high-energy-density lithiumion batteries with extended cycle/calendar life. In this article, the physical model of the solid electrolyte interphase, as well as the recent research effort to under the nature and role SEI are summarized, and future perspectives on this important research field will also be presented.« less

Interfacial reactions in lithium batteries

DOE PAGES

Chen, Zonghai; Amine, Rachid; Ma, Zi-Feng; ...

2017-06-29

The lithium-ion battery was first commercially introduced by Sony Corporation on 1991 using LiCoO 2 as the cathode material and mesocarbon microbeads as the anode material. After continuous research and development for 25 years, lithium-ion batteries have been the dominant energy storage devices for modern portable electronics, as well as for the emerging application for electric vehicles and smart grids. It has been a common sense that the success of lithium-ion technologies is rooted to the existence of a solid electrolyte interphase (SEI) that kinetically suppresses the parasitic reactions between the lithiated 2 graphitic anodes and the carbonate-based non-aqueous electrolytes.more » Recently, major attention has been paid to the importance of a similar passivation/protection layer on the surface of cathode materials, aiming for rational design of high-energy-density lithiumion batteries with extended cycle/calendar life. In this article, the physical model of the solid electrolyte interphase, as well as the recent research effort to under the nature and role SEI are summarized, and future perspectives on this important research field will also be presented.« less

Sensor apparatus using an electrochemical cell

DOEpatents

Thakur, Mrinal

2002-01-01

A novel technology for sensing mechanical quantities such as force, stress, strain, pressure and acceleration has been invented. This technology is based on a change in the electrochemically generated voltage (electromotive force) with application of force, stress, strain, pressure or acceleration. The change in the voltage is due to a change in the internal resistance of the electrochemical cell with a change in the relative position or orientation of the electrodes (anode and cathode) in the cell. The signal to be detected (e.g. force, stress, strain, pressure or acceleration) is applied to one of the electrodes to cause a change in the relative position or orientation between the electrodes. Various materials, solid, semisolid, gel, paste or liquid can be utilized as the electrolyte. The electrolyte must be an ion conductor. The examples of solid electrolytes include specific polymer conductors, polymer composites, ion conducting glasses and ceramics. The electrodes are made of conductors such as metals with dissimilar electronegativities. Significantly enhanced sensitivities, up to three orders of magnitude higher than that of comparable commercial sensors, are obtained. The materials are substantially less expensive than commercially used materials for mechanical sensors.

Tetraarylborate polymer networks as single-ion conducting solid electrolytes

DOE PAGES

Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; ...

2015-06-23

A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymerizations using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted derivative. Promising initial conductivity metrics have been observed, including high room temperature conductivities (up to 2.7 × 10 -4 S cm -1), moderate activation energies (0.25–0.28 eV), and high lithium ion transport numbers (up to t Li+ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphology, porosity, fluorination, and other chemical modification, provide starting designmore » parameters for further development of this new class of solid electrolytes.« less

High temperature lithium cells with solid polymer electrolytes

DOEpatents

Yang, Jin; Eitouni, Hany Basam; Singh, Mohit

2017-03-07

Electrochemical cells that use electrolytes made from new polymer compositions based on poly(2,6-dimethyl-1,4-phenylene oxide) and other high-softening-temperature polymers are disclosed. These materials have a microphase domain structure that has an ionically-conductive phase and a phase with good mechanical strength and a high softening temperature. In one arrangement, the structural block has a softening temperature of about 210.degree. C. These materials can be made with either homopolymers or with block copolymers. Such electrochemical cells can operate safely at higher temperatures than have been possible before, especially in lithium cells. The ionic conductivity of the electrolytes increases with increasing temperature.

Anode material for lithium batteries

DOEpatents

Belharouak, Ilias [Westmont, IL; Amine, Khalil [Downers Grove, IL

2012-01-31

Primary and secondary Li-ion and lithium-metal based electrochemical cell systems. The suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of respective cell, or to the cell itself whether it be a liquid, a solid- or plasticized polymer electrolyte system. The gas suppression additives are primarily based on unsaturated hydrocarbons.

Anode material for lithium batteries

DOEpatents

Belharouak, Ilias [Bolingbrook, IL; Amine, Khalil [Downers Grove, IL

2008-06-24

Primary and secondary Li-ion and lithium-metal based electrochemical cell system. The suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of respective cell, or to the cell itself whether it be a liquid, a solid- or plastized polymer electrolyte system. The gas suppression additives are primarily based on unsaturated hydrocarbons.

Anode material for lithium batteries

DOEpatents

Belharouak, Ilias [Bolingbrook, IL; Amine, Khalil [Oak Brook, IL

2011-04-05

Primary and secondary Li-ion and lithium-metal based electrochemical cell systems. The suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of respective cell, or to the cell itself whether it be a liquid, a solid- or plasticized polymer electrolyte system. The gas suppression additives are primarily based on unsaturated hydrocarbons.

Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

PubMed

Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

2017-06-22

Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm -1 ) and dry-air-stable SEs (Li 4 SnS 4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO 2 ) coated by solidified Li 4 SnS 4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO 2 to aqueous solutions are minimized by using predissolved Li 4 SnS 4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of Novel Garnet-Type Solid Electrolytes for Potential Application in Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Narayanan, Sumaletha

The development of promising solid electrolytes having a garnet-like structure has been successfully achieved through solid state (ceramic) method. Various approaches to improve the Li ion conductivity were employed. The first approach involved creating oxide ion vacancies into the crystal structure of parent garnet-like oxide, Li5La3Nb2O 12 to create a novel family of compounds with nominal composition, Li 5La3Nb2-xYxO12-δ (0 ≤ x ≤ 1). The second approach was Li stuffing into the garnet-like oxides to develop a series of Li stuffed novel Li5+2xLa3Nb 2-xYxO12 (0.05 ≤ x ≤ 0.75) and Li6.5 La2.5Ba0.5ZrTaO12. Powder X-ray diffraction (PXRD), thermo gravimetric analysis (TGA), scanning electron microscopy (SEM), electron probe microanalysis (EPMA) coupled with a wavelength-dispersive spectrometer (WDS), 7Li nuclear magnetic resonance (Li-NMR), and AC impedance spectroscopy were employed to characterize the structure, morphology, elemental composition, Li ion sites, and Li ion conductivity. Studies have shown that Li5+2xLa 3Nb2-xYxO12 have turned out to be promising solid electrolytes with high Li ion conductivity (10-4 Scm -1 at ambient temperatures). In addition, all families of garnets are found to be chemically stable with Li cathode materials (Li2MMn 3O8, where M = Fe, Co) up to 400 °C in air. The developed electrolyte materials have the potential to be used in all-solid-state Li ion batteries.

3D-Printing Electrolytes for Solid-State Batteries.

PubMed

McOwen, Dennis W; Xu, Shaomao; Gong, Yunhui; Wen, Yang; Godbey, Griffin L; Gritton, Jack E; Hamann, Tanner R; Dai, Jiaqi; Hitz, Gregory T; Hu, Liangbing; Wachsman, Eric D

2018-05-01

Solid-state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid-state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D-print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li 7 La 3 Zr 2 O 12 solid electrolyte. Using these 3D-printing ink formulations to further study and optimize electrolyte structure could lead to solid-state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocrystalline cerium oxide materials for solid fuel cell systems

DOEpatents

Brinkman, Kyle S

2015-05-05

Disclosed are solid fuel cells, including solid oxide fuel cells and PEM fuel cells that include nanocrystalline cerium oxide materials as a component of the fuel cells. A solid oxide fuel cell can include nanocrystalline cerium oxide as a cathode component and microcrystalline cerium oxide as an electrolyte component, which can prevent mechanical failure and interdiffusion common in other fuel cells. A solid oxide fuel cell can also include nanocrystalline cerium oxide in the anode. A PEM fuel cell can include cerium oxide as a catalyst support in the cathode and optionally also in the anode.

Solid lithium electrolyte via addition of lithium salts to metal-organic frameworks

DOEpatents

Wiers, Brian M.; Balsara, Nitash P.; Long, Jeffrey R.

2016-03-29

Various embodiments of the invention disclose that the uptake of LiO.sup.iPr in Mg.sub.2(dobdc) (dobdc.sup.4-=1,4-dioxido-2,5-benzenedicarboxylate) followed by soaking in a typical electrolyte solution leads to a new solid lithium electrolyte Mg.sub.2(dobdc).0.35LiO.sup.iPr.0.25LiBF.sub.4.EC.DEC. Two-point ac impedance data show a pressed pellet of this material to have a conductivity of 3.1.times.10.sup.-4 S/cm at 300 K. In addition, the results from variable-temperature measurements reveal an activation energy of approximately 0.15 eV, while single-particle data suggest that intraparticle transport dominates conduction.

Solid lithium electrolyte via addition of lithium salts to metal-organic frameworks

DOEpatents

Wiers, Brian M.; Balsara, Nitash P.; Long, Jeffrey R.

2016-12-20

Various embodiments of the invention disclose that the uptake of LiO.sup.iPr in Mg.sub.2(dobdc) (dobdc.sup.4-=1,4-dioxido-2,5-benzenedicarboxylate) followed by soaking in a typical electrolyte solution leads to a new solid lithium electrolyte Mg.sub.2(dobdc).0.35LiO.sup.iPr.0.25LiBF.sub.4.EC.DEC. Two-point ac impedance data show a pressed pellet of this material to have a conductivity of 3.1.times.10.sup.-4 S/cm at 300 K. In addition, the results from variable-temperature measurements reveal an activation energy of approximately 0.15 eV, while single-particle data suggest that intraparticle transport dominates conduction.

Low temperature solid oxide electrolytes (LT-SOE): A review

NASA Astrophysics Data System (ADS)

Singh, B.; Ghosh, S.; Aich, S.; Roy, B.

2017-01-01

Low temperature solid oxide fuel cell (LT-SOFC) can be a source of power for vehicles, online grid, and at the same time reduce system cost, offer high reliability, and fast start-up. A huge amount of research work, as evident from the literature has been conducted for the enhancement of the ionic conductivity of LT electrolytes in the last few years. The basic conduction mechanisms, advantages and disadvantages of different LT oxide ion conducting electrolytes {BIMEVOX systems, bilayer systems including doped cerium oxide/stabilised bismuth oxide and YSZ/DCO}, mixed ion conducting electrolytes {doped cerium oxides/alkali metal carbonate composites}, and proton conducting electrolytes {doped and undoped BaCeO3, BaZrO3, etc.} are discussed here based on the recent research articles. Effect of various material aspects (composition, doping, layer thickness, etc.), fabrication methods (to achieve different microstructures and particle size), design related strategies (interlayer, sintering aid etc.), characterization temperature & environment on the conductivity of the electrolytes and performance of the fuel cells made from these electrolytes are shown in tabular form and discussed. The conductivity of the electrolytes and performance of the corresponding fuel cells are compared. Other applications of the electrolytes are mentioned. A few considerations regarding the future prospects are pointed.

Solid State Ionics Advanced Materials for Emerging Technologies

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Careem, M. A.; Dissanayake, M. A. K. L.; Rajapakse, R. M. G.; Seneviratne, V. A.

2006-06-01

Keynote lecture. Challenges and opportunities of solid state ionic devices / W. Weppner -- pt. I. Ionically conducting inorganic solids. Invited papers. Multinuclear NMR studies of mass transport of phosphoric acid in water / J. R. P. Jayakody ... [et al.]. Crystalline glassy and polymeric electrolytes: similarities and differences in ionic transport mechanisms / J.-L. Souquet. 30 years of NMR/NQR experiments in solid electrolytes / D. Brinkmann. Analysis of conductivity and NMR measurements in Li[symbol]La[symbol]TiO[symbol] fast Li[symbol] ionic conductor: evidence for correlated Li[symbol] motion / O. Bohnké ... [et al.]. Transport pathways for ions in disordered solids from bond valence mismatch landscapes / S. Adams. Proton conductivity in condensed phases of water: implications on linear and ball lightning / K. Tennakone -- Contributed papers. Proton transport in nanocrystalline bioceramic materials: an investigative study of synthetic bone with that of natural bone / H. Jena, B. Rambabu. Synthesis and properties of the nanostructured fast ionic conductor Li[symbol]La[symbol]TiO[symbol] / Q. N. Pham ... [et al.]. Hydrogen production: ceramic materials for high temperature water electrolysis / A. Hammou. Influence of the sintering temperature on pH sensor ability of Li[symbol]La[symbol]TiO[symbol]. Relationship between potentiometric and impedance spectroscopy measurements / Q. N. Pham ... [et al.]. Microstructure chracterization and ionic conductivity of nano-sized CeO[symbol]-Sm[symbol]O[symbol] system (x=0.05 - 0.2) prepared by combustion route / K. Singh, S. A. Acharya, S. S. Bhoga. Red soil in Northern Sri Lanka is a natural magnetic ceramic / K. Ahilan ... [et al.]. Neutron scattering of LiNiO[symbol] / K. Basar ... [et al.]. Preparation and properties of LiFePO[symbol] nanorods / L. Q. Mai ... [et al.]. Structural and electrochemical properties of monoclinic and othorhombic MoO[symbol] phases / O. M. Hussain ... [et al.]. Preparation of Zircon (ZrSiO[symbol]) ceramics via solid state sintering of Zr)[symbol] and SiO[symbol] and the effect of dopants on the zircon yield / U. Dhanayake, B. S. B. Karunaratne. Preparation and properties of vanadium doped ZnTe cermet thin films / M. S. Hossain, R. Islam, K. A. Khan. Dynamical properties and electronic structure of lithium-ion conductor / M. Kobayashi ... [et al.]. Cuprous ion conducting Montmorillonite-Polypyrrole nanocomposites / D. M. M. Krishantha ... [et al.]. Frequency dependence of conductivity studies on a newly synthesized superionic solid solution/mixed system: [0.75AgI: 0.25AgCl] / R. K. Nagarch, R. Kumar. Diffuse X-ray and neutron scattering from Powder PbS / X. Lian ... [et al.]. Electron affinity and work function of Pyrolytic MnO[symbol] thin films prepared from Mn(C[symbol]H[symbol]O[symbol])[symbol].4H[symbol]) / A. K. M. Farid Ul Islam, R. Islam, K. A. Khan. Crystal structure and heat capacity of Ba[symbol]Ca[symbol]Nb[symbol]O[symbol] / T. Shimoyama ... [et al.]. XPS and impedance investigations on amorphous vanadium oxide thin films / M. Kamalanathan ... [et al.]. Sintering and mixed electronic-ionic conducting properties of La[symbol]Sr[symbol]NiO[symbol] derived from a polyaminocarboxylate complex precursor / D.-P. Huang ... [et al.]. Preparation and characteristics of ball milled MgH[symbol] + M (M= Fe, VF[symbol] and FeF[symbol]) nanocomposites for hydrogen storage / N. W. B. Balasooriya, Ch. Poinsignon. Structural studies of oxysulfide glasses by X-ray diffraction and molecular dynamics simulation / R. Prasada Rao, M. Seshasayee, J. Dheepa. Synthesis, sintering and oxygen ionic conducting properties of Bi[symbol]V[symbol]Cu[symbol]O[symbol] / F. Zhang ... [et al.]. Synthesis and transport characteristics of PbI[symbol]-Ag[symbol]O-Cr[symbol]O[symbol] superioninc system / S. A. Suthanthiraraj, V. Mathew. Electronic conductivity of La[symbol]Sr[symbol]Ga[symbol]Mg[symbol]Co[symbol]O[symbol] electrolytes / K. Yamaji ... [et al.] -- pt. II. Electrode materials. Invited papers. Cathodic properties of Al-doped LiCoO[symbol] prepared by molten salt method Li-Ion batteries / M. V. Reddy, G. V. Subba Rao, B. V. R. Chowdari. Layered ion-electron conducting materials / M. A. Santa Ana, E. Benavente, G. González. LiNi[symbol]Co[symbol]O[symbol] cathode thin-film prepared by RF sputtering for all-solid-state rechargeable microbatteries / X. J. Zhu ... [et al.] -- Contributed papers. Contributed papers. Nanocomposite cathode for SOFCs prepared by electrostatic spray deposition / A. Princivalle, E. Djurado. Effect of the addition of nanoporous carbon black on the cycling characteristics of Li[symbol]Co[symbol](MoO[symbol])[symbol] for lithium batteries / K. M. Begam, S. R. S. Prabaharan. Protonic conduction in TiP[symbol]O[symbol] / V. Nalini, T. Norby, A. M. Anuradha. Preparation and electrochemical LiMn[symbol]O[symbol] thin film by a solution deposition method / X. Y. Gan ... [et al.]. Synthesis and characterization LiMPO[symbol] (M = Ni, Co) / T. Savitha, S. Selvasekarapandian, C. S. Ramya. Synthesis and electrical characterization of LiCoO[symbol] LiFeO[symbol] and NiO compositions / A. Wijayasinghe, B. Bergman. Natural Sri Lanka graphite as conducting enhancer in manganese dioxide (Emd type) cathode of alkaline batteries / N. W. B. Balasooriya ... [et al.]. Electrochemical properties of LiNi[symbol]Al[symbol]Zn[symbol]O[symbol] cathode material synthesized by emulsion method / B.-H. Kim ... [et al.]. LiNi[symbol]Co[symbol]O[symbol] cathode materials synthesized by particulate sol-gel method for lithium ion batteries / X. J. Zhu ... [et al.]. Pulsed laser deposition of highly oriented LiCoO[symbol] and LiMn[symbol]O[symbol] thin films for microbattery applications / O. M. Hussain ... [et al.]. Preparation of LiNi[symbol]Co[symbol]O[symbol] thin films by a sol-gel method / X. J. Zhu ... [et al.]. Electrochemical lithium insertion into a manganese dioxide electrode in aqueous solutions / M. Minakshi ... [et al.]. AC impedance spectroscopic analysis of thin film LiNiVO[symbol] prepared by pulsed laser deposition technique / S. Selvasekarapandian ... [et al.]. Synthesis and characterization of LiFePO[symbol] cathode materials by microwave processing / J. Zhou ... [et al.]. Characterization of Nd[symbol]Sr[symbol]CoO[symbol] including Pt second phase as the cathode material for low-temperature SOFCs / J. W. Choi ... [et al.]. Thermodynamic behavior of lithium intercalation into natural vein and synthetic graphite / N. W. B. Balasooriya, P. W. S. K. Bandaranayake, Ph. Touzain -- pt. III. Electroactive polymers. Invited papers. Organised or disorganised? looking at polymer electrolytes from both points of view / Y.-P. Liao ... [et al.]. Polymer electrolytes - simple low permittivity solutions? / I. Albinsson, B.-E. Mellander. Dependence of conductivity enhancement on the dielectric constant of the dispersoid in polymer-ferroelectric composite electrolytes / A. Chandra, P. K. Singh, S. Chandra. Design and application of boron compounds for high-performance polymer electrolytes / T. Fujinami. Structural, vibrational and AC impedance analysis of nano composite polymer electrolytes based on PVAC / S. Selvasekarapandian ... [et al.]. Absorption intensity variation with ion association in PEO based electrolytes / J. E. Furneaux ... [et al.]. Study of ion-polymer interactions in cationic and anionic ionomers from the dependence of conductivity on pressure and temperature / M. Duclot ... [et al.]. Triol based polyurethane gel electrolytes for electrochemical devices / A. R. Kulkarni. Contributed papers. Accurate conductivity measurements to solvation energies in nafion / M. Maréchal, J.-L Souquet. Ion conducting behaviour of composite polymer gel electrolyte: PEG-PVA-(NH[symbol]CH[symbol]CO[symbol])[symbol] system / S. L. Agrawal, A. Awadhia, S. K. Patel. Impedance spectroscopy and DSC studies of poly(vinylalcohol)/ silicotungstic acid crosslinked composite membranes / A. Anis, A. K. Banthia. (PEO)[symbol]:Na[symbol]P[symbol]O[symbol]: a report on complex formation / A. Bhide, K. Hariharan. Experimental studies on (PVC+LiClO[symbol]+DMP) polymer electrolyte systems for lithium battery / Ch. V. S. Reddy. Stability of the gel electrolyte, PAN: EC: PC: LiCF[symbol]SO[symbol] towards lithium / K. Perera ... [et al.]. Montmorillonite as a conductivity enhancer in (PEO)[symbol]LiCF[symbol]SO[symbol] polymer electrolyte / C. H. Manoratne ... [et al.]. Polymeric gel electrolytes for electrochemical capacitors / M. Morita ... [et al.]. Electrical conductivity studies on proton conducting polymer electrolytes based on poly (viniyl acetate) / D. Arun Kumar ... [et al.]. Conductivity and thermal studies on plasticized PEO:LiTf-Al[symbol]O[symbol] composite polymer electrolyte / H. M. J. C. Pitawala, M. A. K. L. Dissanayake, V. A. Seneviratne. Investigation of transport properties of a new biomaterials - gum mangosteen / S. S. Pradhan, A. Sarkar. Investigation of ionic conductivity of PEO-MgCl[symbol] based solid polymer electrolyte / M. Sundar ... [et al.]. [symbol]H NMR and Raman analysis of proton conducting polymer electrolytes based on partially hydrolyzed poly (vinyl alcohol) / G. Hirankumar ... [et al.]. Influence of Al[symbol]O[symbol] nanoparticles on the phase matrix of polyethylene oxide-silver triflate polymer electrolytes / S. Austin Suthanthiraraj, D. Joice Sheeba. Effect of different types of ceramic fillers on thermal, dielectric and transport properties of PEO[symbol]LiTf solid polymer electrolyte / K. Vignarooban ... [et al.]. Characterization of PVP based solid polymer electrolytes using spectroscopic techniques / C. S. Ramya ... [et al.]. Electrochemical and structural properties of poly vinylidene fluoride - silver triflate solid polymer electrolyte system / S. Austin Suthanthiraraj, B. Joseph Paul. Micro Raman, Li NMR and AC impedance analysis of PVAC:LiClO[symbol] solid polymer eectrolytes / R. Baskaran ... [et al.].Study of Na+ ion conduction in PVA-NaSCN solid polymer electrolytes / G. M. Brahmanandhan ... [et al.]. Effect of filler addition on plasticized polymer electrolyte systems / M. Sundar, S. Selladurai. Ionic motion in PEDOT and PPy conducting polymer bilayers / U. L. Zainudeen, S. Skaarup, M. A. Careem. Film formation mechanism and electrochemical characterization of V[symbol]O[symbol] xerogel intercalated by polyaniniline / Q. Zhu ... [et al.]. Effect of NH[symbol]NO[symbol] concentration on the conductivity of PVA based solid polymer electrolyte / M. Hema ... [et al.]. Dielectric and conductivity studies of PVA-KSCN based solid polymer electrolytes / J. Malathi ... [et al.] -- pt. IV. Emerging applications. Invited papers. The use of solid state ionic materials and devices in medical applications / R. Linford. Development of all-solid-state lithium batteries / V. Thangadurai, J. Schwenzei, W. Weppner. Reversible intermediate temperature solid oxide fuel cells / B.-E. Mellander, I. Albinsson. Nano-size effects in lithium batteries / P. Balaya, Y. Hu, J. Maier. Electrochromics: fundamentals and applications / C. G. Granqvist. Electrochemical CO[symbol] gas sensor / K. Singh. Polypyrrole for artificial muscles: ionic mechanisms / S. Skaarup. Development and characterization of polyfluorene based light emitting diodes and their colour tuning using Forster resonance energy transfer / P. C. Mattur ... [et al.]. Mesoporous and nanoparticulate metal oxides: applications in new photocatalysis / C. Boxall. Proton Conducting (PC) perovskite membranes for hydrogen separation and PC-SOFC electrodes and electrolytes / H. Jena, B. Rambabu. Contributed papers. Electroceramic materials for the development of natural gas fuelled SOFC/GT plant in developing country (Trinidad and Tobogo (T&T)) / R. Saunders, H. Jena, B. Rambabu. Thin film SOFC supported on nano-porous substrate / J. Hoon Joo, G. M. Choi. Characterization and fabrication of silver solid state battery Ag/AGI-AgPO[symbol]/I[symbol], C / E. Kartini ... [et al.]. Performance of lithium polymer cells with polyacrylonitrile based electrolyte / K. Perera ... [et al.]. Hydrothermal synthesis and electrochemical behavior of MoO[symbol] nanobelts for lithium batteries / Y. Qi ... [et al.]. Electrochemical behaviour of a PPy (DBS)/polyacrylonitrile: LiTF:EC:PC/Li cell / K. Vidanapathirana ... [et al.]. Characteristics of thick film CO[symbol] sensors based on NASICON using Li[symbol]CO[symbol]-CaCO[symbol] auxiliary phases / H. J. Kim ... [et al.]. Solid state battery discharge characteristic study on fast silver ion conducting composite system: 0.9[0.75AgI:0.25AgCl]: 0.1TiO[symbol] / R. K. Nagarch, R. Kumar, P. Rawat. Intercalating protonic solid-state batteries with series and parallel combination / K. Singh, S. S. Bhoga, S. M. Bansod. Synthesis and characterization of ZnO fiber by microwave processing / Lin Wang ... [et al.]. Preparation of Sn-Ge alloy coated Ge nanoparticles and Sn-Si alloy coated Si nanoparticles by ball-milling / J. K. D. S. Jayanett, S. M. Heald. Synthesis of ultrafine and crystallized TiO[symbol] by alalkoxied free polymerizable precursor method / M. Vijayakumar ... [et al.]. Development and characterization of polythiophene/fullerene composite solar cells and their degradation studies / P. K. Bhatnagar ... [et al.].

MATERIAL AND PROCESS DEVELOPMENT LEADING TO ECONOMICAL HIGH-PERFORMANCE THIN-FILM SOLID OXIDE FUEL CELLS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jie Guan; Atul Verma; Nguyen Minh

2003-04-01

This document summarizes the technical progress from September 2002 to March 2003 for the program, Material and Process Development Leading to Economical High-Performance Thin-Film Solid Oxide Fuel Cells, contract number DE-AC26-00NT40711. The causes have been identified for the unstable open circuit voltage (OCV) and low performance exhibited by the anode-supported lanthanum gallate based cells from the earlier development. Promising results have been obtained in the area of synthesis of electrolyte and cathode powders, which showed excellent sintering and densification at low temperatures. The fabrication of cells using tapecalendering process for anode-supported thin lanthanum gallate electrolyte cells and their performance optimizationmore » is in progress.« less

Collection-efficient, axisymmetric vacuum sublimation module for the purification of solid materials.

PubMed

May, Michael; Paul, Elizabeth; Katovic, Vladimir

2015-11-01

A vacuum sublimation module of axisymmetric geometry was developed and employed to purify solid-phase materials. The module provides certain practical advantages and it comprises: a metering valve, glass collector, glass lower body, main seal, threaded bushing, and glass internal cartridge (the latter to contain starting material). A complementary process was developed to de-solvate, sublime, weigh, and collect solid chemical materials exemplified by oxalic acid, ferrocene, pentachlorobenzene, chrysene, and urea. The oxalic acid sublimate was analyzed by titration, melting range, Fourier Transform Infrared (FT-IR) Spectroscopy, cyclic voltammetry, and its (aqueous phase) electrolytically generated gas. The analytical data were consistent with a high-purity, anhydrous oxalic acid sublimate. Cyclic voltammograms of 0.11 mol. % oxalic acid in water displayed a 2.1 V window on glassy carbon electrode beyond which electrolytic decomposition occurs. During module testing, fifteen relatively pure materials were sublimed with (energy efficient) passive cooling and the solid-phase recovery averaged 95 mass %. Key module design features include: compact vertical geometry, low-angle conical collector, uniformly compressed main seal, modest power consumption, transparency, glovebox compatibility, cooling options, and preferential conductive heat transfer. To help evaluate the structural (module) heat transfer, vertical temperature profiles along the dynamically evacuated lower body were measured versus electric heater power: for example, an input of 18.6 W generated a temperature 443-K at the bottom. Experimental results and engineering calculations indicate that during sublimation, solid conduction is the primary mode of heat transfer to the starting material.

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

PubMed

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

2015-12-15

The synthesis of polymer gel electrolyte having high ionic conductivity, excellent compatibility with active electrode material, mechanical tractability and long life is crucial to obtain majestic electrochemical performance for flexible solid state supercapacitors (FSS-SCs). Our present work describes effect of different polymers gel electrolytes on electrochemical properties of MnO2 based FSS-SCs device. It is revealed that, MnO2-FSS-SCs with polyvinyl alcohol (PVA)-Lithium perchlorate (LiClO4) gel electrolyte demonstrate excellent electrochemical features such as maximum operating potential window (1.2V), specific capacitance of 112Fg(-1) and energy density of 15Whkg(-1) with extended cycling stability up to 2500CV cycles. Moreover, the calendar life suggests negligible decrease in the electrochemical performance of MnO2-FSS-SCs after 20days. Copyright © 2015 Elsevier Inc. All rights reserved.

Structural and optical characterization of PVA:KMnO4 based solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Abdullah, Omed Gh.; Aziz, Shujahadeen B.; Rasheed, Mariwan A.

Solid polymer electrolyte films of polyvinyl alcohol (PVA) doped with a different weight percent of potassium permanganate (KMnO4) were prepared by standard solution cast method. XRD and FTIR techniques were performed for structural study. Complex formation between the PVA polymer and KMnO4 salt was confirmed by Fourier transform infrared (FTIR) spectroscopy. The description of crystalline nature of the solid polymer electrolyte films has been confirmed by XRD analysis. The UV-Visible absorption spectra were analyzed in terms of absorption formula for non-crystalline materials. The fundamental optical parameters such as optical band gap energy, refractive index, optical conductivity, and dielectric constants have been investigated and showed a clear dependence on the KMnO4 concentration. The observed value of optical band gap energy for pure PVA is about 6.27 eV and decreases to a value 3.12 eV for the film sample formed with 4 wt% KMnO4 salt. The calculated values of refractive index and the dielectric constants of the polymer electrolyte films increase with increasing KMnO4 content.

Polarization study on doped lanthanum gallate electrolyte using impedance spectroscopy

NASA Astrophysics Data System (ADS)

Gong, Wenquan; Gopalan, Srikanth; Pal, Uday B.

2004-06-01

Alternating current complex impedance spectroscopy studies were conducted on symmetrical cells of the type [gas, electrode/La1-x Sr x Ga1-y Mg y O3 (LSGM) electrolyte/electrode, gas]. The electrode materials were slurry-coated on both sides of the LSGM electrolyte support. The electrodes selected for this investigation are candidate materials for solid oxide fuel cell (SOFC) electrodes. Cathode materials include La1-x Sr x MnO3 (LSM), La1-x Sr x Co y Fe1-y O3 (LSCF), a two-phase particulate composite consisting of LSM and doped-lanthanum gallate (LSGM), and LSCF + LSGM. Pt metal electrodes were also used for the purpose of comparison. Anode material investigated was the Ni + Ce0.85Gd0.15O2 composite. The study revealed important details pertaining to the charge-transfer reactions that occur in such electrodes. The information obtained can be used to design electrodes for intermediate temperature SOFCs based on LSGM electrolytes.

Towards High-Performance Aqueous Sodium-Ion Batteries: Stabilizing the Solid/Liquid Interface for NASICON-Type Na2 VTi(PO4 )3 using Concentrated Electrolytes.

PubMed

Zhang, Huang; Jeong, Sangsik; Qin, Bingsheng; Vieira Carvalho, Diogo; Buchholz, Daniel; Passerini, Stefano

2018-04-25

Aqueous Na-ion batteries may offer a solution to the cost and safety issues of high-energy batteries. However, substantial challenges remain in the development of electrode materials and electrolytes enabling high performance and long cycle life. Herein, we report the characterization of a symmetric Na-ion battery with a NASICON-type Na 2 VTi(PO 4 ) 3 electrode material in conventional aqueous and "water-in-salt" electrolytes. Extremely stable cycling performance for 1000 cycles at a high rate (20 C) is found with the highly concentrated aqueous electrolytes owing to the formation of a resistive but protective interphase between the electrode and electrolyte. These results provide important insight for the development of aqueous Na-ion batteries with stable long-term cycling performance for large-scale energy storage. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge and discharge characteristics of lithium-ion graphite electrodes in solid-state cells

NASA Astrophysics Data System (ADS)

Lemont, S.; Billaud, D.

Lithium ions have been electrochemically intercalated into graphite in solid-state cells operating with solid polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO 4). The working composite electrode is composed of active-divided natural graphite associated with P(EO) 8-LiClO 4 acting as a binder and a Li + ionic conductor. Intercalation and de-intercalation of Li + were performed using galvanostatic or voltammetry techniques. The curves obtained in our solid-state cells were compared with those performed in liquid ethylene carbonate-LiClO 4 electrolyte. It is shown that in solid-state cells, side reactions occur both in the reduction and in the oxidation processes which leads to some uncertainty in the determination of the maximum reversible capacity of the graphite material.

First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-12-11

All-solid-state Li-ion batteries based on ceramic solid electrolyte materials are a promising next-generation energy storage technology with high energy density and enhanced cycle life. The poor interfacial conductance is one of the key limitations in enabling all-solid-state Li-ion batteries. However, the origin of this poor conductance has not been understood, and there is limited knowledge about the solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries. In this paper, we performed first principles calculations to evaluate the thermodynamics of the interfaces between solid electrolyte and electrode materials and to identify the chemical and electrochemical stabilities of these interfaces. Our computation results revealmore » that many solid electrolyte–electrode interfaces have limited chemical and electrochemical stability, and that the formation of interphase layers is thermodynamically favorable at these interfaces. These formed interphase layers with different properties significantly affect the electrochemical performance of all-solid-state Li-ion batteries. The mechanisms of applying interfacial coating layers to stabilize the interface and to reduce interfacial resistance are illustrated by our computation. This study demonstrates a computational scheme to evaluate the chemical and electrochemical stability of heterogeneous solid interfaces. Finally, the enhanced understanding of the interfacial phenomena provides the strategies of interface engineering to improve performances of all-solid-state Li-ion batteries.« less

Superior Blends Solid Polymer Electrolyte with Integrated Hierarchical Architectures for All-Solid-State Lithium-Ion Batteries.

PubMed

Zhang, Dechao; Zhang, Long; Yang, Kun; Wang, Hongqiang; Yu, Chuang; Xu, Di; Xu, Bo; Wang, Li-Min

2017-10-25

Exploration of advanced solid electrolytes with good interfacial stability toward electrodes is a highly relevant research topic for all-solid-state batteries. Here, we report PCL/SN blends integrating with PAN-skeleton as solid polymer electrolyte prepared by a facile method. This polymer electrolyte with hierarchical architectures exhibits high ionic conductivity, large electrochemical windows, high degree flexibility, good flame-retardance ability, and thermal stability (workable at 80 °C). Additionally, it demonstrates superior compatibility and electrochemical stability toward metallic Li as well as LiFePO 4 cathode. The electrolyte/electrode interfaces are very stable even subjected to 4.5 V at charging state for long time. The LiFePO 4 /Li all-solid-state cells based on this electrolyte deliver high capacity, outstanding cycling stability, and superior rate capability better than those based on liquid electrolyte. This solid polymer electrolyte is eligible for next generation high energy density all-solid-state batteries.

Materials for suspension (semi-solid) electrodes for energy and water technologies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hatzell, Kelsey B.; Boota, Muhammad; Gogotsi, Yury

2015-01-01

Suspension or semi-solid electrodes have recently gained increased attention for large-scale applications such as grid energy storage, capacitive water deionization, and wastewater treatment. A suspension electrode is a multiphase material system comprised of an active (charge storing) material suspended in ionic solution (electrolyte). Gravimetrically, the electrolyte is the majority component and aids in physical transport of the active material. For the first time, this principle enables, scalability of electrochemical energy storage devices (supercapacitors and batteries) previously limited to small and medium scale applications. This critical review describes the ongoing material challenges encompassing suspension-based systems. The research described here combines classicalmore » aspects of electrochemistry, colloidal science, material science, fluid mechanics, and rheology to describe ion and charge percolation, adsorption of ions, and redox charge storage processes in suspension electrodes. Our review summarizes the growing inventory of material systems, methods and practices used to characterize suspension electrodes, and describes universal material system properties (rheological, electrical, and electrochemical) that are pivotal in the design of high performing systems. We include a discussion of the primary challenges and future research directions.« less

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

NASA Technical Reports Server (NTRS)

West, William; Whitacre, Jay; Lim, James

2008-01-01

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

Thermostable gel polymer electrolyte based on succinonitrile and ionic liquid for high-performance solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Pandey, Gaind P.; Liu, Tao; Hancock, Cody; Li, Yonghui; Sun, Xiuzhi Susan; Li, Jun

2016-10-01

A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10-4 S cm-1 at -30 °C up to ∼1.5 × 10-2 S cm-1 at 80 °C) with good electrochemical stability window (-2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from -30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g-1 at 0.18 A g-1 and 138 F g-1 at 8 A g-1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.

High-Performance All-Solid-State Na-S Battery Enabled by Casting-Annealing Technology.

PubMed

Fan, Xiulin; Yue, Jie; Han, Fudong; Chen, Ji; Deng, Tao; Zhou, Xiuquan; Hou, Singyuk; Wang, Chunsheng

2018-04-24

Room-temperature all-solid-state Na-S batteries (ASNSBs) using sulfide solid electrolytes are a promising next-generation battery technology due to the high energy, enhanced safety, and earth abundant resources of both sodium and sulfur. Currently, the sulfide electrolyte ASNSBs are fabricated by a simple cold-pressing process leaving with high residential stress. Even worse, the large volume change of S/Na 2 S during charge/discharge cycles induces additional stress, seriously weakening the less-contacted interfaces among the solid electrolyte, active materials, and the electron conductive agent that are formed in the cold-pressing process. The high and continuous increase of the interface resistance hindered its practical application. Herein, we significantly reduce the interface resistance and eliminate the residential stress in Na 2 S cathodes by fabricating Na 2 S-Na 3 PS 4 -CMK-3 nanocomposites using melting-casting followed by stress-release annealing-precipitation process. The casting-annealing process guarantees the close contact between the Na 3 PS 4 solid electrolyte and the CMK-3 mesoporous carbon in mixed ionic/electronic conductive matrix, while the in situ precipitated Na 2 S active species from the solid electrolyte during the annealing process guarantees the interfacial contact among these three subcomponents without residential stress, which greatly reduces the interfacial resistance and enhances the electrochemical performance. The in situ synthesized Na 2 S-Na 3 PS 4 -CMK-3 composite cathode delivers a stable and highly reversible capacity of 810 mAh/g at 50 mA/g for 50 cycles at 60 °C. The present casting-annealing strategy should provide opportunities for the advancement of mechanically robust and high-performance next-generation ASNSBs.

Rechargeable solid polymer electrolyte battery cell

DOEpatents

Skotheim, Terji

1985-01-01

A rechargeable battery cell comprising first and second electrodes sandwiching a solid polymer electrolyte comprising a layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte adjacent said polymer blend and a layer of dry solid polymer electrolyte adjacent said layer of polymer blend and said second electrode.

Copper Antimonide Nanowire Array Lithium Ion Anodes Stabilized by Electrolyte Additives.

PubMed

Jackson, Everett D; Prieto, Amy L

2016-11-09

Nanowires of electrochemically active electrode materials for lithium ion batteries represent a unique system that allows for intensive investigations of surface phenomena. In particular, highly ordered nanowire arrays produced by electrodeposition into anodic aluminum oxide templates can lead to new insights into a material's electrochemical performance by providing a high-surface-area electrode with negligible volume expansion induced pulverization. Here we show that for the Li-Cu x Sb ternary system, stabilizing the surface chemistry is the most critical factor for promoting long electrode life. The resulting solid electrolyte interphase is analyzed using a mix of electron microscopy, X-ray photoelectron spectroscopy, and lithium ion battery half-cell testing to provide a better understanding of the importance of electrolyte composition on this multicomponent alloy anode material.

Carbon dioxide electrolysis with solid oxide electrolyte cells for oxygen recovery in life support systems

NASA Technical Reports Server (NTRS)

Isenberg, Arnold O.; Cusick, Robert J.

1988-01-01

The direct electrochemical reduction of carbon dioxide (CO2) is achieved without catalysts and at sufficiently high temperatures to avoid carbon formation. The tubular electrolysis cell consists of thin layers of anode, electrolyte, cathode and cell interconnection. The electrolyte is made from yttria-stabilized zirconia which is an oxygen ion conductor at elevated temperatures. Anode and cell interconnection materials are complex oxides and are electronic conductors. The cathode material is a composite metal-ceramic structure. Cell performance characteristics have been determined using varying feed gas compositions and degrees of electrochemical decomposition. Cell test data are used to project the performance of a three-person CO2-electrolysis breadboard system.

The main directions in technology investigation of soid oxide fuel cell in Russian Federal Research Center Institute of Physics & Power Engineering (IPPE)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ievleva, J.I.; Kolesnikov, V.P.; Mezhertisky, G.S.

1996-04-01

The main direction of science investigations for creation of efficient solid oxide fuel cells (SOFC) in IPPE are considered in this work. The development program of planar SOFC with thin-film electrolyte is shown. General design schemes of experimental SOFC units are presented. The flow design schemes of processes for initial materials and electrodes fabrication are shown. The results of investigations for creation thin-film solid oxide electrolyte at porous cathode by magnetron sputtering from complex metal target in oxidative environment are presented.

Ionic liquids and derived materials for lithium and sodium batteries.

PubMed

Yang, Qiwei; Zhang, Zhaoqiang; Sun, Xiao-Guang; Hu, Yong-Sheng; Xing, Huabin; Dai, Sheng

2018-03-21

The ever-growing demand for advanced energy storage devices in portable electronics, electric vehicles and large scale power grids has triggered intensive research efforts over the past decade on lithium and sodium batteries. The key to improve their electrochemical performance and enhance the service safety lies in the development of advanced electrode, electrolyte, and auxiliary materials. Ionic liquids (ILs) are liquids consisting entirely of ions near room temperature, and are characterized by many unique properties such as ultralow volatility, high ionic conductivity, good thermal stability, low flammability, a wide electrochemical window, and tunable polarity and basicity/acidity. These properties create the possibilities of designing batteries with excellent safety, high energy/power density and long-term stability, and also provide better ways to synthesize known materials. IL-derived materials, such as poly(ionic liquids), ionogels and IL-tethered nanoparticles, retain most of the characteristics of ILs while being endowed with other favourable features, and thus they have received a great deal of attention as well. This review provides a comprehensive review of the various applications of ILs and derived materials in lithium and sodium batteries including Li/Na-ion, dual-ion, Li/Na-S and Li/Na-air (O 2 ) batteries, with a particular emphasis on recent advances in the literature. Their unique characteristics enable them to serve as advanced resources, medium, or ingredient for almost all the components of batteries, including electrodes, liquid electrolytes, solid electrolytes, artificial solid-electrolyte interphases, and current collectors. Some thoughts on the emerging challenges and opportunities are also presented in this review for further development.

Structure and transport properties of a plastic crystal ion conductor: diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate.

PubMed

Jin, Liyu; Nairn, Kate M; Forsyth, Craig M; Seeber, Aaron J; MacFarlane, Douglas R; Howlett, Patrick C; Forsyth, Maria; Pringle, Jennifer M

2012-06-13

Understanding the ion transport behavior of organic ionic plastic crystals (OIPCs) is crucial for their potential application as solid electrolytes in various electrochemical devices such as lithium batteries. In the present work, the ion transport mechanism is elucidated by analyzing experimental data (single-crystal XRD, multinuclear solid-state NMR, DSC, ionic conductivity, and SEM) as well as the theoretical simulations (second moment-based solid static NMR line width simulations) for the OIPC diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate ([P(1,2,2,4)][PF(6)]). This material displays rich phase behavior and advantageous ionic conductivities, with three solid-solid phase transitions and a highly "plastic" and conductive final solid phase in which the conductivity reaches 10(-3) S cm(-1). The crystal structure shows unique channel-like packing of the cations, which may allow the anions to diffuse more easily than the cations at lower temperatures. The strongly phase-dependent static NMR line widths of the (1)H, (19)F, and (31)P nuclei in this material have been well simulated by different levels of molecular motions in different phases. Thus, drawing together of the analytical and computational techniques has allowed the construction of a transport mechanism for [P(1,2,2,4)][PF(6)]. It is also anticipated that utilization of these techniques will allow a more detailed understanding of the transport mechanisms of other plastic crystal electrolyte materials.

Robert Tenent | NREL

Science.gov Websites

improved electrochemical devices, in particular electrochromic windows and lithium ion batteries. At NREL Materials Design and Integration for Electrochromic Devices and Li-ion Batteries Gel/Solid Electrolyte

Solid state potentiometric gaseous oxide sensor

NASA Technical Reports Server (NTRS)

Wachsman, Eric D. (Inventor); Azad, Abdul Majeed (Inventor)

2003-01-01

A solid state electrochemical cell (10a) for measuring the concentration of a component of a gas mixture (12) includes first semiconductor electrode (14) and second semiconductor electrode (16) formed from first and second semiconductor materials, respectively. The materials are selected so as to undergo a change in resistivity upon contacting a gas component, such as CO or NO. An electrolyte (18) is provided in contact with the first and second semiconductor electrodes. A reference cell can be included in contact with the electrolyte. Preferably, a voltage response of the first semiconductor electrode is opposite in slope direction to that of the second semiconductor electrode to produce a voltage response equal to the sum of the absolute values of the control system uses measured pollutant concentrations to direct adjustment of engine combustion conditions.

Gradiently Polymerized Solid Electrolyte Meets with Micro/Nano-Structured Cathode Array.

PubMed

Dong, Wei; Zeng, Xian-Xiang; Zhang, Xu-Dong; Li, Jin-Yi; Shi, Ji-Lei; Xiao, Yao; Shi, Yang; Wen, Rui; Yin, Ya-Xia; Wang, Tai-Shan; Wang, Chun-Ru; Guo, Yu-Guo

2018-05-02

The poor contact between the solid-state electrolyte and cathode materials leads to high interfacial resistance, severely limiting the rate capability of solid Li metal batteries. Herein, an integrative battery design is introduced with a gradiently polymerized solid electrolyte (GPSE), a micro-channel current collector array and nano-sized cathode particles. In-situ formed GPSE encapsulates cathode nanoparticles in the micro-channel with ductile inclusions to lower interfacial impedance, and the stiff surface layer of GPSE toward anode suppresses Li dendrites growth. Li metal batteries based on GPSE and Li-free hydrogenated V2O5 (V2O5-H) cathode exhibit an outstanding high-rate response of up to 5 C (the capacity ratio of 5 C / 1 C is 90.3%) and an ultralow capacity fade rate of 0.07% per cycle over 300 cycles. Other Li-containing cathodes as LiFePO4 and LiNi0.5Mn0.3Co0.2O2 can also operate effectively at 5 C and 2 C rate, respectively. Such an ingenious design may provide new insights into other solid metal batteries through interfacial engineering manipulation at micro and nano level.

A p-nitroaniline redox-active solid-state electrolyte for battery-like electrochemical capacitive energy storage combined with an asymmetric supercapacitor based on metal oxide functionalized β-polytype porous silicon carbide electrodes.

PubMed

Kim, Myeongjin; Yoo, Jeeyoung; Kim, Jooheon

2017-05-23

A unique redox active flexible solid-state asymmetric supercapacitor with ultra-high capacitance and energy density was fabricated using a composite comprising MgCo 2 O 4 nanoneedles and micro and mesoporous silicon carbide flakes (SiCF) (SiCF/MgCo 2 O 4 ) as the positive electrode material. Due to the synergistic effect of the two materials, this hybrid electrode has a high specific capacitance of 516.7 F g -1 at a scan rate of 5 mV s -1 in a 1 M KOH aqueous electrolyte. To obtain a reasonable matching of positive and negative electrode pairs, a composite of Fe 3 O 4 nanoparticles and SiCF (SiCF/Fe 3 O 4 ) was synthesized for use as a negative electrode material, which shows a high capacitance of 423.2 F g -1 at a scan rate of 5 mV s -1 . Therefore, by pairing the SiCF/MgCo 2 O 4 positive electrode and the SiCF/Fe 3 O 4 negative electrode with a redox active quasi-solid-state PVA-KOH-p-nitroaniline (PVA-KOH-PNA) gel electrolyte, a novel solid-state asymmetric supercapacitor device was assembled. Because of the synergistic effect between the highly porous SiCF and the vigorous redox-reaction of metal oxides, the hybrid nanostructure electrodes exhibited outstanding charge storage and transport. In addition, the redox active PVA-KOH-PNA electrolyte adds additional pseudocapacitance, which arises from the nitro-reduction and oxidation and reduction process of the reduction product of p-phenylenediamine, resulting in an enhancement of the capacitance (a specific capacitance of 161.77 F g -1 at a scan rate of 5 mV s -1 ) and energy density (maximum energy density of 72.79 Wh kg -1 at a power density of 727.96 W kg -1 ).

S-containing copolymer as cathode material in poly(ethylene oxide)-based all-solid-state Li-S batteries

NASA Astrophysics Data System (ADS)

Gracia, Ismael; Ben Youcef, Hicham; Judez, Xabier; Oteo, Uxue; Zhang, Heng; Li, Chunmei; Rodriguez-Martinez, Lide M.; Armand, Michel

2018-06-01

Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur and divinylbenzene (DVB) have been studied as cathode active materials in poly(ethylene oxide) (PEO)-based all-solid-state Li-S cells. The Li-S cell comprising the optimized p(S-DVB) cathode (80:20 w/w S/DVB ratio) and lithium bis(fluorosulfonyl)imide/PEO (LiFSI/PEO) electrolyte shows high specific capacity (ca. 800 mAh g-1) and high Coulombic efficiency for 50 cycles. Most importantly, polysulfide (PS) shuttle is highly mitigated due to the strong interactions of PS species with polymer backbone in p(S-DVB). This is demonstrated by the stable cycling of the p(S-DVB)-based cell using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PEO electrolyte, where successful charging cannot be achieved even at the first cycle with plain elemental S-based cathode material due to the severe PS shuttle phenomenon. These results suggest that inverse vulcanization copolymers are promising alternatives to elemental sulfur for enhancing the electrochemical performance of PEO-based all-solid-state Li-S cells.

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennett, William R.

2007-01-01

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

Low temperature sulfur and sodium metal battery for grid-scale energy storage application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Gao; Wang, Dongdong

A re-chargeable battery comprising a non-dendrite forming sodium (Na)/potassium (K) liquid metal alloy anode, a sulfur and polyacrylonitrile (PAN) conductive polymer composite cathode, a polyethyleneoxide (PEO) solid electrolyte, a solid electrolyte interface (SEI) formed on the PEO solid electrolyte; and a cell housing, wherein the anode, cathode, and electrolyte are assembled into the cell housing with the PEO solid electrolyte disposed between the cathode and anode.

Bulk-Type All-Solid-State Lithium-Ion Batteries: Remarkable Performances of a Carbon Nanofiber-Supported MgH2 Composite Electrode.

PubMed

Zeng, Liang; Ichikawa, Takayuki; Kawahito, Koji; Miyaoka, Hiroki; Kojima, Yoshitsugu

2017-01-25

Magnesium hydride, MgH 2 , a recently developed compound for lithium-ion batteries, is considered to be a promising conversion-type negative electrode material due to its high theoretical lithium storage capacity of over 2000 mA h g -1 , suitable working potential, and relatively small volume expansion. Nevertheless, it suffers from unsatisfactory cyclability, poor reversibility, and slow kinetics in conventional nonaqueous electrolyte systems, which greatly limit the practical application of MgH 2 . In this work, a vapor-grown carbon nanofiber was used to enhance the electrical conductivity of MgH 2 using LiBH 4 as the solid-state electrolyte. It shows that a reversible capacity of over 1200 mA h g -1 with an average voltage of 0.5 V (vs Li/Li + ) can be obtained after 50 cycles at a current density of 1000 mA g -1 . In addition, the capacity of MgH 2 retains over 1100 mA h g -1 at a high current density of 8000 mA g -1 , which indicates the possibility of using MgH 2 as a negative electrode material for high power and high capacity lithium-ion batteries in future practical applications. Moreover, the widely studied sulfide-based solid electrolyte was also used to assemble battery cells with MgH 2 electrode in the same system, and the electrochemical performance was as good as that using LiBH 4 electrolyte.

Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakamoto, Y.; Ishii, Y.; Kawasaki, S., E-mail: kawasaki.shinji@nitech.ac.jp

2016-07-06

Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

DOEpatents

Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

2015-02-24

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

Efficient and Stable Photovoltaic Characteristics of Quasi-Solid State DSSC using Polymer Gel Electrolyte Based on Ionic Liquid in Organosiloxane Polymer Gels

NASA Astrophysics Data System (ADS)

Pujiarti, H.; Arsyad, W. S.; Shobih; Muliani, L.; Hidayat, R.

2018-04-01

Dye-Sensitized Solar Cell (DSSC) is still one of the promising solar cell types among the third generation of solar cells because of easiness of fabrication and variety of available materials. In this type of solar cell, the electrolyte is one of the important components for regenerating excited dyes and transporting electric charge carriers to the counter electrode. Indeed, the power conversion efficiency of DSSC can be then significantly affected by the chemical and physical properties of the electrolyte. The simplest electrolyte system of an I-/I3 - redox couple in an organic solvent, however, has some drawbacks due to corrosive properties, volatile and leakage problem. Use of solid phase or gel phase electrolyte may overcome those problems, but it is often considered to suppress the efficiency due to low ion diffusion. Here, we report the photovoltaic characteristics of DSSC using polymer gel electrolyte (PGE), which is composed of ionic liquid and an organosiloxane polymer gel. The better cell performance with power conversion efficiency of about 6% has been obtained by optimizing the mesoporous size of the TiO2 layer and the PGE viscosity.

A Highly Reversible Room-Temperature Sodium Metal Anode

PubMed Central

2015-01-01

Owing to its low cost and high natural abundance, sodium metal is among the most promising anode materials for energy storage technologies beyond lithium ion batteries. However, room-temperature sodium metal anodes suffer from poor reversibility during long-term plating and stripping, mainly due to formation of nonuniform solid electrolyte interphase as well as dendritic growth of sodium metal. Herein we report for the first time that a simple liquid electrolyte, sodium hexafluorophosphate in glymes (mono-, di-, and tetraglyme), can enable highly reversible and nondendritic plating–stripping of sodium metal anodes at room temperature. High average Coulombic efficiencies of 99.9% were achieved over 300 plating–stripping cycles at 0.5 mA cm–2. The long-term reversibility was found to arise from the formation of a uniform, inorganic solid electrolyte interphase made of sodium oxide and sodium fluoride, which is highly impermeable to electrolyte solvent and conducive to nondendritic growth. As a proof of concept, we also demonstrate a room-temperature sodium–sulfur battery using this class of electrolytes, paving the way for the development of next-generation, sodium-based energy storage technologies. PMID:27163006

A Highly Reversible Room-Temperature Sodium Metal Anode.

PubMed

Seh, Zhi Wei; Sun, Jie; Sun, Yongming; Cui, Yi

2015-11-25

Owing to its low cost and high natural abundance, sodium metal is among the most promising anode materials for energy storage technologies beyond lithium ion batteries. However, room-temperature sodium metal anodes suffer from poor reversibility during long-term plating and stripping, mainly due to formation of nonuniform solid electrolyte interphase as well as dendritic growth of sodium metal. Herein we report for the first time that a simple liquid electrolyte, sodium hexafluorophosphate in glymes (mono-, di-, and tetraglyme), can enable highly reversible and nondendritic plating-stripping of sodium metal anodes at room temperature. High average Coulombic efficiencies of 99.9% were achieved over 300 plating-stripping cycles at 0.5 mA cm(-2). The long-term reversibility was found to arise from the formation of a uniform, inorganic solid electrolyte interphase made of sodium oxide and sodium fluoride, which is highly impermeable to electrolyte solvent and conducive to nondendritic growth. As a proof of concept, we also demonstrate a room-temperature sodium-sulfur battery using this class of electrolytes, paving the way for the development of next-generation, sodium-based energy storage technologies.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seh, Zhi Wei; Sun, Jie; Sun, Yongming

Owing to its low cost and high natural abundance, sodium metal is among the most promising anode materials for energy storage technologies beyond lithium ion batteries. However, room-temperature sodium metal anodes suffer from poor reversibility during long-term plating and stripping, mainly due to formation of nonuniform solid electrolyte interphase as well as dendritic growth of sodium metal. Herein we report for the first time that a simple liquid electrolyte, sodium hexafluorophosphate in glymes (mono-, di-, and tetraglyme), can enable highly reversible and nondendritic plating–stripping of sodium metal anodes at room temperature. High average Coulombic efficiencies of 99.9% were achieved overmore » 300 plating–stripping cycles at 0.5 mA cm –2. In this study, the long-term reversibility was found to arise from the formation of a uniform, inorganic solid electrolyte interphase made of sodium oxide and sodium fluoride, which is highly impermeable to electrolyte solvent and conducive to nondendritic growth. As a proof of concept, we also demonstrate a room-temperature sodium–sulfur battery using this class of electrolytes, paving the way for the development of next-generation, sodium-based energy storage technologies.« less

Interface Engineering of Garnet Solid Electrolytes

NASA Astrophysics Data System (ADS)

Cheng, Lei

Solid lithium ion conductors represent a promising class of materials for next generation high energy density batteries, with the potential for enabling use of high capacity Li metal anodes and providing opportunities for novel lithium-free cathode materials. However, highly resistive interfaces stymie their practical use. This urgent scientific challenge requires mechanistic understanding of ion transport at interfaces, as well as development of novel processes to achieve low interfacial resistances. The goal of this PhD dissertation was to generate fundamental understandings of garnet-structured Al substituted Li7La3Zr2O 12 (LLZO) electrolyte surfaces and interfaces with lithium metal electrodes. Specifically in this research, the topmost surface microstructure, local chemical environment, and surface chemistry were carefully studied. The ceramic processing of garnet is discussed and ways to control the sintering behavior and microstructures were explored and successfully demonstrated. Factors contributing to high interfacial resistance were systematically studied. The source of the high interfacial impedance has been traced to the presence of Li2CO 3 on pellet surfaces resulting from air exposure after processing. In addition, it was discovered that surface grain boundaries are surprisingly fast ion transport pathways and surface microstructure is critically important to lithium ion transport at interfaces. Complex homo- and heterostructured LLZO solid electrolytes with controllable surface and bulk microstructures were successfully fabricated, which allowed the comparison and separation of the contribution from the surface and the bulk. Engineered pellet surfaces allowed us to achieve the lowest interfacial resistance ever reported for this composition, resulting in significantly improved cycling behavior. Lastly, it was found that LLZO surfaces can be effectively stabilized under air exposure conditions, preventing Li2CO3 formation and maintaining low interfacial resistances. This opens new opportunities for garnet solid electrolyte in practical applications.

Facile synthesis of Li2S-P2S5 glass-ceramics electrolyte with micron range particles for all-solid-state batteries via a low-temperature solution technique (LTST)

NASA Astrophysics Data System (ADS)

Choi, Sunho; Lee, Sewook; Park, Jongyeop; Nichols, William T.; Shin, Dongwook

2018-06-01

A lithium ion conductive 75Li2Sṡ25P2S5 glass-ceramics electrolyte is, for the first time, successfully synthesized via a new low-temperature solution technique (LTST) and compared to the conventional mechanical-milling technique. Both samples are composed of the highly lithium ion conductive thio-LISICON III analog phase. Due to the uniform dispersion of reactants in an organic liquid, the use of LTST produced significantly smaller and more uniform particle sizes (2.2 ± 1.68 μm) resulting in a 6.5 times higher specific surface area compared to the mechanically-milled sample. A pronounced enhancement of both the rate capability and cyclability is demonstrated for the LTST solid electrolyte sample due to the more intimate contact with the LiCoO2 active material. Furthermore, the LTST sample shows excellent electrochemical stability throughout the potential range of -1 to 5 V. These results suggest that the proposed technique using the optimized LTST process is promising for the preparation of 75Li2Sṡ25P2S5 solid electrolytes for use in advanced Li-ion batteries.

Modeling Solvation Structure and Charge Transfer at the Solid Electrolyte Interphase for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Raguette, Lauren Elizabeth

Rechargeable lithium-ion battery technology is providing a revolution in energy storage. However, in order to fully realize this revolution, a better understanding is required of both the bulk properties of battery materials and their interfaces. This work endeavors to use classical molecular dynamics (MD) to investigate the electrochemical interfaces present in lithium-ion batteries to understand the impact of chemical reactions on ion transport. When batteries containing cyclic carbonates and lithium salts are charge cycled, both species can react with the electrodes to form complex solid mixtures at the electrode/electrolyte interface, known as a solid electrolyte interphase (SEI). While decades of experiments have yielded significant insights into the structure of these films and their chemical composition, there remains a lack of connection between the properties of the films and observed ion transport when interfaced with the electrolyte. A combination of MD and enhanced sampling methods will be presented to elucidate the link between the SEI, containing mixtures of dilithium ethylene dicarbonate (Li2EDC), lithium fluoride, and lithium carbonate, and battery performance. By performing extensive free energy calculations, clarity is provided to the impact of ion desolvation on the measured resistance to ion transport within lithium ion batteries.

A Self-Binding, Melt-Castable, Crystalline Organic Electrolyte for Sodium Ion Conduction.

PubMed

Chinnam, Parameswara Rao; Fall, Birane; Dikin, Dmitriy A; Jalil, AbdelAziz; Hamilton, Clifton R; Wunder, Stephanie L; Zdilla, Michael J

2016-12-05

The preparation and characterization of the cocrystalline solid-organic sodium ion electrolyte NaClO 4 (DMF) 3 (DMF=dimethylformamide) is described. The crystal structure of NaClO 4 (DMF) 3 reveals parallel channels of Na + and ClO 4 - ions. Pressed pellets of microcrystalline NaClO 4 (DMF) 3 exhibit a conductivity of 3×10 -4  S cm -1 at room temperature with a low activation barrier to conduction of 25 kJ mol -1 . SEM revealed thin liquid interfacial contacts between crystalline grains, which promote conductivity. The material melts gradually between 55-65 °C, but does not decompose, and upon cooling, it resolidifies as solid NaClO 4 (DMF) 3 , permitting melt casting of the electrolyte into thin films and the fabrication of cells in the liquid state and ensuring penetration of the electrolyte between the electrode active particles. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolyte bi-layering strategy to improve the performance of an intermediate temperature solid oxide fuel cell: A review

NASA Astrophysics Data System (ADS)

Shri Prakash, B.; Pavitra, R.; Senthil Kumar, S.; Aruna, S. T.

2018-03-01

Lowering of operation temperature has become one of the primary goals of solid oxide fuel (SOFC) research as reduced temperature improves the prospects for widespread commercialization of this energy system. Reduced operational temperature also mitigates the issues associated with high temperature SOFCs and paves way not only for the large scale stationary power generation but also makes SOFCs viable for portable and transport applications. However, there are issues with electrolyte and cathode materials at low temperatures, individually as well as in association with other components, which makes the performance of the SOFCs less satisfactory than expected at lowered temperatures. Bi-layering of electrolytes and impregnation of cathodes have emerged as two important strategies to overcome these issues and achieve higher performance at low temperatures. This review article provides the perspective on the strategy of bi-layering of electrolyte to achieve the desired high performance from SOFC at low to intermediate temperatures.

Lithium-ion batteries having conformal solid electrolyte layers

DOEpatents

Kim, Gi-Heon; Jung, Yoon Seok

2014-05-27

Hybrid solid-liquid electrolyte lithium-ion battery devices are disclosed. Certain devices comprise anodes and cathodes conformally coated with an electron insulating and lithium ion conductive solid electrolyte layer.

A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte.

PubMed

Gao, Tao; Li, Xiaogang; Wang, Xiwen; Hu, Junkai; Han, Fudong; Fan, Xiulin; Suo, Liumin; Pearse, Alex J; Lee, Sang Bok; Rubloff, Gary W; Gaskell, Karen J; Noked, Malachi; Wang, Chunsheng

2016-08-16

Aluminum metal is a promising anode material for next generation rechargeable batteries owing to its abundance, potentially dendrite-free deposition, and high capacity. The rechargeable aluminum/sulfur (Al/S) battery is of great interest owing to its high energy density (1340 Wh kg(-1) ) and low cost. However, Al/S chemistry suffers poor reversibility owing to the difficulty of oxidizing AlSx . Herein, we demonstrate the first reversible Al/S battery in ionic-liquid electrolyte with an activated carbon cloth/sulfur composite cathode. Electrochemical, spectroscopic, and microscopic results suggest that sulfur undergoes a solid-state conversion reaction in the electrolyte. Kinetics analysis identifies that the slow solid-state sulfur conversion reaction causes large voltage hysteresis and limits the energy efficiency of the system. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Li conduction pathways in solid-state electrolytes: Insights from dynamics and polarizability

NASA Astrophysics Data System (ADS)

Takahashi, Tsukasa; Nagagiri, Koki; Iwadate, Yasuhiko; Utsuno, Futoshi; Yamaguchi, Hiroshi; Ohkubo, Takahiro

2018-04-01

We investigated the dynamical and polarizable properties of Li7P3S11, which is a fast Li-conducting material, by performing ab initio molecular dynamics simulations. A zone analysis based on Li migration highlighted the effective path along which Li diffuses in the crystal. The effective Li diffusion was analyzed in terms of the dynamics and polarizability of the sulfur surrounding the Li migration path. High flexibility and large anisotropic polarizability were the characteristics identified as necessary for the formation of an effective Li migration path. These findings provide principles for understanding Li conduction in solid-state electrolytes.

Characterization of ceria electrolyte in solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Milliken, Christopher Edward

The goal of this research effort is to characterize cation doped cerium dioxide for use as an electrolyte material in solid oxide fuel cell applications. A variety of analytical techniques including thermogravimetric analysis, controlled atmosphere dilatometry, and AC/DC electronic measurements on single cells and stacks have been coupled with thermodynamic calculations to evaluate the suitability of several doping schemes. The results of this analysis indicate that doping CeOsb2 with 20% SmOsb{1.5} or codoping with 19% GdOsb{1.5} + 1% PrOsb{1.83} provides the best combination of stability and performance. Under dual atmosphere fuel cell conditions, these dopants do not provide sufficient stabilization energy to prevent the reduction of ceria. A significant oxygen leakage current can be expected, particularly near open circuit conditions. Incorporation of 10% SrO provides similar short-term advantages to the lanthanide doped system but this electrolyte material undergoes an irreversible degradation mechanism that results in cell failure within 1500 hours of test. Under fuel cell conditions, the maximum efficiency of such systems in stacks will be below 40% at 200 mW/cmsp2 when operated on humidified hydrogen fuels. This compares to an expected efficiency of 45-50% at a similar power density for nonmixed conducting electrolyte (e.g., YSZ).

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials.

PubMed

Ma, Ya; Cui, Yan; Zuo, Xiaoxi; Huang, Shanna; Hu, Keshui; Xiao, Xin; Nan, Junmin

2014-10-01

A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn-Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organic separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H2SO4 (2 mol L(-1)) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ⩾99.8% is recovered in an electrolytic cell with a cathode efficiency of ⩾85% under the conditions of 37-40°C and 300 A m(-2). The most of MnO2 and a small quantity of electrolytic MnO2 are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi0.5Mn1.5O4 material of lithium-ion battery. The as-synthesized LiNi0.5Mn1.5O4 discharges 118.3 mAh g(-1) capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO2. This process can recover the substances in the spent Zn-Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable. Copyright © 2014 Elsevier Ltd. All rights reserved.

The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling

DOE PAGES

An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

2016-04-09

An in-depth review is presented on the science of lithium-ion battery (LIB) solid electrolyte interphase (SEI) formation on the graphite anode, including structure, morphology, chemical composition, electrochemistry, formation mechanism, and LIB formation cycling. During initial operation of LIBs, the SEI layer forms on the graphite surfaces, the most commonly used anode material, due to side reactions with the electrolyte solvent/salt at low electro-reduction potentials. It is accepted that the SEI layer is essential to the long-term performance of LIBs, and it also has an impact on its initial capacity loss, self-discharge characteristics, cycle life, rate capability, and safety. While themore » presence of the anode SEI layer is vital, it is difficult to control its formation and growth, as the chemical composition, morphology, and stability depend on several factors. These factors include the type of graphite, electrolyte composition, electrochemical conditions, and cell temperature. Thus, SEI layer formation and electrochemical stability over long-term operation should be a primary topic of future investigation in the development of LIB technology. We review the progression of knowledge gained about the anode SEI, from its discovery in 1979 to the current state of understanding, and covers its formation process, differences in the chemical and structural makeup when cell materials and components are varied, methods of characterization, and associated reactions with the liquid electrolyte phase. It also discusses the relationship of the SEI layer to the LIB formation step, which involves both electrolyte wetting and subsequent slow charge-discharge cycles to grow the SEI.« less

Oxide-Based Composite Electrolytes Using Na3Zr2Si2PO12/Na3PS4 Interfacial Ion Transfer.

PubMed

Noi, Kousuke; Nagata, Yuka; Hakari, Takashi; Suzuki, Kenji; Yubuchi, So; Ito, Yusuke; Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro

2018-05-31

All-solid-state sodium batteries using Na 3 Zr 2 Si 2 PO 12 (NASICON) solid electrolytes are promising candidates for safe and low-cost advanced rechargeable battery systems. Although NASICON electrolytes have intrinsically high sodium-ion conductivities, their high sintering temperatures interfere with the immediate development of high-performance batteries. In this work, sintering-free NASICON-based composites with Na 3 PS 4 (NPS) glass ceramics were prepared to combine the high grain-bulk conductivity of NASICON and the interfacial formation ability of NPS. Before the composite preparation, the NASICON/NPS interfacial resistance was investigated by modeling the interface between the NASICON sintered ceramic and the NPS glass thin film. The interfacial ion-transfer resistance was very small above room temperature; the area-specific resistances at 25 and 100 °C were 15.8 and 0.40 Ω cm 2 , respectively. On the basis of this smooth ion transfer, NASICON-rich (70-90 wt %) NASICON-NPS composite powders were prepared by ball-milling fine powders of each component. The composite powders were well-densified by pressing at room temperature. Scanning electron microscopy observation showed highly dispersed sub-micrometer NASICON grains in a dense NPS matrix to form closed interfaces between the oxide and sulfide solid electrolytes. The composite green (unfired) compacts with 70 and 80 wt % NASICON exhibited high total conductivities at 100 °C of 1.1 × 10 -3 and 6.8 × 10 -4 S cm -1 , respectively. An all-solid-state Na 15 Sn 4 /TiS 2 cell was constructed using the 70 wt % NASICON composite electrolyte by the uniaxial pressing of the powder materials, and its discharge properties were evaluated at 100 °C. The cell showed the reversible capacities of about 120 mAh g -1 under the current density of 640 μA cm -2 . The prepared oxide-based composite electrolytes were thus successfully applied in all-solid-state sodium rechargeable batteries without sintering.

Graphene nanocomposites for electrochemical cell electrodes

DOEpatents

Zhamu, Aruna; Jang, Bor Z.; Shi, Jinjun

2015-11-19

A composite composition for electrochemical cell electrode applications, the composition comprising multiple solid particles, wherein (a) a solid particle is composed of graphene platelets dispersed in or bonded by a first matrix or binder material, wherein the graphene platelets are not obtained from graphitization of the first binder or matrix material; (b) the graphene platelets have a length or width in the range of 10 nm to 10 .mu.m; (c) the multiple solid particles are bonded by a second binder material; and (d) the first or second binder material is selected from a polymer, polymeric carbon, amorphous carbon, metal, glass, ceramic, oxide, organic material, or a combination thereof. For a lithium ion battery anode application, the first binder or matrix material is preferably amorphous carbon or polymeric carbon. Such a composite composition provides a high anode capacity and good cycling response. For a supercapacitor electrode application, the solid particles preferably have meso-scale pores therein to accommodate electrolyte.

Is alpha-V 2O 5 a cathode material for Mg insertion batteries?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sa, Niya; Wang, Hao; Proffit, Danielle L.

When designing a high energy density battery, one of the critical features is a high voltage, high capacity cathode material. In the development of Mg batteries, oxide cathodes that can reversibly intercalate Mg, while at the same time being compatible with an electrolyte that can deposit Mg reversibly are rare. Herein, we report the compatibility of Mg anodes with a-V 2O 5 by employing magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolytes at very low water levels. Electrolytes that contain a high water level do not reversibly deposit Mg, but interestingly these electrolytes appear to enable much higher capacities for an a-Vmore » 2O 5 cathode. Solid state NMR indicates that the major source of the higher capacity in high water content electrolytes originates from reversible proton insertion. In contrast, we found that lowering the water level of the magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolyte is critical to achieve reversible Mg deposition and direct evidence for reversible Mg intercalation is shown. Findings we report here elucidate the role of proton intercalation in water-containing electrolytes and clarify numerous conflicting reports of Mg insertion into a-V 2O 5.« less

Li 2OHCl crystalline electrolyte for stable metallic lithium anodes

DOE PAGES

Hood, Zachary D.; Wang, Hui; Samuthira Pandian, Amaresh; ...

2016-01-22

In a classic example of stability from instability, we show that Li 2OHCl solid electrolyte forms a stable solid electrolyte interface (SEI) with metallic lithium anode. The Li 2OHCl solid electrolyte can be readily achieved through simple mixing of air-stable LiOH and LiCl precursors with a mild processing temperature under 400 °C. Additionally, we show that continuous, dense Li 2OHCl membranes can be fabricated at temperatures less than 400 °C, standing in great contrast to current processing temperatures of over 1600 °C for most oxide-based solid electrolytes. The ionic conductivity and Arrhenius activation energy were explored for the LiOH-LiCl systemmore » of crystalline solid electrolytes where Li 2OHCl with increased crystal defects was found to have the highest ionic conductivity and reasonable Arrhenius activation energy. The Li 2OHCl solid electrolyte displays stability against metallic lithium, even in extreme conditions past the melting point of lithium metal. Furthermore, to understand this excellent stability, we show that SEI formation is critical in stabilizing the interface between metallic lithium and the Li 2OHCl solid electrolyte.« less

Method of synthesizing polymers from a solid electrolyte

DOEpatents

Skotheim, Terje A.

1985-01-01

A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte wherein an assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

Method of synthesizing polymers from a solid electrolyte

DOEpatents

Skotheim, T.A.

1984-10-19

A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte is disclosed. An assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

Performance comparison: Aluminum electrolytic and solid tantalum capacitor

NASA Technical Reports Server (NTRS)

Hawthornthwaite, B. G.; Piper, J.; Holland, H. W.

1981-01-01

Several key electrical and environmental parameters of latest technology aluminum electrolytic and solid tantalum capacitors were evaluated in terms of price fluctuations of tantalum metal. Performance differences between solid tantalums and aluminum electrolytics are examined.

A zwitterionic gel electrolyte for efficient solid-state supercapacitors

PubMed Central

Peng, Xu; Liu, Huili; Yin, Qin; Wu, Junchi; Chen, Pengzuo; Zhang, Guangzhao; Liu, Guangming; Wu, Changzheng; Xie, Yi

2016-01-01

Gel electrolytes have attracted increasing attention for solid-state supercapacitors. An ideal gel electrolyte usually requires a combination of advantages of high ion migration rate, reasonable mechanical strength and robust water retention ability at the solid state for ensuring excellent work durability. Here we report a zwitterionic gel electrolyte that successfully brings the synergic advantages of robust water retention ability and ion migration channels, manifesting in superior electrochemical performance. When applying the zwitterionic gel electrolyte, our graphene-based solid-state supercapacitor reaches a volume capacitance of 300.8 F cm−3 at 0.8 A cm−3 with a rate capacity of only 14.9% capacitance loss as the current density increases from 0.8 to 20 A cm−3, representing the best value among the previously reported graphene-based solid-state supercapacitors, to the best of our knowledge. We anticipate that zwitterionic gel electrolyte may be developed as a gel electrolyte in solid-state supercapacitors. PMID:27225484

Oxygen partial pressure sensor

DOEpatents

Dees, D.W.

1994-09-06

A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured. 1 fig.

Oxygen partial pressure sensor

DOEpatents

Dees, Dennis W.

1994-01-01

A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured.

3D Fiber-Network-Reinforced Bicontinuous Composite Solid Electrolyte for Dendrite-free Lithium Metal Batteries.

PubMed

Li, Dan; Chen, Long; Wang, Tianshi; Fan, Li-Zhen

2018-02-28

Replacement of flammable organic liquid electrolytes with solid Li + conductors is a promising approach to realize excellent performance of Li metal batteries. However, ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites through their grain boundaries, and polymer electrolytes are also faced with instability on the electrode/electrolyte interface and weak mechanical property. Here, we report a three-dimensional fiber-network-reinforced bicontinuous solid composite electrolyte with flexible Li + -conductive network (lithium aluminum titanium phosphate (LATP)/polyacrylonitrile), which helps to enhance electrochemical stability on the electrode/electrolyte interface by isolating Li and LATP and suppress Li dendrites growth by mechanical reinforcement of fiber network for the composite solid electrolyte. The composite electrolyte shows an excellent electrochemical stability after 15 days of contact with Li metal and has an enlarged tensile strength (10.72 MPa) compared to the pure poly(ethylene oxide)-bistrifluoromethanesulfonimide lithium salt electrolyte, leading to a long-term stability and safety of the Li symmetric battery with a current density of 0.3 mA cm -2 for 400 h. In addition, the composite electrolyte also shows good electrochemical and thermal stability. These results provide such fiber-reinforced membranes that present stable electrode/electrolyte interface and suppress lithium dendrite growth for high-safety all-solid-state Li metal batteries.

Enhanced ionic conductivity with Li 7O 2Br 3 phase in Li 3OBr anti-perovskite solid electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jinlong; Li, Shuai; Zhang, Yi

Cubic anti-perovskites with general formula Li 3OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li 3OBr and layered Li 7O 2Br 3, by solid state reaction routes. The results indicate that with the phase fraction of Li 7O 2Br 3 increasingmore » to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li 3OBr. Formation energy calculations revealed the meta-stable nature of Li 7O 2Br 3, which supports the great difficulty in producing phase-pure Li 7O 2Br 3 at ambient pressure. Here, methods of obtaining phase-pure Li 7O 2Br 3 will continue to be explored, including both high pressure and metathesis techniques.« less

Enhanced ionic conductivity with Li 7O 2Br 3 phase in Li 3OBr anti-perovskite solid electrolyte

DOE PAGES

Zhu, Jinlong; Li, Shuai; Zhang, Yi; ...

2016-09-07

Cubic anti-perovskites with general formula Li 3OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li 3OBr and layered Li 7O 2Br 3, by solid state reaction routes. The results indicate that with the phase fraction of Li 7O 2Br 3 increasingmore » to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li 3OBr. Formation energy calculations revealed the meta-stable nature of Li 7O 2Br 3, which supports the great difficulty in producing phase-pure Li 7O 2Br 3 at ambient pressure. Here, methods of obtaining phase-pure Li 7O 2Br 3 will continue to be explored, including both high pressure and metathesis techniques.« less

Theoretical Design and Experimental Evaluation of Molten Carbonate Modified LSM Cathode for Low Temperature Solid Oxide Fuel Cells

DTIC Science & Technology

2015-01-07

Min Lee, Kevin Huang. Mixed Oxide-Ion and Carbonate-Ion Conductors (MOCCs) as Electrolyte Materials for Solid Oxide Fuel Cells, 218th ECS Meeting... Solid Oxide Fuel Cells The views, opinions and/or findings contained in this report are those of the author(s) and should not contrued as an official...ES) U.S. Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 Solid Oxide Fuel Cell, Oxygen Reduction, Molten Carbonate

Ultrastable Photoelectrodes for Solar Water Splitting Based on Organic Metal Halide Perovskite Fabricated by Lift-Off Process.

PubMed

Nam, SeongSik; Mai, Cuc Thi Kim; Oh, Ilwhan

2018-05-02

Herein, we report an integrated photoelectrolysis of water employing organic metal halide (OMH) perovskite material. As generic OMH perovskite material and device architecture are highly susceptible to degradation by aqueous electrolytes, we have developed a versatile mold-cast and lift-off process to fabricate and assemble multipurpose metal encapsulation onto perovskite devices. With the metal encapsulation effectively protecting the perovskite cell and also functioning as electrocatalyst, the high-performance perovskite photoelectrodes exhibit high photovoltage and photocurrent that are effectively inherited from the original solid-state solar cell. More importantly, thus-fabricated perovskite photoelectrode demonstrates record-long unprecedented stability even at highly oxidizing potential in strong alkaline electrolyte. We expect that this versatile lift-off process can be adapted in a wide variety of photoelectrochemical devices to protect the material surfaces from corroding electrolyte and facilitate various electrochemical reactions.

Structures and fabrication techniques for solid state electrochemical devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2012-10-09

Porous substrates and associated structures for solid-state electrochemical devices, such as solid-oxide fuel cells (SOFCs), are low-cost, mechanically strong and highly electronically conductive. Some preferred structures have a thin layer of an electrocatalytically active material (e.g., Ni--YSZ) coating a porous high-strength alloy support (e.g., SS-430) to form a porous SOFC fuel electrode. Electrode/electrolyte structures can be formed by co-firing or constrained sintering processes.

Structures and fabrication techniques for solid state electrochemical devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2008-04-01

Porous substrates and associated structures for solid-state electrochemical devices, such as solid-oxide fuel cells (SOFCs), are low-cost, mechanically strong and highly electronically conductive. Some preferred structures have a thin layer of an electrocatalytically active material (e.g., Ni--YSZ) coating a porous high-strength alloy support (e.g., SS-430) to form a porous SOFC fuel electrode. Electrode/electrolyte structures can be formed by co-firing or constrained sintering processes.

Influence of carbon nanotubes on the optical properties of plasticized solid polymer electrolytes

NASA Astrophysics Data System (ADS)

Ibrahim, Suriani; Yasin, Siti Mariah Mohd; Johan, Mohd Rafie

2013-07-01

Polyethylene oxide (PEO) based solid polymer electrolyte films complexed with lithium hexafluorophosphate (LiPF6), ethylene carbonate (EC) and carbon nanotubes (CNTs) are prepared by solution-casting technique. The complexation of doping materials with polymer is confirmed by X-ray diffraction and infrared studies. The incorporation of LiPF6, EC and CNTs into the host polymer shows a significant increase in conductivity of 10-10 and 10-3 S cm-1. The optical properties such as direct and indirect band gaps are investigated for pure and doped polymer films within a wavelength range of 200-400 nm. It is found that the energy gaps and band edge values shift towards lower energies upon doping. It is shown that LiPF6, EC and CNTs are responsible for the formation of defects in polymer electrolytes, which increases the degree of disorder in the films.

A highly reversible room-temperature sodium metal anode

DOE PAGES

Seh, Zhi Wei; Sun, Jie; Sun, Yongming; ...

2015-11-02

Owing to its low cost and high natural abundance, sodium metal is among the most promising anode materials for energy storage technologies beyond lithium ion batteries. However, room-temperature sodium metal anodes suffer from poor reversibility during long-term plating and stripping, mainly due to formation of nonuniform solid electrolyte interphase as well as dendritic growth of sodium metal. Herein we report for the first time that a simple liquid electrolyte, sodium hexafluorophosphate in glymes (mono-, di-, and tetraglyme), can enable highly reversible and nondendritic plating–stripping of sodium metal anodes at room temperature. High average Coulombic efficiencies of 99.9% were achieved overmore » 300 plating–stripping cycles at 0.5 mA cm –2. In this study, the long-term reversibility was found to arise from the formation of a uniform, inorganic solid electrolyte interphase made of sodium oxide and sodium fluoride, which is highly impermeable to electrolyte solvent and conducive to nondendritic growth. As a proof of concept, we also demonstrate a room-temperature sodium–sulfur battery using this class of electrolytes, paving the way for the development of next-generation, sodium-based energy storage technologies.« less

Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

DOEpatents

Sharp, Donald J.; Armstrong, Pamela S.; Panitz, Janda Kirk G.

1998-01-01

A solid electrolytic capacitor having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects.

Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

DOEpatents

Sharp, D.J.; Armstrong, P.S.; Panitz, J.K.G.

1998-03-17

A solid electrolytic capacitor is described having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects. 2 figs.

Fuel cells with solid polymer electrolyte and their application on vehicles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fateev, V.

1996-04-01

In Russia, solid polymer electrolyte MF-4-SK has been developed for fuel cells. This electrolyte is based on perfluorinated polymer with functional sulfogroups. Investigations on electrolyte properties and electrocatalysts have been carried out.

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

PubMed Central

Liu, Yayuan; Lin, Dingchang; Jin, Yang; Liu, Kai; Tao, Xinyong; Zhang, Qiuhong; Zhang, Xiaokun; Cui, Yi

2017-01-01

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellent adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g−1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm−2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature. PMID:29062894

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yayuan; Lin, Dingchang; Jin, Yang

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellentmore » adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g -1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm -2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature.« less

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

DOE PAGES

Liu, Yayuan; Lin, Dingchang; Jin, Yang; ...

2017-10-01

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellentmore » adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g -1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm -2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature.« less

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range

NASA Astrophysics Data System (ADS)

Kitaura, Hirokazu; Zhou, Haoshen

2015-08-01

There is need to develop high energy storage devices with high safety to satisfy the growing industrial demands. Here, we show the potential to realize such batteries by assembling a lithium-oxygen cell using an inorganic solid electrolyte without any flammable liquid or polymer materials. The lithium-oxygen battery using Li1.575Al0.5Ge1.5(PO4)3 solid electrolyte was examined in the pure oxygen atmosphere from room temperature to 120 °C. The cell works at room temperature and first full discharge capacity of 1420 mAh g-1 at 10 mA g-1 (based on the mass of carbon material in the air electrode) was obtained. The charge curve started from 3.0 V, and that the majority of it lay below 4.2 V. The cell also safely works at high temperature over 80 °C with the improved battery performance. Furthermore, fundamental data of the electrochemical performance, such as cyclic voltammogram, cycle performance and rate performance was obtained and this work demonstrated the potential of the all-solid-state lithium-oxygen battery for wide temperature application as a first step.

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range

PubMed Central

Kitaura, Hirokazu; Zhou, Haoshen

2015-01-01

There is need to develop high energy storage devices with high safety to satisfy the growing industrial demands. Here, we show the potential to realize such batteries by assembling a lithium-oxygen cell using an inorganic solid electrolyte without any flammable liquid or polymer materials. The lithium-oxygen battery using Li1.575Al0.5Ge1.5(PO4)3 solid electrolyte was examined in the pure oxygen atmosphere from room temperature to 120 °C. The cell works at room temperature and first full discharge capacity of 1420 mAh g−1 at 10 mA g−1 (based on the mass of carbon material in the air electrode) was obtained. The charge curve started from 3.0 V, and that the majority of it lay below 4.2 V. The cell also safely works at high temperature over 80 °C with the improved battery performance. Furthermore, fundamental data of the electrochemical performance, such as cyclic voltammogram, cycle performance and rate performance was obtained and this work demonstrated the potential of the all-solid-state lithium-oxygen battery for wide temperature application as a first step. PMID:26293134

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range.

PubMed

Kitaura, Hirokazu; Zhou, Haoshen

2015-08-21

There is need to develop high energy storage devices with high safety to satisfy the growing industrial demands. Here, we show the potential to realize such batteries by assembling a lithium-oxygen cell using an inorganic solid electrolyte without any flammable liquid or polymer materials. The lithium-oxygen battery using Li1.575Al0.5Ge1.5(PO4)3 solid electrolyte was examined in the pure oxygen atmosphere from room temperature to 120 °C. The cell works at room temperature and first full discharge capacity of 1420 mAh g(-1) at 10 mA g(-1) (based on the mass of carbon material in the air electrode) was obtained. The charge curve started from 3.0 V, and that the majority of it lay below 4.2 V. The cell also safely works at high temperature over 80 °C with the improved battery performance. Furthermore, fundamental data of the electrochemical performance, such as cyclic voltammogram, cycle performance and rate performance was obtained and this work demonstrated the potential of the all-solid-state lithium-oxygen battery for wide temperature application as a first step.

Lithium-Sulfur Batteries: from Liquid to Solid Cells?

DOE PAGES

Lin, Zhan; Liang, Chengdu

2014-11-11

Lithium-sulfur (Li-S) batteries supply a theoretical specific energy 5 times higher than that of lithium-ion batteries (2,500 vs. ~500 Wh kg-1). However, the insulating properties and polysulfide shuttle effects of the sulfur cathode and the safety concerns of the lithium anode in liquid electrolytes are still key limitations to practical use of traditional Li-S batteries. In this review, we start with a brief discussion on fundamentals of Li-S batteries and key challenges associated with the conventional liquid cells. Then, we introduce the most recent progresses in the liquid systems, including the sulfur positive electrodes, the lithium negative electrodes, and themore » electrolytes and binders. We discuss the significance of investigating electrode reaction mechanisms in liquid cells using in-situ techniques to monitor the compositional and morphological changes. By moving from the traditional liquid cells to recent solid cells, we discuss the importance of this game-changing shift with positive advances in both solid electrolytes and electrode materials. Finally, the opportunities and perspectives for future research on Li-S batteries are presented.« less

Solid oxide fuel cell operable over wide temperature range

DOEpatents

Baozhen, Li; Ruka, Roswell J.; Singhal, Subhash C.

2001-01-01

Solid oxide fuel cells having improved low-temperature operation are disclosed. In one embodiment, an interfacial layer of terbia-stabilized zirconia is located between the air electrode and electrolyte of the solid oxide fuel cell. The interfacial layer provides a barrier which controls interaction between the air electrode and electrolyte. The interfacial layer also reduces polarization loss through the reduction of the air electrode/electrolyte interfacial electrical resistance. In another embodiment, the solid oxide fuel cell comprises a scandia-stabilized zirconia electrolyte having high electrical conductivity. The scandia-stabilized zirconia electrolyte may be provided as a very thin layer in order to reduce resistance. The scandia-stabilized electrolyte is preferably used in combination with the terbia-stabilized interfacial layer. The solid oxide fuel cells are operable over wider temperature ranges and wider temperature gradients in comparison with conventional fuel cells.

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2016-07-05

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at least 5 mAh/cm.sup.2 at a C-rate of C/2.

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2015-11-10

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at least 5 mAh/cm.sup.2 at a C-rate of C/2.

Principles and Applications of Solid Polymer Electrolyte Reactors for Electrochemical Hydrodehalogenation of Organic Pollutants

NASA Astrophysics Data System (ADS)

Cheng, Hua; Scott, Keith

The ability to re-cycle halogenated liquid wastes, based on electrochemical hydrodehalogenation (EHDH), will provide a significant economic advantage and will reduce the environmental burden in a number of processes. The use of a solid polymer electrolyte (SPE) reactor is very attractive for this purpose. Principles and features of electrochemical HDH technology and SPE EHDH reactors are described. The SPE reactor enables selective dehalogenation of halogenated organic compounds in both aqueous and non-aqueous media with high current efficiency and low energy consumption. The influence of operating conditions, including cathode material, current density, reactant concentration and temperature on the HDH process and its stability are examined.

Electrode-Electrolyte Interfaces in Lithium-Sulfur Batteries with Liquid or Inorganic Solid Electrolytes.

PubMed

Yu, Xingwen; Manthiram, Arumugam

2017-11-21

Electrode-electrolyte interfacial properties play a vital role in the cycling performance of lithium-sulfur (Li-S) batteries. The issues at an electrode-electrolyte interface include electrochemical and chemical reactions occurring at the interface, formation mechanism of interfacial layers, compositional/structural characteristics of the interfacial layers, ionic transport across the interface, and thermodynamic and kinetic behaviors at the interface. Understanding the above critical issues is paramount for the development of strategies to enhance the overall performance of Li-S batteries. Liquid electrolytes commonly used in Li-S batteries bear resemblance to those employed in traditional lithium-ion batteries, which are generally composed of a lithium salt dissolved in a solvent matrix. However, due to a series of unique features associated with sulfur or polysulfides, ether-based solvents are generally employed in Li-S batteries rather than simply adopting the carbonate-type solvents that are generally used in the traditional Li + -ion batteries. In addition, the electrolytes of Li-S batteries usually comprise an important additive, LiNO 3 . The unique electrolyte components of Li-S batteries do not allow us to directly take the interfacial theories of the traditional Li + -ion batteries and apply them to Li-S batteries. On the other hand, during charging/discharging a Li-S battery, the dissolved polysulfide species migrate through the battery separator and react with the Li anode, which magnifies the complexity of the interfacial problems of Li-S batteries. However, current Li-S battery development paths have primarily been energized by advances in sulfur cathodes. Insight into the electrode-electrolyte interfacial behaviors has relatively been overshadowed. In this Account, we first examine the state-of-the-art contributions in understanding the solid-electrolyte interphase (SEI) formed on the Li-metal anode and sulfur cathode in conventional liquid-electrolyte Li-S batteries and how the resulting chemical and physical properties of the SEI affect the overall battery performance. A few strategies recently proposed for improving the stability of SEI are briefly summarized. Solid Li + -ion conductive electrolytes have been attempted for the development of Li-S batteries to eliminate the polysulfide shuttle issues. One approach is based on a concept of "all-solid-state Li-S battery," in which all the cell components are in the solid state. Another approach is based on a "hybrid-electrolyte Li-S battery" concept, in which the solid electrolyte plays roles both as a Li + -ion conductor for the electrochemical reaction and as a separator to prevent polysulfide shuttle. However, these endeavors with the solid electrolyte are not able to provide an overall satisfactory cell performance. In addition to the low ionic conductivity of solid-state electrolytes, a critical issue lies in the poor interfacial properties between the electrode and the solid electrolyte. This Account provides a survey of the relevant research progress in understanding and manipulating the interfaces of electrode and solid electrolytes in both the "all-solid-state Li-S batteries" and the "hybrid-electrolyte Li-S batteries". A recently proposed "semi-solid-state Li-S battery" concept is also briefly discussed. Finally, future research and development directions in all the above areas are suggested.

Review on solid electrolytes for all-solid-state lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zheng, Feng; Kotobuki, Masashi; Song, Shufeng; Lai, Man On; Lu, Li

2018-06-01

All-solid-state (ASS) lithium-ion battery has attracted great attention due to its high safety and increased energy density. One of key components in the ASS battery (ASSB) is solid electrolyte that determines performance of the ASSB. Many types of solid electrolytes have been investigated in great detail in the past years, including NASICON-type, garnet-type, perovskite-type, LISICON-type, LiPON-type, Li3N-type, sulfide-type, argyrodite-type, anti-perovskite-type and many more. This paper aims to provide comprehensive reviews on some typical types of key solid electrolytes and some ASSBs, and on gaps that should be resolved.

Room-Temperature Performance of Poly(Ethylene Ether Carbonate)-Based Solid Polymer Electrolytes for All-Solid-State Lithium Batteries.

PubMed

Jung, Yun-Chae; Park, Myung-Soo; Kim, Duck-Hyun; Ue, Makoto; Eftekhari, Ali; Kim, Dong-Won

2017-12-13

Amorphous poly(ethylene ether carbonate) (PEEC), which is a copolymer of ethylene oxide and ethylene carbonate, was synthesized by ring-opening polymerization of ethylene carbonate. This route overcame the common issue of low conductivity of poly(ethylene oxide)(PEO)-based solid polymer electrolytes at low temperatures, and thus the solid polymer electrolyte could be successfully employed at the room temperature. Introducing the ethylene carbonate units into PEEC improved the ionic conductivity, electrochemical stability and lithium transference number compared with PEO. A cross-linked solid polymer electrolyte was synthesized by photo cross-linking reaction using PEEC and tetraethyleneglycol diacrylate as a cross-linking agent, in the form of a flexible thin film. The solid-state Li/LiNi 0.6 Co 0.2 Mn 0.2 O 2 cell assembled with solid polymer electrolyte based on cross-linked PEEC delivered a high initial discharge capacity of 141.4 mAh g -1 and exhibited good capacity retention at room temperature. These results demonstrate the feasibility of using this solid polymer electrolyte in all-solid-state lithium batteries that can operate at ambient temperatures.

Symposium Report. Battery materials : amorphous carbons and polymer electrolytes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerald, R. E., II; Chemical Engineering

2000-01-01

The motivation for research in battery materials lies in the expanding consumer demand for compact, high-energy density power sources for portable electronic devices, and environmental issues such as global warming and air pollution that have provided the impetus for mass transportation by electric vehicles. The Battery Materials Symposium, chaired by Jacqueline Johnson (ANL), focused on three topics: the structure and electrochemical properties of new and existing electrolytes, devices for fabricating and investigating thin films, and large-scale computer simulations. The symposium opened with a presentation by the author on a recently invented device for in situ investigations of batteries using nuclearmore » magnetic resonance. Joop Schoonman (Delft University) described several methods for preparing and analyzing thin films made of solid electrolytes. These methods included chemical vapor deposition, electrostatic spray deposition and the Solufill process. Aiichiro Nakano discussed large-scale (10 million to 2 billion atoms) computer simulations of polymer and ceramic systems. An overview was given of a DOE Cooperative Research 2000 program, in the initial stages, that was set up to pursue these atomistic simulations. Doug MacFarlane (Monash University) described conductive plastic crystals based on pyrrolidinium imides. Joseph Pluth (U of Chicago) presented his recent crystallographic studies of Pb compounds found in the ubiquitous lead-acid battery. He showed the structures of tribasic lead sulfate and tetrabasic lead sulfate. Austen Angell (Arizona State Univ.) discussed the general problem of electrolyte polarization in Li-ion battery systems with cation transference numbers less than unity. Steven Greenbaum (Hunter College) provided an introduction of NMR interactions that are useful for investigations of lithium-ion battery materials. Analysis by NMR is nuclear specific, probes local environments and dynamics, and is non-destructive. He discussed {sup 7}Li NMR results of a solid electrolyte system composed of LiI dissolved in PEO. Work on oriented polymer electrolyte samples is ongoing. Yuri Andreev (U. of St. Andrews) gave a historical overview of a number of crystal structures of polymer electrolytes solved using XRD in the group of Peter Bruce. The last speaker of the symposium was Peter Papanek (U. of Pennsylvania). He spoke about various disordered carbon materials used as anodes in Li-ion batteries. He also described his inelastic neutron scattering studies of carbon materials derived from pyrolyzed epoxy novolak resins. His data supports the graphene sheet model and is also consistent with calculations of interior and edge carbon atoms in pyrene that chemically reacted with lithium.« less

High temperature solid state storage cell

DOEpatents

Rea, Jesse R.; Kallianidis, Milton; Kelsey, G. Stephen

1983-01-01

A completely solid state high temperature storage cell comprised of a solid rechargeable cathode such as TiS.sub.2, a solid electrolyte which remains solid at the high temperature operating conditions of the cell and which exhibits high ionic conductivity at such elevated temperatures such as an electrolyte comprised of lithium iodide, and a solid lithium or other alkali metal alloy anode (such as a lithium-silicon alloy) with 5-50% by weight of said anode being comprised of said solid electrolyte.

Optimized performance of quasi-solid-state DSSC with PEO-bismaleimide polymer blend electrolytes filled with a novel procedure.

PubMed

Lee, Dong Ha; Sun, Kyung Chul; Qadir, Muhammad Bilal; Jeong, Sung Hoon

2014-12-01

Dye-sensitized solar cell (DSSC) is an attractive renewable energy technology currently under intense investigation. Electrolyte plays an important role in the photovoltaic performance of the DSSCs and many efforts have been contributed to study different kinds of electrolytes with various characteristics such as liquid electrolytes, polymer electrolytes and so on. In this study, DSSC is developed by using quasi-solid electrolyte and a novel procedure is adopted for filling this electrolyte. The quasi-solid-state electrolyte was prepared by mixing Poly ethylene oxide (PEO) and bismaleimide together and constitution was taken as PEO (15 wt%) at various bismaleimide concentrations (1, 3, 5 wt%). The novel procedure of filling electrolyte consists of three major steps (first step: filling liquid electrolyte, second step: vaporization of liquid electrolyte, third step: refilling quasi-solid-state electrolyte). The electrochemical and photovoltaic performances of DSSCs with these electrolytes were also investigated. The electrochemical impedance spectroscopy (EIS) indicated that TiO2/Dye/electrolyte impedance is reduced and electron lifetime is increased, and consequently efficiency of cell has been improved after using this novel procedure. The photovoltaic power conversion efficiency of 6.39% has been achieved under AM 1.5 simulated sunlight (100 W/cm2) through this novel procedure and by using specified blend of polymers.

Electrolyte for batteries with regenerative solid electrolyte interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Jie; Lu, Dongping; Shao, Yuyan

2017-08-01

An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature.

PubMed

Miara, Lincoln; Windmüller, Anna; Tsai, Chih-Long; Richards, William D; Ma, Qianli; Uhlenbruck, Sven; Guillon, Olivier; Ceder, Gerbrand

2016-10-12

The reactivity of mixtures of high voltage spinel cathode materials Li 2 NiMn 3 O 8 , Li 2 FeMn 3 O 8 , and LiCoMnO 4 cosintered with Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 and Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li 2 MnO 3 and then decompose to form stable and often insulating phases such as La 2 Zr 2 O 7 , La 2 O 3 , La 3 TaO 7 , TiO 2 , and LaMnO 3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 mixtures, the Mn tends to oxidize to MnO 2 or Mn 2 O 3 , supplying lithium to the electrolyte for the formation of Li 3 PO 4 and metal phosphates such as AlPO 4 and LiMPO 4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.

New Solid Polymer Electrolytes for Improved Lithium Batteries

NASA Technical Reports Server (NTRS)

Hehemann, David G.

2002-01-01

The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

Vertically Aligned and Continuous Nanoscale Ceramic-Polymer Interfaces in Composite Solid Polymer Electrolytes for Enhanced Ionic Conductivity.

PubMed

Zhang, Xiaokun; Xie, Jin; Shi, Feifei; Lin, Dingchang; Liu, Yayuan; Liu, Wei; Pei, Allen; Gong, Yongji; Wang, Hongxia; Liu, Kai; Xiang, Yong; Cui, Yi

2018-06-13

Among all solid electrolytes, composite solid polymer electrolytes, comprised of polymer matrix and ceramic fillers, garner great interest due to the enhancement of ionic conductivity and mechanical properties derived from ceramic-polymer interactions. Here, we report a composite electrolyte with densely packed, vertically aligned, and continuous nanoscale ceramic-polymer interfaces, using surface-modified anodized aluminum oxide as the ceramic scaffold and poly(ethylene oxide) as the polymer matrix. The fast Li + transport along the ceramic-polymer interfaces was proven experimentally for the first time, and an interfacial ionic conductivity higher than 10 -3 S/cm at 0 °C was predicted. The presented composite solid electrolyte achieved an ionic conductivity as high as 5.82 × 10 -4 S/cm at the electrode level. The vertically aligned interfacial structure in the composite electrolytes enables the viable application of the composite solid electrolyte with superior ionic conductivity and high hardness, allowing Li-Li cells to be cycled at a small polarization without Li dendrite penetration.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kazyak, Eric; Chen, Kuan-Hung; Wood, Kevin N.

Lithium solid electrolytes are a promising platform for achieving high energy density, long-lasting, and safe rechargeable batteries, which could have widespread societal impact. In particular, the ceramic oxide garnet Li7La3Zr2O12 (LLZO) has been shown to be a promising electrolyte due to its stability and high ionic conductivity. Two major challenges for commercialization are manufacturing of thin layers and creating stable, low-impedance, interfaces with both anode and cathode materials. Atomic Layer Deposition (ALD) has recently been shown as a potential method for depositing both solid electrolytes and interfacial layers to improve the stability and performance at electrode-electrolyte interfaces in battery systems.more » Herein we present the first reported ALD process for LLZO, demonstrating the ability to tune composition within the amorphous film and anneal to achieve the desired cubic garnet phase. Formation of the cubic phase was observed at temperatures as low as 555°C, significantly lower than is required for bulk processing. Additionally, challenges associated with achieving a dense garnet phase due to substrate reactivity, morphology changes and Li loss under the necessary high temperature annealing are quantified via in situ synchrotron diffraction.« less

Electrolytic pretreatment unit gaseous effluent conditioning

NASA Technical Reports Server (NTRS)

Colombo, G. V.; Putnam, D. F.

1976-01-01

The electrolytic pretreatment of urine is an advanced process that eliminates the need for handling and storing the highly corrosive chemicals that are normally used in water reclamation systems. The electrolytic pretreatment process also converts the organic materials in urine to gases (N2 and O2) that can be used to replenish those lost to space by leakage, venting, and air lock operations. The electrolytic process is more than a pretreatment, since it decreases the urine solids content by approximately one third, thus reducing the load and eventual solids storage requirements of the urine processing system. The evolved gases from the pretreatment step cannot, however, be returned directly to the atmosphere of a spacecraft without first removing several impurities including hydrogen, chlorine, and certain organic compounds. A treatment concept was developed that would decrease the impurities in the gas stream that emanates from an electrolysis unit to levels sufficiently low to allow the conditioned gas stream to be safely discharged to a spacecraft atmosphere. Two methods were experimentally demonstrated that can accomplish the desired cleanup. The bases of the two methods are, repectively: (1) raw urine scrubbing and (2) silica gel sorption.

Stresses due to Relative Sliding between Particles Surrounded by an Electrolyte Solution with Application to Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Zhang, Cong; Conlisk, A. T.

2013-11-01

Mechanical stresses in the solid phase of the electrodes within lithium-ion batteries have been the subject of much work recently with the emphasis on the stresses induced by lithium insertion to or extraction from the active solid material. The particles within lithium-ion battery electrodes can undergo relative motion with relative velocities of different magnitudes and directions. One mode of the relative motion, resembling the slider bearing motion, manifests itself as two particles sliding relative to each other within an electrolyte solution. The electrolyte solution within the narrow pores between the particles is the medium through which the particles interact with each other. The effect of the electrolyte solution is not conventionally considered. The relative motion of the particles induces significant pressures. The primary objective of this work is to develop a model based on the lubrication approximation to investigate the magnitude and direction of the stresses induced by this sliding motion. Other applications in the biomedical field are also discussed. Supported by DOE Graduate Automotive Technology Education (GATE) and OSU Center for Automotive Research.

Polypropylene oil as fuel for solid oxide fuel cell with samarium doped-ceria (SDC)-carbonate as electrolyte

NASA Astrophysics Data System (ADS)

Syahputra, R. J. E.; Rahmawati, F.; Prameswari, A. P.; Saktian, R.

2017-03-01

The research focusses on converting polypropylene oil as pyrolysis product of polypropylene plastic into an electricity. The converter was a direct liquid fuel-solid oxide fuel cell (SOFC) with cerium oxide based material as electrolyte. The polypropylene vapor flowed into fuel cell, in the anode side and undergo oxidation reaction, meanwhile, the Oxygen in atmosphere reduced into oxygen ion at cathode. The fuel cell test was conducted at 400 - 600 °C. According to GC-MS analysis, the polypropylene oil consist of C8 to C27 hydrocarbon chain. The XRD analysis result shows that Na2CO3 did not change the crystal structure of SDC even increases the electrical conductivity. The maximum power density is 0.079 mW.cm-2 at 773 K. The open circuite voltage is 0.77 volt. Chemical stability test by analysing the single cell at before and after fuel cell test found that ionic migration occured during fuel cell operation. It is supported by the change of elemental composition in the point position of electrolyte and at the electrolyte-electrode interface

Assessment of bioburden encapsulated in bulk materials

NASA Astrophysics Data System (ADS)

Schubert, Wayne W.; Newlin, Laura; Chung, Shirley Y.; Ellyin, Raymond

2016-05-01

The National Aeronautics and Space Administration (NASA) imposes bioburden limitations on all spacecraft destined for solar system bodies that might harbor evidence of extant or extinct life. The subset of microorganisms trapped within solid materials during manufacture and assembly is referred to as encapsulated bioburden. In the absence of spacecraft-specific data, NASA relies on specification values to estimate total spacecraft encapsulated bioburden, typically 30 endospores/cm3 or 300 viable cells/cm3 in non-electronic materials. Specification values for endospores have been established conservatively, and represent no less than an order of magnitude greater abundance than that derived from empirical assessments of actual spacecraft materials. The goal of this study was to generate data germane to determining whether revised bulk encapsulated material values (lower than those estimated by historical specifications) tailored specifically to the materials designated in modern-day spacecraft design could be used, on a case-by-case basis, to comply with planetary protection requirements. Organic materials having distinctly different chemical properties and configurations were selected. This required more than one experimental and analytical approach. Filtration was employed for liquid electrolytes, lubricants were suspended in an aqueous solution and solids (wire and epoxy sealant) were cryogenically milled. The final data characteristic for all bioburden estimates was microbial colony formation in rich agar growth medium. To assess survival potential, three non-spore-forming bacterial cell lines were systematically encapsulated in an epoxy matrix, liberated via cryogenic grinding, and cultured. Results suggest that bulk solid materials harbor significantly fewer encapsulated microorganisms than are estimated by specification values. Lithium-ion battery electrolyte reagents housed fewer than 1 CFU/cm3. Results also demonstrated that non-spore-forming microorganisms are capable of surviving encapsulation within, and liberation from, epoxy solids. It must be noted, however, that all purposely spiked experimental solids, resulted in very low recovery (1 × 10-3-1 × 10-5 CFU/cm3) of viable organisms.

Electrophoretic separator for purifying biologicals

NASA Technical Reports Server (NTRS)

1976-01-01

This technique separates a single narrow zone of sample mixture in an electrolyte medium into many zones containing a single component of the mixture and electrolyte between them. Since the densities of the separated zones generally differ from that of the intervening medium, such systems are gravitationally unstable and stabilization is required. The various techniques for stabilization include using the capillary space provided by thin films, the interstices of solid material such as filter paper and a variety of gel-forming substances.

Stability of the Solid Electrolyte Interface on the Li Electrode in Li–S Batteries

DOE PAGES

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

2016-04-05

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

Solid polymer electrolyte composite membrane comprising laser micromachined porous support

DOEpatents

Liu, Han [Waltham, MA; LaConti, Anthony B [Lynnfield, MA; Mittelsteadt, Cortney K [Natick, MA; McCallum, Thomas J [Ashland, MA

2011-01-11

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 5 microns, are made by laser micromachining and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

Solid polymer electrolyte composite membrane comprising plasma etched porous support

DOEpatents

Liu, Han; LaConti, Anthony B.

2010-10-05

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 0.1 to 5 microns, are made by plasma etching and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

A New Miniaturized Inkjet Printed Solid State Electrolyte Sensor for Applications in Life Support Systems - First Results

NASA Astrophysics Data System (ADS)

Hill, Christine; Stefanos Fasoulas, -; Eberhart, Martin; Berndt, Felix

New generations of integrated closed loop systems will combine life support systems (incl. biological components) and energy systems such as fuel cell and electrolysis systems. Those systems and their test beds also contain complex safety sensor monitoring systems. Especially in fuel cells and electrolysis systems, the hydrogen and oxygen flows and exchange into other areas due to diffusion processes or leaks need to be monitored. Knowledge of predominant gas concentrations at all times is essential to avoid explosive gas mixtures. Solid state electrolyte sensors are promising for use as safety sensors. They have already been developed and produced at various institutes, but the power consumption for heating an existing solid state electrolyte sensor element still lies between 1 to 1.5 W and the operational readiness still takes about 20 to 30 s. This is partially due to the current manufacturing process for the solid state electrolyte sensor elements that is based on screen printing technology. However this technology has strong limitations in flexibility of the layout and re-designs. It is therefore suitable for mass production, but not for a flexible development and the production of specific individual sensors, e.g. for space applications. Moreover a disadvantage is the relatively high material consumption, especially in combination with the sensors need of expensive noble metal and ceramic pastes, which leads to a high sensor unit price. The Inkjet technology however opens up completely new possibilities in terms of dimensions, geometries, structures, morphologies and materials of sensors. This new approach is capable of printing finer high-resolution layers without the necessity of meshes or masks for patterning. Using the Inkjet technology a design change is possible at any time on the CAD screen. Moreover the ink is only deposited where it is needed. Custom made sensors, as they are currently demanded in space sensor applications, are thus realized simply, economically and ecologically. Based on the knowledge of the screen printing sensor production a complete solid state electrolyte oxygen sensor could be produced using Inkjet technology. First measurements in oxygen environment already show promising results. A defined oxygen concentration could be seen during exposition of the Inkjet sensors in an oxygen environment. The obtained results demonstrate the potential to use the technology development in other applications such as in situ respiratory gas analysis systems for human spaceflight. Further approaches at the Institute of Space Systems include the implementation of Inkjet printed solid state electrolyte sensors for the use as redundant safety sensors for the Institute's hybrid life support test beds including fuel cells and algal photo bioreactor elements.

Fabrication of ultrathin solid electrolyte membranes of β-Li 3PS 4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

DOE PAGES

Wang, Hui; Hood, Zachary D.; Xia, Younan; ...

2016-04-25

All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li 3PS 4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreasedmore » to achieve ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li 3PS 4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.« less

One step shift towards flexible supercapacitors based on carbon nanotubes - A review

NASA Astrophysics Data System (ADS)

Yar, A.; Dennis, J. O.; Mohamed, N. M.; Mumtaz, A.; Irshad, M. I.; Ahmad, F.

2014-10-01

Supercapacitors have emerged as prominent energy storage devices that offer high energy density compared to conventional capacitors and high power density which is not found in batteries. Carbon nanotubes (CNTs) because of their high surface area and tremendous electrical properties are used as electrode material for supercapacitors. In this review we focused on the factors like surface area, role of the electrolyte and techniques adopted to improve performance of CNTs based supercapacitors. The supercapacitors are widely tested in liquid electrolytes which are normally hazardous in nature, toxic, flammable and their leakage has safety concerns. This review also focuses on research which is replacing these unsafe electrolytes by solid electrolytes with the combination of low cost CNTs deposited flexible supports for supercapacitors.

Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells

DOEpatents

Kuo, L.J.H.; Singh, P.; Ruka, R.J.; Vasilow, T.R.; Bratton, R.J.

1997-11-11

A low cost, lanthanide-substituted, dimensionally and thermally stable, gas permeable, electrically conductive, porous ceramic air electrode composition of lanthanide-substituted doped lanthanum manganite is provided which is used as the cathode in high temperature, solid oxide electrolyte fuel cells and generators. The air electrode composition of this invention has a much lower fabrication cost as a result of using a lower cost lanthanide mixture, either a natural mixture or an unfinished lanthanide concentrate obtained from a natural mixture subjected to incomplete purification, as the raw material in place of part or all of the higher cost individual lanthanum. The mixed lanthanide primarily contains a mixture of at least La, Ce, Pr, and Nd, or at least La, Ce, Pr, Nd and Sm in its lanthanide content, but can also include minor amounts of other lanthanides and trace impurities. The use of lanthanides in place of some or all of the lanthanum also increases the dimensional stability of the air electrode. This low cost air electrode can be fabricated as a cathode for use in high temperature, solid oxide fuel cells and generators. 4 figs.

Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells

DOEpatents

Kuo, Lewis J. H.; Singh, Prabhakar; Ruka, Roswell J.; Vasilow, Theodore R.; Bratton, Raymond J.

1997-01-01

A low cost, lanthanide-substituted, dimensionally and thermally stable, gas permeable, electrically conductive, porous ceramic air electrode composition of lanthanide-substituted doped lanthanum manganite is provided which is used as the cathode in high temperature, solid oxide electrolyte fuel cells and generators. The air electrode composition of this invention has a much lower fabrication cost as a result of using a lower cost lanthanide mixture, either a natural mixture or an unfinished lanthanide concentrate obtained from a natural mixture subjected to incomplete purification, as the raw material in place of part or all of the higher cost individual lanthanum. The mixed lanthanide primarily contains a mixture of at least La, Ce, Pr, and Nd, or at least La, Ce, Pr, Nd and Sm in its lanthanide content, but can also include minor amounts of other lanthanides and trace impurities. The use of lanthanides in place of some or all of the lanthanum also increases the dimensional stability of the air electrode. This low cost air electrode can be fabricated as a cathode for use in high temperature, solid oxide fuel cells and generators.

Construction of nanostructures for selective lithium ion conduction using self-assembled molecular arrays in supramolecular solids

NASA Astrophysics Data System (ADS)

Moriya, Makoto

2017-12-01

In the development of innovative molecule-based materials, the identification of the structural features in supramolecular solids and the understanding of the correlation between structure and function are important factors. The author investigated the development of supramolecular solid electrolytes by constructing ion conduction paths using a supramolecular hierarchical structure in molecular crystals because the ion conduction path is an attractive key structure due to its ability to generate solid-state ion diffusivity. The obtained molecular crystals exhibited selective lithium ion diffusion via conduction paths consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and small molecules such as ether or amine compounds. In the present review, the correlation between the crystal structure and ion conductivity of the obtained molecular crystals is addressed based on the systematic structural control of the ionic conduction paths through the modification of the component molecules. The relationship between the crystal structure and ion conductivity of the molecular crystals provides a guideline for the development of solid electrolytes based on supramolecular solids exhibiting rapid and selective lithium ion conduction.

Yttria-stabilized zirconia solid oxide electrolyte fuel cells: Monolithic solid oxide fuel cells

NASA Astrophysics Data System (ADS)

1990-10-01

The monolithic solid oxide fuel cell (MSOFC) is currently under development for a variety of applications including coal-based power generation. The MSOFC is a design concept that places the thin components of a solid oxide fuel cell in lightweight, compact, corrugated structure, and so achieves high efficiency and excellent performance simultaneously with high power density. The MSOFC can be integrated with coal gasification plants and is expected to have high overall efficiency in the conversion of the chemical energy of coal to electrical energy. This report describes work aimed at: (1) assessing manufacturing costs for the MSOFC and system costs for a coal-based plant; (2) modifying electrodes and electrode/electrolyte interfaces to improve the electrochemical performance of the MSOFC; and (3) testing the performance of the MSOFC on hydrogen and simulated coal gas. Manufacturing costs for both the coflow and crossflow MSOFC's were assessed based on the fabrication flow charts developed by direct scaleup of tape calendering and other laboratory processes. Integrated coal-based MSOFC systems were investigated to determine capital costs and costs of electricity. Design criteria were established for a coal-fueled 200-Mw power plant. Four plant arrangements were evaluated, and plant performance was analyzed. Interfacial modification involved modification of electrodes and electrode/electrolyte interfaces to improve the MSOFC electrochemical performance. Work in the cathode and cathode/electrolyte interface was concentrated on modification of electrode porosity, electrode morphology, electrode material, and interfacial bonding. Modifications of the anode and anode/electrolyte interface included the use of additives and improvement of nickel distribution. Single cells have been tested for their electrochemical performance. Performance data were typically obtained with humidified H2 or simulated coal gas and air or oxygen.

Integrated Interface Strategy toward Room Temperature Solid-State Lithium Batteries.

PubMed

Ju, Jiangwei; Wang, Yantao; Chen, Bingbing; Ma, Jun; Dong, Shanmu; Chai, Jingchao; Qu, Hongtao; Cui, Longfei; Wu, Xiuxiu; Cui, Guanglei

2018-04-25

Solid-state lithium batteries have drawn wide attention to address the safety issues of power batteries. However, the development of solid-state lithium batteries is substantially limited by the poor electrochemical performances originating from the rigid interface between solid electrodes and solid-state electrolytes. In this work, a composite of poly(vinyl carbonate) and Li 10 SnP 2 S 12 solid-state electrolyte is fabricated successfully via in situ polymerization to improve the rigid interface issues. The composite electrolyte presents a considerable room temperature conductivity of 0.2 mS cm -1 , an electrochemical window exceeding 4.5 V, and a Li + transport number of 0.6. It is demonstrated that solid-state lithium metal battery of LiFe 0.2 Mn 0.8 PO 4 (LFMP)/composite electrolyte/Li can deliver a high capacity of 130 mA h g -1 with considerable capacity retention of 88% and Coulombic efficiency of exceeding 99% after 140 cycles at the rate of 0.5 C at room temperature. The superior electrochemical performance can be ascribed to the good compatibility of the composite electrolyte with Li metal and the integrated compatible interface between solid electrodes and the composite electrolyte engineered by in situ polymerization, which leads to a significant interfacial impedance decrease from 1292 to 213 Ω cm 2 in solid-state Li-Li symmetrical cells. This work provides vital reference for improving the interface compatibility for room temperature solid-state lithium batteries.

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

Polymer electrolytes are an effective way to gate organic semiconductors and nanomaterials, such as nanotubes and 2D materials, by establishing an electrostatic double layer with large capacitance. Widely used solid electrolytes, such as those based on polyethylene oxide, have a glass transition temperature below room temperature. This permits relatively fast ion mobility at T = 23 °C, but requires a constant applied field to maintain a doping profile. Moreover, PEO-based electrolytes cannot withstand a variety of solvents, limiting its use. Here, we demonstrate a polymer electrolyte using polyvinyl alcohol (PVA) with Tg >23 °C, through which a doping profile can be defined by a potential applied when the polymer is heated above Tg, then ``locked-in'' by cooling the electrolyte to room temperature (

From Two-Phase to Three-Phase: The New Electrochemical Interface by Oxide Electrocatalysts

NASA Astrophysics Data System (ADS)

Xu, Zhichuan J.

2018-03-01

Electrochemical reactions typically occur at the interface between a solid electrode and a liquid electrolyte. The charge exchange behaviour between these two phases determines the kinetics of electrochemical reactions. In the past few years, significant advances have been made in the development of metal oxide electrocatalysts for fuel cell and electrolyser reactions. However, considerable gaps remain in the fundamental understanding of the charge transfer pathways and the interaction between the metal oxides and the conducting substrate on which they are located. In particular, the electrochemical interfaces of metal oxides are significantly different from the traditional (metal) ones, where only a conductive solid electrode and a liquid electrolyte are considered. Oxides are insulating and have to be combined with carbon as a conductive mediator. This electrode configuration results in a three-phase electrochemical interface, consisting of the insulating oxide, the conductive carbon, and the liquid electrolyte. To date, the mechanistic insights into this kind of non-traditional electrochemical interface remain unclear. Consequently conventional electrochemistry concepts, established on classical electrode materials and their two-phase interfaces, are facing challenges when employed for explaining these new electrode materials. [Figure not available: see fulltext.

Advanced electrolyte/additive for lithium-ion batteries with silicon anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Shuo; He, Meinan; Su, Chi-Cheung

State-of-the-art lithium-ion batteries (LIBs) are based on a lithium transition metal oxide cathode, a graphite anode and a nonaqueous carbonate electrolyte. To further increase the energy and power density of LIBs, silicon anodes have been intensively explored due to their high theoretical capacity, low operation potential, and low cost. However, the main challenges for Si anode are the large volume change during lithiation/delithiation process and the instability of the solid-electrolyte-interphase associated with this process. Recently, significant progress has been achieved via advanced material fabrication technologies and rational electrolyte design in terms of improving the Coulombic efficiency and capacity retention. Inmore » this paper, new developments in advanced electrolyte and additive for LIBs with Si anode were systematically reviewed, and perspectives over future research were suggested.« less

Solid polymer electrolyte lithium batteries

DOEpatents

Alamgir, M.; Abraham, K.M.

1993-10-12

This invention pertains to Lithium batteries using Li ion (Li[sup +]) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride). 3 figures.

Solid polymer electrolyte lithium batteries

DOEpatents

Alamgir, Mohamed; Abraham, Kuzhikalail M.

1993-01-01

This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

Flexible poly(ethylene carbonate)/garnet composite solid electrolyte reinforced by poly(vinylidene fluoride-hexafluoropropylene) for lithium metal batteries

NASA Astrophysics Data System (ADS)

He, Zijian; Chen, Long; Zhang, Bochen; Liu, Yongchang; Fan, Li-Zhen

2018-07-01

Solid-state electrolytes with high ionic conductivities, great flexibility, and easy processability are needed for high-performance solid-state rechargeable lithium batteries. In this work, we synthesize nanosized cubic Li6.25Al0.25La3Zr2O12 (LLZO) by solution combustion method and develop a flexible garnet-based composite solid electrolyte composed of LLZO, poly(ethylene carbonate) (PEC), poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP) and lithium bis(fluorosulfonyl)imide (LiFSI)). In the flexible composite solid electrolytes, LLZO nanoparticles, as ceramic matrix, have a positive effect on ionic conductivities and lithium ion transference number (tLi+). PEC, as a fast ion-conducting polymer, possesses high tLi+ inherently. P(VdF-HFP), as a binder, can strengthen mechanical properties. Consequently, the as-prepared composite solid electrolyte demonstrates high tLi+ (0.82) and superb thermal stability (remaining LLZO matrix after burning). All-solid-state LiFePO4|Li cells assembled with the flexible composite solid electrolyte deliver a high initial discharge specific capacity of 121.4 mAh g-1 and good cycling stability at 55 °C.

Sodium Ion Diffusion in Nasicon (Na3Zr2Si2PO12) Solid Electrolytes: Effects of Excess Sodium.

PubMed

Park, Heetaek; Jung, Keeyoung; Nezafati, Marjan; Kim, Chang-Soo; Kang, Byoungwoo

2016-10-04

The Na superionic conductor (aka Nasicon, Na 1+x Zr 2 Si x P 3-x O 12 , where 0 ≤ x ≤ 3) is one of the promising solid electrolyte materials used in advanced molten Na-based secondary batteries that typically operate at high temperature (over ∼270 °C). Nasicon provides a 3D diffusion network allowing the transport of the active Na-ion species (i.e., ionic conductor) while blocking the conduction of electrons (i.e., electronic insulator) between the anode and cathode compartments of cells. In this work, the standard Nasicon (Na 3 Zr 2 Si 2 PO 12 , bare sample) and 10 at% Na-excess Nasicon (Na 3.3 Zr 2 Si 2 PO 12 , Na-excess sample) solid electrolytes were synthesized using a solid-state sintering technique to elucidate the Na diffusion mechanism (i.e., grain diffusion or grain boundary diffusion) and the impacts of adding excess Na at relatively low and high temperatures. The structural, thermal, and ionic transport characterizations were conducted using various experimental tools including X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). In addition, an ab initio atomistic modeling study was carried out to computationally examine the detailed microstructures of Nasicon materials, as well as to support the experimental observations. Through this combination work comprising experimental and computational investigations, we show that the predominant mechanisms of Na-ion transport in the Nasicon structure are the grain boundary and the grain diffusion at low and high temperatures, respectively. Also, it was found that adding 10 at% excess Na could give rise to a substantial increase in the total conductivity (e.g., ∼1.2 × 10 -1 S/cm at 300 °C) of Nasicon electrolytes resulting from the enlargement of the bottleneck areas in the Na diffusion channels of polycrystalline grains.

Glass-ceramic material and method of making

DOEpatents

Meinhardt, Kerry D [Richland, WA; Vienna, John D [West Richland, WA; Armstrong, Timothy R [Pasco, WA; Pederson, Larry R [Kennewick, WA

2002-08-13

The present invention is a glass-ceramic material and method of making useful for joining at least two solid ceramic parts. The seal is a blend of M.sub.A O--M.sub.B O.sub.y --SiO.sub.2 that substantially matches a coefficient of thermal expansion of the solid electrolyte. According to the present invention, a series of glass ceramics in the M.sub.A O--M.sub.B O.sub.y --SiO.sub.2 system can be used to join or seal both tubular and planar ceramic solid oxide fuel cells, oxygen electrolyzers, and membrane reactors for the production of syngas, commodity chemicals and other products.

A stable perovskite electrolyte in moist air for Li-ion batteries.

PubMed

Li, Yutao; Xu, Henghui; Chien, Po-Hsiu; Wu, Nan; Xin, Sen; Xue, Leigang; Park, Kyusung; Hu, Yan-Yan; Goodenough, John B

2018-05-07

Solid-oxide Li+ electrolytes of a rechargeable cell are generally sensitive to moisture in the air, H+ exchanges for the mobile Li+ of the electrolyte and forms insulating surface phases at the electrolyte interfaces and in the grain boundaries of a polycrystalline membrane. These surface phases dominate the total interfacial resistance of a conventional rechargeable cell having a solid-electrolyte separator. We report a new perovskite Li+ solid electrolyte, Li0.38Sr0.44Ta0.7Hf0.3O2.95F0.05, having a Li-ion conductivity σLi = 4.8×10-4 S cm-1 at 25 oC that does not react with water having 3≤pH≤14. The solid electrolyte with a thin Li+-conducting polymer on its surface to prevent reduction of Ta5+ is wet by metallic lithium and provides low-impedance dendrite-free plating/stripping of a lithium anode. It is also stable on contact with a composite polymer cathode. With this solid electrolyte, we demonstrate excellent cycling performance of an all-solid-state Li/LiFePO4 cell, a Li-S cell with a polymer-gel cathode, and a supercapacitor. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2016-06-07

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode and a semi-solid cathode. The semi-solid cathode includes a suspension of an active material of about 35% to about 75% by volume of an active material and about 0.5% to about 8% by volume of a conductive material in a non-aqueous liquid electrolyte. An ion-permeable membrane is disposed between the anode and the semi-solid cathode. The semi-solid cathode has a thickness of about 250 .mu.m to about 2,000 .mu.m, and the electrochemical cell has an area specific capacity of at least about 7 mAh/cm.sup.2 at a C-rate of C/4. In some embodiments, the semi-solid cathode slurry has a mixing index of at least about 0.9.

Synthesis, Characterization and Conductivity Study of Poly(vinyl 4-HYDROXY-3-METHOXY Benzal) and its Sodio Salt in Solid State

NASA Astrophysics Data System (ADS)

Borah, P.; Hussain, S.; Dutta, A.

Among the various ion-conducting materials, polymer salt complexes are of current interest due to their possible application as solid electrolyte as well as their physical nature in advanced high-energy electrochemical devices such as batteries, fuel cells, electrochromic display devices, photo electro-chemical solar cells52-55 etc. The main advantages of polymeric electrolytes are their mechanical properties, ease of fabrication of thin films of desired sizes and their ability to form proper electrode-electrolyte contact. Polymer electrolyte usually consists of a polymer and a salt and is considered to be solid solutions in which the polymer functions as solvent. In the present paper the synthesis, characterization and the conductivity study of the polymer poly (vinyl 4-hydroxy-3-methoxy benzal) (PV-HMB) and its sodio salt (PV-HMB-Na) have been reported. The polymer was prepared by carrying out homogenous acetalization between the prepolymer poly vinylalcohol (PVA) and 4-hydroxy-3-methoxy benzaldehyde (vanilline). PVA was dissolved in dimethyl formamide (DMF) and lithium chloride (LiCl) system i.e., in non-aqueous medium. The sodio salt was prepared by alkalization. The polymer and its salt were characterized by IR, 1H NMR and DSC. Frequency and temperature dependence of ac conductivity has been studied to learn about the electrical conduction behaviour in this material. The electrical conductivity of the new polymeric salt was found to be in the range 10-4 to 10-6 Scm-1. There is about 103 to 104 fold increase in the conductivity of the new polymer salt. Apparent activation energy of the polymer and its salt were found to be 0.139 and 0.08998 ev respectively.

A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes

NASA Astrophysics Data System (ADS)

Liu, Nian; Lu, Zhenda; Zhao, Jie; McDowell, Matthew T.; Lee, Hyun-Wook; Zhao, Wenting; Cui, Yi

2014-03-01

Silicon is an attractive material for anodes in energy storage devices, because it has ten times the theoretical capacity of its state-of-the-art carbonaceous counterpart. Silicon anodes can be used both in traditional lithium-ion batteries and in more recent Li-O2 and Li-S batteries as a replacement for the dendrite-forming lithium metal anodes. The main challenges associated with silicon anodes are structural degradation and instability of the solid-electrolyte interphase caused by the large volume change (~300%) during cycling, the occurrence of side reactions with the electrolyte, and the low volumetric capacity when the material size is reduced to a nanometre scale. Here, we propose a hierarchical structured silicon anode that tackles all three of these problems. Our design is inspired by the structure of a pomegranate, where single silicon nanoparticles are encapsulated by a conductive carbon layer that leaves enough room for expansion and contraction following lithiation and delithiation. An ensemble of these hybrid nanoparticles is then encapsulated by a thicker carbon layer in micrometre-size pouches to act as an electrolyte barrier. As a result of this hierarchical arrangement, the solid-electrolyte interphase remains stable and spatially confined, resulting in superior cyclability (97% capacity retention after 1,000 cycles). In addition, the microstructures lower the electrode-electrolyte contact area, resulting in high Coulombic efficiency (99.87%) and volumetric capacity (1,270 mAh cm-3), and the cycling remains stable even when the areal capacity is increased to the level of commercial lithium-ion batteries (3.7 mAh cm-2).

Ultra-thin Solid-State Li-Ion Electrolyte Membrane Facilitated by a Self-Healing Polymer Matrix.

PubMed

Whiteley, Justin M; Taynton, Philip; Zhang, Wei; Lee, Se-Hee

2015-11-18

Thin solid membranes are formed by a new strategy, whereby an in situ derived self-healing polymer matrix that penetrates the void space of an inorganic solid is created. The concept is applied as a separator in an all-solid-state battery with an FeS2 -based cathode and achieves tremendous performance for over 200 cycles. Processing in dry conditions represents a paradigm shift for incorporating high active-material mass loadings into mixed-matrix membranes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relaxation and transport properties of Li+ ion conducting biocompatible material for battery application

NASA Astrophysics Data System (ADS)

Hegde, Shreedatta; Ravindrachary, V.; Praveena, S. D.; Guruswamy, B.; Sagar, Rohan N.; Sanjeev, Ganesh

2018-04-01

Solid polymer electrolyte based on lithium chloride doped Poly (vinyl) alcohol composites are prepared by solution casting method. XRD results show that the crystallinity of the polymer interrupted upon LiCl doping and amorphous nature increases with dopant concentration. Impedance analysis revealed that conductivity of PVA increases with doping level and maximum ionic conductivity is observed to be 6.69 × 10-3 S/cm for 15 wt% LiCl doped PVA composite at 353K. Wagner's polarization technique has been followed to calculate ion transport number for high conducting electrolyte and transient study confirmed the presence of single charge species within the polymer electrolyte.

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Ya; Cui, Yan; Zuo, Xiaoxi

2014-10-15

Highlights: • The spent Zn–Mn batteries collected from manufacturers is the target waste. • A facile reclaiming process is presented. • The zinc is reclaimed to valuable electrolytic zinc by electrodepositing method. • The manganese elements are to produce valuable LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} battery material. • The reclamation process features environmental friendliness and saving resource. - Abstract: A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn–Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organicmore » separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H{sub 2}SO{sub 4} (2 mol L{sup −1}) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ⩾99.8% is recovered in an electrolytic cell with a cathode efficiency of ⩾85% under the conditions of 37–40 °C and 300 A m{sup −2}. The most of MnO{sub 2} and a small quantity of electrolytic MnO{sub 2} are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} material of lithium-ion battery. The as-synthesized LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} discharges 118.3 mAh g{sup −1} capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO{sub 2}. This process can recover the substances in the spent Zn–Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable.« less

Solid polymer electrolyte compositions

DOEpatents

Garbe, James E.; Atanasoski, Radoslav; Hamrock, Steven J.; Le, Dinh Ba

2001-01-01

An electrolyte composition is featured that includes a solid, ionically conductive polymer, organically modified oxide particles that include organic groups covalently bonded to the oxide particles, and an alkali metal salt. The electrolyte composition is free of lithiated zeolite. The invention also features cells that incorporate the electrolyte composition.

Toward highly stable solid-state unconventional thin-film battery-supercapacitor hybrid devices: Interfacing vertical core-shell array electrodes with a gel polymer electrolyte

NASA Astrophysics Data System (ADS)

Pandey, Gaind P.; Klankowski, Steven A.; Liu, Tao; Wu, Judy; Li, Jun

2017-02-01

A novel solid-state battery-supercapacitor hybrid device is fabricated for high-performance electrical energy storage using a Si anode and a TiO2 cathode in conjunction with a flexible, solid-like gel polymer electrolyte film as the electrolyte and separator. The electrodes were fabricated as three-dimensional nanostructured vertical arrays by sputtering active materials as conformal shells on vertically aligned carbon nanofibers (VACNFs) which serve as the current collector and structural template. Such nanostructured vertical core-shell array-electrodes enable short Li-ion diffusion path and large pseudocapacitive contribution by fast surface reactions, leading to the hybrid features of batteries and supercapacitors that can provide high specific energy over a wide range of power rates. Due to the improved mechanical stability of the infiltrated composite structure, the hybrid cell shows excellent cycling stability and is able to retain more than 95% of the original capacity after 3500 cycles. More importantly, this solid-state device can stably operate in a temperature range from -20 to 60 °C with a very low self-discharge rate and an excellent shelf life. This solid-state architecture is promising for the development of highly stable thin-film hybrid energy storage devices for unconventional applications requiring largely varied power, wider operation temperature, long shelf-life and higher safety standards.

Assessment of Lithium-based Battery Electrolytes Developed under the NASA PERS Program

NASA Technical Reports Server (NTRS)

Bennett, William R.; Baldwin, Richard S.

2006-01-01

Recently, NASA formally completed the Polymer Energy Rechargeable System (PERS) Program, which was established in 2000 in collaboration with the Air Force Research Laboratory (AFRL) to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The goal of this program was to ultimately develop an advanced, space-qualified battery technology, which embodied a solid polymer electrolyte (SPE) and complementary components, with improved performance characteristics that would address future aerospace battery requirements. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. A variety of cell and polymeric electrolyte concepts were pursued as part of the development efforts undertaken at numerous governmental, industrial and academic laboratories. Numerous candidate electrolyte materials were developed, synthesized and optimized for evaluation. Utilizing the component screening facility and the "standardized" test procedures developed at the NASA Glenn Research Center, electrochemical screening and performance evaluations of promising candidate materials were completed. This overview summarizes test results for a variety of candidate electrolyte materials that were developed under the PERS Program. Electrolyte properties are contrasted and compared to the original project goals, and the strengths and weaknesses of the electrolyte chemistries are discussed. Limited cycling data for full-cells using lithium metal and vanadium oxide electrodes are also presented. Based on measured electrolyte properties, the projected performance characteristics and temperature limitations of batteries utilizing the advanced electrolytes and components have been estimated. Limitations for the achievement of practical performance levels are also discussed, as well as needs for future research and development.

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

PubMed

Yi, Jin; Zhou, Haoshen

2016-09-08

In the context of the development of electric vehicle to solve the contemporary energy and environmental issues, the possibility of pushing future application of Li-O2 batteries as a power source for electric vehicles is particularly attractive. However, safety concerns, mainly derived from the use of flammable organic liquid electrolytes, become a major bottleneck for the strategically crucial applications of Li-O2 batteries. To overcome this issue, rechargeable solid-state Li-O2 batteries with enhanced safety is regarded as an appealing candidate. In this study, a hybrid quasi-solid-state electrolyte combing a polymer electrolyte with a ceramic electrolyte is first designed and explored for Li-O2 batteries. The proposed rechargeable solid-state Li-O2 battery delivers improved cycle life (>100 cycles) and safety. The feasibility study demonstrates that the hybrid quasi-solid-state electrolytes could be employed as a promising alternative strategy for the development of rechargeable Li-O2 batteries, hence encouraging more efforts devoted to explore other hybrid solid-state electrolytes for Li-O2 batteries upon future application. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

PubMed Central

Li, Yutao; Zhou, Weidong; Chen, Xi; Lü, Xujie; Cui, Zhiming; Xin, Sen; Xue, Leigang; Jia, Quanxi; Goodenough, John B.

2016-01-01

A solid electrolyte with a high Li-ion conductivity and a small interfacial resistance against a Li metal anode is a key component in all-solid-state Li metal batteries, but there is no ceramic oxide electrolyte available for this application except the thin-film Li-P oxynitride electrolyte; ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites in a short time. Here, we introduce a solid electrolyte LiZr2(PO4)3 with rhombohedral structure at room temperature that has a bulk Li-ion conductivity σLi = 2 × 10−4 S⋅cm−1 at 25 °C, a high electrochemical stability up to 5.5 V versus Li+/Li, and a small interfacial resistance for Li+ transfer. It reacts with a metallic lithium anode to form a Li+-conducting passivation layer (solid-electrolyte interphase) containing Li3P and Li8ZrO6 that is wet by the lithium anode and also wets the LiZr2(PO4)3 electrolyte. An all-solid-state Li/LiFePO4 cell with a polymer catholyte shows good cyclability and a long cycle life. PMID:27821751

Solid-state rechargeable magnesium battery

DOEpatents

Shao, Yuyan; Liu, Jun; Liu, Tianbiao; Li, Guosheng

2016-09-06

Embodiments of a solid-state electrolyte comprising magnesium borohydride, polyethylene oxide, and optionally a Group IIA or transition metal oxide are disclosed. The solid-state electrolyte may be a thin film comprising a dispersion of magnesium borohydride and magnesium oxide nanoparticles in polyethylene oxide. Rechargeable magnesium batteries including the disclosed solid-state electrolyte may have a coulombic efficiency .gtoreq.95% and exhibit cycling stability for at least 50 cycles.

Toward practical all-solid-state lithium-ion batteries with high energy density and safety: Comparative study for electrodes fabricated by dry- and slurry-mixing processes

NASA Astrophysics Data System (ADS)

Nam, Young Jin; Oh, Dae Yang; Jung, Sung Hoo; Jung, Yoon Seok

2018-01-01

Owing to their potential for greater safety, higher energy density, and scalable fabrication, bulk-type all-solid-state lithium-ion batteries (ASLBs) employing deformable sulfide superionic conductors are considered highly promising for applications in battery electric vehicles. While fabrication of sheet-type electrodes is imperative from the practical point of view, reports on relevant research are scarce. This might be attributable to issues that complicate the slurry-based fabrication process and/or issues with ionic contacts and percolation. In this work, we systematically investigate the electrochemical performance of conventional dry-mixed electrodes and wet-slurry fabricated electrodes for ASLBs, by varying the different fractions of solid electrolytes and the mass loading. This information calls for a need to develop well-designed electrodes with better ionic contacts and to improve the ionic conductivity of solid electrolytes. As a scalable proof-of-concept to achieve better ionic contacts, a premixing process for active materials and solid electrolytes is demonstrated to significantly improve electrochemical performance. Pouch-type 80 × 60 mm2 all-solid-state LiNi0·6Co0·2Mn0·2O2/graphite full-cells fabricated by the slurry process show high cell-based energy density (184 W h kg-1 and 432 W h L-1). For the first time, their excellent safety is also demonstrated by simple tests (cutting with scissors and heating at 110 °C).

Sensor apparatus using an electrochemical cell

DOEpatents

Thakur, Mrinal

2003-07-01

A method for sensing mechanical quantities such as force, stress, strain, pressure and acceleration is disclosed. This technology is based on a change in the electrochemically generated voltage (electromotive force) with application of force, stress, strain, pressure or acceleration. The change in the voltage is due to a change in the internal resistance of the electrochemical cell with a change in the relative position or orientation of the electrodes (anode and cathode) in the cell. The signal to be detected (e.g. force, stress, strain, pressure or acceleration) is applied to one of the electrodes to cause a change in the relative position or orientation between the electrodes. Various materials, solid, semisolid, gel, paste or liquid can be utilized as the electrolyte. The electrolyte must be an ion conductor. The examples of solid electrolytes include specific polymer conductors, polymer composites, ion conducting glasses and ceramics. The electrodes are made of conductors such as metals with dissimilar electro negativities. Significantly enhanced sensitivities, up to three orders of magnitude higher than that of comparable commercial sensors, are obtained. The materials are substantially less expensive than commercially used materials for mechanical sensors. An apparatus for sensing such mechanical quantities using materials such as doped 1,4 cis-polyisopropene and nafion. The 1,4 cis-polyisopropene may be doped with lithium perchlorate or iodine. The output voltage signal increases with an increase of the sensing area for a given stress. The device can be used as an intruder alarm, among other applications.

Optimisation of oxygen ion transport in materials for ceramic membrane devices.

PubMed

Kilner, J A

2007-01-01

Oxygen transport in ceramic oxide materials has received much attention over the past few decades. Much of this interest has stemmed from the desire to construct high temperature electrochemical devices for energy conversion, an example being the solid oxide fuel cell. In order to achieve high performance for these devices, insights are needed in how to achieve optimum performance from the functional components such as the electrolytes and electrodes. This includes the optimisation of oxygen transport through the crystal lattice of electrode and electrolyte materials and across the homogeneous (grain boundary) and heterogeneous interfaces that exist in real devices. Strategies are discussed for the optimisation of these quantities and current problems in the characterisation of interfacial transport are explored.

Tuning the Solid Electrolyte Interphase for Selective Li- and Na-Ion Storage in Hard Carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soto, Fernando A.; Yan, Pengfei; Engelhard, Mark H.

Solid-electrolyte interphase (SEI) with controllable properties are highly desirable to improve battery performance. In this paper, we use a combined experimental and simulation approach to study the SEI formation on hard carbon in Li and Na-ion batteries. We show that with proper additives, stable SEI can be formed on hard carbon by pre-cycling the electrode materials in Li or Na-ion electrolyte. Detailed mechanistic studies suggest that the ion transport in the SEI layer is kinetically controlled and can be tuned by the applied voltage. Selective Na and Li-ion SEI membranes are produced using the Na or Li-ion based electrolytes respectively.more » The large Na ion SEI allows easy transport of Li ions, while the small Li ion SEI shuts off the Na-ion transport. Na-ion storage can be manipulated by tuning the SEI with film-forming electrolyte additives or preforming a SEI on the electrodes’ surface. The Na specific capacity can be controlled to <25 mAh/g, ~1/10 of the normal capacity (250 mAh/g). Unusual selective/preferential transport of Li-ion is demonstrated by preforming a SEI on the electrode’s surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion selective conductors using electrochemical approaches in the future.« less

Ionically self-assembled monolayers (ISAMs)

NASA Astrophysics Data System (ADS)

Janik, John

2001-04-01

Ionically self-assembled monolayers (ISAMs), fabricated by alternate adsorption of cationic and anionic components, yield exceptionally homogeneous thin films with sub-nanometer control of the thickness and relative special location of the component materials. Using organic electrochromic materials such as polyaniline, we report studies of electrochromic responses in ISAM films. Reversible changes in the absorption spectrum are observed with the application of voltages on the order of 1.0 V. Measurements are made using both liquid electrolytes and in all-solid state devices incorporating solid polyelectrolytes such as poly(2-acylamido 2-methyl propane sulfonic acid) (PAMPS).

All-Solid-State Batteries with Thick Electrode Configurations.

PubMed

Kato, Yuki; Shiotani, Shinya; Morita, Keisuke; Suzuki, Kota; Hirayama, Masaaki; Kanno, Ryoji

2018-02-01

We report the preparation of thick electrode all-solid-state lithium-ion cells in which a large geometric capacity of 15.7 mAh cm -2 was achieved at room temperature using a 600 μm-thick cathode layer. The effect of ionic conductivity on the discharge performance was then examined using two different materials for the solid electrolyte. Furthermore, important morphological information regarding the tortuosity factor was electrochemically extracted from the capacity-current data. The effect of tortuosity on cell performance was also quantitatively discussed.

Shear Thickening Electrolytes for High Impact Resistant Batteries

DOE PAGES

Veith, Gabriel M.; Armstrong, Beth L.; Wang, Hsin; ...

2017-08-16

In this paper, we demonstrate a shear thickening electrolyte that stiffens into a solid-like barrier during a high energy event, like a car crash. This barrier prevents the electrodes from shorting during an impact, reducing the risk of fire or catastrophic safety events. In addition, we have demonstrated the ability to cycle NMC/graphite lithium ion cells over 200 cycles with no loss of capacity after formation. Finally, this chemistry introduces multifunctionality to a material previously feared due to its flammability.

Shear Thickening Electrolytes for High Impact Resistant Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veith, Gabriel M.; Armstrong, Beth L.; Wang, Hsin

In this paper, we demonstrate a shear thickening electrolyte that stiffens into a solid-like barrier during a high energy event, like a car crash. This barrier prevents the electrodes from shorting during an impact, reducing the risk of fire or catastrophic safety events. In addition, we have demonstrated the ability to cycle NMC/graphite lithium ion cells over 200 cycles with no loss of capacity after formation. Finally, this chemistry introduces multifunctionality to a material previously feared due to its flammability.

Copper Chloride Cathode For Liquid-Sodium Cell

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V.; Distefano, Salvador; Nagasubramanian, Ganesan; Bankston, Clyde P.

1990-01-01

Rechargeable liquid-sodium cell with copper chloride cathode offers substantial increase in energy density over cells made with other cathode materials. Unit has theoretical maximum energy density of 1135 W.h/kg. Generates electricity by electrochemical reaction of molten sodium and solid copper chloride immersed in molten electrolyte, sodium tetrachloroaluminate at temperature of equal to or greater than 200 degrees C. Wall of alumina tube separates molten electrolyte from molten sodium anode. Copper chloride cathode embedded in pores of sintered nickel cylinder or directly sintered.

Recent Developments of All-Solid-State Lithium Secondary Batteries with Sulfide Inorganic Electrolytes.

PubMed

Xu, Ruochen; Zhang, Shengzhao; Wang, Xiuli; Xia, Yan; Xia, Xinhui; Wu, Jianbo; Gu, Changdong; Tu, Jiangping

2018-04-20

Due to the increasing demand of security and energy density, all-solid-state lithium ion batteries have become the promising next-generation energy storage devices to replace the traditional liquid batteries with flammable organic electrolytes. In this Minireview, we focus on the recent developments of sulfide inorganic electrolytes for all-solid-state batteries. The challenges of assembling bulk-type all-solid-state batteries for industrialization are discussed, including low ionic conductivity of the present sulfide electrolytes, high interfacial resistance and poor compatibility between electrolytes and electrodes. Many efforts have been focused on the solutions for these issues. Although some progresses have been achieved, it is still far away from practical application. The perspectives for future research on all-solid-state lithium ion batteries are presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfonated polystyrene and its characterization as a material of electrolyte polymer

NASA Astrophysics Data System (ADS)

Ngadiwiyana; Ismiyarto; Gunawan; Purbowatiningrum, RS; Prasetya, N. B. A.; Kusworo, T. D.; Susanto, H.

2018-05-01

The research of polystyrene modification from Styrofoam waste and its application as a main material of electrolyte polymer had been done. The sulfonation reaction of polystyrene was conducted using sulfuric acid as sufonation agent and the reactions were done with variation times of 1, 2, 3, 4 and 5 h. The characterization of the sulfonated products covered analysis of functional groups using FT-IR spectrophotometer, sulfonation degree, measurements of ion exchange capacity, conductivity and swelling degree. The sulfonated polystyrene product was white solid as confirmed by the spectra of FT-IR with the presence of wide band absorption of O=S=O at the wavenumber of 1080-1411 cm-1 as indication. The research showed the best sulfonated polystyrene prepared in 4 h as a material of electrolyte polymer, since it had the highest degree of sulfonation, ion exchange capacity, conductivity and swelling degree with the values were 28.52 %, 1.550 meg/g, 15,924.10-6 Ω-1cm-1 and 332.4 %, respectively.

Facilitated ion transport in all-solid-state flexible supercapacitors.

PubMed

Choi, Bong Gill; Hong, Jinkee; Hong, Won Hi; Hammond, Paula T; Park, HoSeok

2011-09-27

The realization of highly flexible and all-solid-state energy-storage devices strongly depends on both the electrical properties and mechanical integrity of the constitutive materials and the controlled assembly of electrode and solid electrolyte. Herein we report the preparation of all-solid-state flexible supercapacitors (SCs) through the easy assembly of functionalized reduced graphene oxide (f-RGO) thin films (as electrode) and solvent-cast Nafion electrolyte membranes (as electrolyte and separator). In particular, the f-RGO-based SCs (f-RGO-SCs) showed a 2-fold higher specific capacitance (118.5 F/g at 1 A/g) and rate capability (90% retention at 30 A/g) compared to those of all-solid-state graphene SCs (62.3 F/g at 1A/g and 48% retention at 30 A/g). As proven by the 4-fold faster relaxation of the f-RGO-SCs than that of the RGO-SCs and more capacitive behavior of the former at the low-frequency region, these results were attributed to the facilitated ionic transport at the electrical double layer by means of the interfacial engineering of RGO by Nafion. Moreover, the superiority of all-solid-state flexible f-RGO-SCs was demonstrated by the good performance durability under the 1000 cycles of charging and discharging due to the mechanical integrity as a consequence of the interconnected networking structures. Therefore, this research provides new insight into the rational design and fabrication of all-solid-state flexible energy-storage devices as well as the fundamental understanding of ion and charge transport at the interface. © 2011 American Chemical Society

Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

NASA Astrophysics Data System (ADS)

de Jongh, P. E.; Blanchard, D.; Matsuo, M.; Udovic, T. J.; Orimo, S.

2016-03-01

A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible with Li-metal anodes, prevent Li dendrite formation, and eliminate risks associated with flammable organic solvents. Less than 10 years ago, LiBH4 was proposed as a solid-state electrolyte. It showed a high ionic conductivity, but only at elevated temperatures. Since then a range of other complex metal hydrides has been reported to show similar characteristics. Strategies have been developed to extend the high ionic conductivity of LiBH4 down to room temperature by partial anion substitution or nanoconfinement. The present paper reviews the recent developments in complex metal hydrides as solid electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries.

One step shift towards flexible supercapacitors based on carbon nanotubes - A review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yar, A., E-mail: asfandyarhargan@gmail.com, E-mail: johndennis@petronas.com.my, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: asad-032@yahoo.com, E-mail: imrancssp@gmail.com; Dennis, J. O., E-mail: asfandyarhargan@gmail.com, E-mail: johndennis@petronas.com.my, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: asad-032@yahoo.com, E-mail: imrancssp@gmail.com; Mohamed, N. M., E-mail: asfandyarhargan@gmail.com, E-mail: johndennis@petronas.com.my, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: asad-032@yahoo.com, E-mail: imrancssp@gmail.com

2014-10-24

Supercapacitors have emerged as prominent energy storage devices that offer high energy density compared to conventional capacitors and high power density which is not found in batteries. Carbon nanotubes (CNTs) because of their high surface area and tremendous electrical properties are used as electrode material for supercapacitors. In this review we focused on the factors like surface area, role of the electrolyte and techniques adopted to improve performance of CNTs based supercapacitors. The supercapacitors are widely tested in liquid electrolytes which are normally hazardous in nature, toxic, flammable and their leakage has safety concerns. This review also focuses on researchmore » which is replacing these unsafe electrolytes by solid electrolytes with the combination of low cost CNTs deposited flexible supports for supercapacitors.« less

Towards flexible solid-state supercapacitors for smart and wearable electronics.

PubMed

Dubal, Deepak P; Chodankar, Nilesh R; Kim, Do-Heyoung; Gomez-Romero, Pedro

2018-03-21

Flexible solid-state supercapacitors (FSSCs) are frontrunners in energy storage device technology and have attracted extensive attention owing to recent significant breakthroughs in modern wearable electronics. In this study, we review the state-of-the-art advancements in FSSCs to provide new insights on mechanisms, emerging electrode materials, flexible gel electrolytes and novel cell designs. The review begins with a brief introduction on the fundamental understanding of charge storage mechanisms based on the structural properties of electrode materials. The next sections briefly summarise the latest progress in flexible electrodes (i.e., freestanding and substrate-supported, including textile, paper, metal foil/wire and polymer-based substrates) and flexible gel electrolytes (i.e., aqueous, organic, ionic liquids and redox-active gels). Subsequently, a comprehensive summary of FSSC cell designs introduces some emerging electrode materials, including MXenes, metal nitrides, metal-organic frameworks (MOFs), polyoxometalates (POMs) and black phosphorus. Some potential practical applications, such as the development of piezoelectric, photo-, shape-memory, self-healing, electrochromic and integrated sensor-supercapacitors are also discussed. The final section highlights current challenges and future perspectives on research in this thriving field.

First-principles investigations of ionic conduction in Li and Na borohydrides

NASA Astrophysics Data System (ADS)

Varley, Joel; Heo, Tae-Wook; Ray, Keith; Bonev, Stanimir; Wood, Brandon

Recent experimental studies have identified a family of alkali borohydride materials that exhibit superionic transition temperatures approaching room temperature and ionic conductivities exceeding 0.1 S/cm-1, making them highly promising solid electrolytes for next-generation batteries. Despite the rapid advances in improving the superionic conductivity in these materials, an understanding of the exact mechanisms driving the transport remains unknown. Here we use ab initio molecular dynamics calculations to address this issue by characterizing the diffusivity of the Li and Na species in a representative set of closoborane ionic conductors. We investigate both the Na and Li-containing borohydrides with icosahedral (B12H12) and double-capped square antiprism (B10H10) anion species and discuss the trends in ionic conductivity as a function of stoichiometry and the incorporation of various dopants. Our results support the borohydrides as a subset of a larger family of very promising solid electrolytes and identify strategies to improving the conductivity in these materials. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

ZrB 2-HfB 2 solid solutions as electrode materials for hydrogen reaction in acidic and basic solutions

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-11-09

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Electro-mechanical characterization of structural supercapacitors

NASA Astrophysics Data System (ADS)

Gallagher, T.; LaMaster, D.; Ciocanel, C.; Browder, C.

2012-04-01

The paper presents electrical and mechanical properties of structural supercapacitors and discusses limitations associated with the approach taken for the electrical properties evaluation. The structural supercapacitors characterized in this work had the electrodes made of carbon fiber weave, separator made of several cellulose based products, and the solid electrolyte made as PEGDGE based polymer blend. The reported electrical properties include capacitance and leakage resistance; the former was measured using cyclic voltammetry. Mechanical properties have been evaluated thorough tensile and three point bending tests performed on structural supercapacitor coupons. The results indicate that the separator material plays an important role on the electrical as well as mechanical properties of the structural capacitor, and that Celgard 3501 used as separator leads to most benefits for both mechanical and electrical properties. Specific capacitance and leakage resistance as high as 1.4kF/m3 and 380kΩ, respectively, were achieved. Two types of solid polymer electrolytes were used in fabrication, with one leading to higher and more consistent leakage resistance values at the expense of a slight decrease in specific capacitance when compared to the other SPE formulation. The ultimate tensile strength and modulus of elasticity of the developed power storage composite were evaluated at 466MPa and 18.9MPa, respectively. These values are 58% and 69% of the tensile strength and modulus of elasticity values measured for a single layer composite material made with the same type of carbon fiber and with a West System 105 epoxy instead of solid polymer electrolyte.

Nano-sponge ionic liquid-polymer composite electrolytes for solid-state lithium power sources

NASA Astrophysics Data System (ADS)

Liao, Kang-Shyang; Sutto, Thomas E.; Andreoli, Enrico; Ajayan, Pulickel; McGrady, Karen A.; Curran, Seamus A.

Solid polymer gel electrolytes composed of 75 wt.% of the ionic liquid, 1- n-butyl-2,3-dimethylimidazolium bis-trifluoromethanesulfonylimide with 1.0 M lithium bis-trifluoromethanesulfonylimide and 25 wt.% poly(vinylidenedifluoro-hexafluoropropene) are characterized as the electrolyte/separator in solid-state lithium batteries. The ionic conductivity of these gels ranges from 1.5 to 2.0 mS cm -1, which is several orders of magnitude more conductive than any of the more commonly used solid polymers, and comparable to the best solid gel electrolytes currently used in industry. TGA indicates that these polymer gel electrolytes are thermally stable to over 280 °C, and do not begin to thermally decompose until over 300 °C; exhibiting a significant advancement in the safety of lithium batteries. Atomic force microscopy images of these solid thin films indicate that these polymer gel electrolytes have the structure of nano-sponges, with a sub-micron pore size. For these thin film batteries, 150 charge-discharge cycles are run for Li xCoO 2 where x is cycled between 0.95 down to 0.55. Minimal internal resistance effects are observed over the charging cycles, indicating the high ionic conductivity of the ionic liquid solid polymer gel electrolyte. The overall cell efficiency is approximately 98%, and no significant loss in battery efficiency is observed over the 150 cycles.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

NASA Astrophysics Data System (ADS)

Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

2015-12-01

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles.

PubMed

Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A

2015-12-04

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

PubMed Central

Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

2015-01-01

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries. PMID:26634644

Formation of thin walled ceramic solid oxide fuel cells

DOEpatents

Claar, Terry D.; Busch, Donald E.; Picciolo, John J.

1989-01-01

To reduce thermal stress and improve bonding in a high temperature monolithic solid oxide fuel cell (SOFC), intermediate layers are provided between the SOFC's electrodes and electrolyte which are of different compositions. The intermediate layers are comprised of a blend of some of the materials used in the electrode and electrolyte compositions. Particle size is controlled to reduce problems involving differential shrinkage rates of the various layers when the entire structure is fired at a single temperature, while pore formers are provided in the electrolyte layers to be removed during firing for the formation of desired pores in the electrode layers. Each layer includes a binder in the form of a thermosetting acrylic which during initial processing is cured to provide a self-supporting structure with the ceramic components in the green state. A self-supporting corrugated structure is thus formed prior to firing, which the organic components of the binder and plasticizer removed during firing to provide a high strength, high temperature resistant ceramic structure of low weight and density.

Electrolyte volume effects on electrochemical performance and solid electrolyte interphase in Si-graphite/NMC lithium-ion pouch cells

DOE PAGES

An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

2017-05-15

This study aims to explore the correlations between electrolyte volume, electrochemical performance, and properties of the solid electrolyte interphase in pouch cells with Si-graphite composite anodes. The electrolyte is 1.2 M LiPF 6 in ethylene carbonate:ethylmethyl carbonate with 10 wt.% fluoroethylene carbonate. Single layer pouch cells (100 mAh) were constructed with 15 wt.% Si-graphite/LiNi 0.5Mn 0.3CO 0.2O 2 electrodes. It is found that a minimum electrolyte volume factor of 3.1 times the total pore volume of cell components (cathode, anode, and separator) is needed for better cycling stability. Less electrolyte causes increases in ohmic and charge transfer resistances. Lithium dendritesmore » are observed when the electrolyte volume factor is low. The resistances from the anodes become significant as the cells are discharged. As a result, solid electrolyte interphase thickness grows as the electrolyte volume factor increases and is non-uniform after cycling.« less

Characterization of thin films of the solid electrolyte Li(x)Mg(1-2x)Al(2+x)O4 (x = 0, 0.05, 0.15, 0.25).

PubMed

Put, Brecht; Vereecken, Philippe M; Mees, Maarten J; Rosciano, Fabio; Radu, Iuliana P; Stesmans, Andre

2015-11-21

RF-sputtered thin films of spinel Li(x)Mg(1-2x)Al(2+x)O4 were investigated for use as solid electrolyte. The usage of this material can enable the fabrication of a lattice matched battery stack, which is predicted to lead to superior battery performance. Spinel Li(x)Mg(1-2x)Al(2+x)O4 thin films, with stoichiometry (x) ranging between 0 and 0.25, were formed after a crystallization anneal as shown by X-ray diffraction and transmission electron microscopy. The stoichiometry of the films was evaluated by elastic recoil detection and Rutherford backscattering and found to be slightly aluminum rich. The excellent electronic insulation properties were confirmed by both current-voltage measurements as well as by copper plating tests. The electrochemical stability window of the material was probed using cyclic voltammetry. Lithium plating and stripping was observed together with the formation of a Li-Pt alloy, indicating that Li-ions passed through the film. This observation contradicted with impedance measurements at open circuit potential, which showed no apparent Li-ion conductivity of the film. Impedance spectroscopy as a function of potential showed the occurrence of Li-ion intercalation into the Li(x)Mg(1-2x)Al(2+x)O4 layers. When incorporating Li-ions in the material the ionic conductivity can be increased by 3 orders of magnitude. Therefore it is anticipated that the response of Li(x)Mg(1-2x)Al(2+x)O4 is more adequate for a buffer layer than as the solid electrolyte.

A Newly Designed Composite Gel Polymer Electrolyte Based on Poly(Vinylidene Fluoride-Hexafluoropropylene) (PVDF-HFP) for Enhanced Solid-State Lithium-Sulfur Batteries.

PubMed

Xia, Yan; Wang, Xiuli; Xia, Xinhui; Xu, Ruochen; Zhang, Shengzhao; Wu, Jianbo; Liang, Yanfei; Gu, Changdong; Tu, Jiangping

2017-10-26

Developing high-performance solid-state electrolytes is crucial for the innovation of next-generation lithium-sulfur batteries. Herein, a facile method for preparation of a novel gel polymer electrolyte (GPE) based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) is reported. Furthermore, Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 (LATP) nanoparticles as the active fillers are uniformly embedded into the GPE to form the final PVDF-HFP/LATP composite gel polymer electrolyte (CPE). Impressively, the obtained CPE demonstrates a high lithium ion transference number of 0.51 and improved electrochemical stability as compared to commercial liquid electrolyte. In addition, the assembled solid-sate Li-S battery with the composite gel polymer electrolyte membrane presents a high initial capacity of 918 mAh g -1 at 0.05 C, and better cycle performance than the counterparts with liquid electrolyte. Our designed PVDF-HFP/LATP composite can be a promising electrolyte for next-generation solid-state batteries with high cycling stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Approach for Analyzing Electrolyte Transport Properties and Their Effect on Protonic Ceramic Fuel Cell Performance.

PubMed

Danilov, Nikolay; Lyagaeva, Julia; Vdovin, Gennady; Medvedev, Dmitry; Demin, Anatoly; Tsiakaras, Panagiotis

2017-08-16

The design and development of highly conductive materials with wide electrolytic domain boundaries are among the most promising means of enabling solid oxide fuel cells (SOFCs) to demonstrate outstanding performance across low- and intermediate-temperature ranges. While reducing the thickness of the electrolyte is an extensively studied means for diminishing the total resistance of SOFCs, approaches involving an improvement in the transport behavior of the electrolyte membranes have been less-investigated. In the present work, a strategy for analyzing the electrolyte properties and their effect on SOFC output characteristics is proposed. To this purpose, a SOFC based on a recently developed BaCe 0.5 Zr 0.3 Dy 0.2 O 3-δ proton-conducting ceramic material was fabricated and tested. The basis of the strategy consists of the use of traditional SOFC testing techniques combined with the current interruption method and electromotive force measurements with a modified polarization-correction assessment. This allows one to determine simultaneously such important parameters as maximal power density; ohmic and polarization resistances; average ion transport numbers; and total, ionic, and electronic film conductivities and their activation energies. The proposed experimental procedure is expected to expand both fundamental and applied basics that could be further adopted to improve the technology of electrochemical devices based on proton-conducting electrolytes.

Combined soft and hard X-ray ambient pressure photoelectron spectroscopy studies of semiconductor/electrolyte interfaces

DOE PAGES

Starr, David E.; Favaro, Marco; Abdi, Fatwa F.; ...

2017-05-18

The development of solar fuel generating materials would greatly benefit from a molecular level understanding of the semiconductor/electrolyte interface and changes in the interface induced by an applied potential and illumination by solar light. Ambient pressure photoelectron spectroscopy techniques with both soft and hard X-rays, AP-XPS and AP-HAXPES respectively, have the potential to markedly contribute to this understanding. In this paper we initially provide two examples of current challenges in solar fuels material development that AP-XPS and AP-HAXPES can directly a ddress. This will be followed by a brief description of the distinguishing and complementary characteristics of soft and hardmore » X-ray AP-XPS and AP-HAXPES and best approaches to achieving monolayer sensitivity in solid/aqueous electrolyte studies. In particular we focus on the detection of surface adsorbed hydroxyl groups in the presence of aqueous hydroxide anions in the electrolyte, a common situation when investigating photoanodes for solar fuel generating applications. Finally, the article concludes by providing an example of a combined AP-XPS and AP-HAXPES study of a semiconductor/aqueous electrolyte interface currently used in water splitting devices specifically the BiVO 4/aqueous potassium phosphate electrolyte interface.« less

Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

PubMed

Sun, Che-Nan; Zawodzinski, Thomas A; Tenhaeff, Wyatt E; Ren, Fei; Keum, Jong Kahk; Bi, Sheng; Li, Dawen; Ahn, Suk-Kyun; Hong, Kunlun; Rondinone, Adam J; Carrillo, Jan-Michael Y; Do, Changwoo; Sumpter, Bobby G; Chen, Jihua

2015-03-28

Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xuefeng; Zhang, Minghao; Alvarado, Judith

Lithium metal has been considered as the “holy grail” anode material for rechargeable batteries though the dendritic growth and low Coulombic efficiency (CE) have crippled its practical use for decades. Its high chemical reactivity and low stability make it difficult to explore the intrinsic chemical and physical properties of the electrochemically deposited lithium (EDLi) and its accompanied solid electrolyte interphase (SEI). To prevent the dendritic growth and enhance the electrochemical reversibility, it is crucial to understand the nano- and meso- structures of EDLi. However, Li metal is very sensitive to beam damage and has low contrast for commonly used characterizationmore » techniques such as electron microscopy. Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)- electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nano scale while minimizing beam damage during imaging. Surprisingly, the results show that the nucleation dominated EDLi (five minutes at 0.5 mA cm-2) is amorphous while there is some crystalline LiF present in the SEI. The EDLi grown from various electrolytes with different additives exhibits distinctive surface properties. Consequently, these results highlight the importance of the SEI and its relationship with the CE. Our findings not only illustrate the capabilities of cryogenic microscopy for beam (thermal)-sensitive materials, but it yields crucial structural information of the EDLi evolution with and without electrolyte additives.« less

Detonation nanodiamond introduced into samarium doped ceria electrolyte improving performance of solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Pei, Kai; Li, Hongdong; Zou, Guangtian; Yu, Richeng; Zhao, Haofei; Shen, Xi; Wang, Liying; Song, Yanpeng; Qiu, Dongchao

2017-02-01

A novel electrolyte materials of introducing detonation nanodiamond (DNDs) into samarium doped ceria (SDC) is reported here. 1%wt. DNDs doping SDC (named SDC/ND) can enlarge the electrotyle grain size and change the valence of partial ceria. DNDs provide the widen channel to accelerate the mobility of oxygen ions in electrolyte. Larger grain size means that oxygen ions move easier in electrolyte, it can also reduce the alternating current (AC) impedance spectra of internal grains. The lower valence of partial Ce provides more oxygen vacancies to enhance mobility rate of oxygen ions. Hence all of them enhance the transportation of oxygen ions in SDC/ND electrolyte and the OCV. Ultimately the power density of SOFC can reach 762 mw cm-2 at 800 °C (twice higher than pure SDC, which is 319 mw cm-2 at 800 °C), and it remains high power density in the intermediate temperature (600-800 °C). It is relatively high for the electrolyte supported (300 μm) cells.

Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface.

PubMed

Yu, Chuang; Ganapathy, Swapna; Eck, Ernst R H van; Wang, Heng; Basak, Shibabrata; Li, Zhaolong; Wagemaker, Marnix

2017-10-20

Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode-electrolyte interface. However, direct assessment of the lithium-ion transport across realistic electrode-electrolyte interfaces is tedious. Here we report two-dimensional lithium-ion exchange NMR accessing the spontaneous lithium-ion transport, providing insight on the influence of electrode preparation and battery cycling on the lithium-ion transport over the interface between an argyrodite solid-electrolyte and a sulfide electrode. Interfacial conductivity is shown to depend strongly on the preparation method and demonstrated to drop dramatically after a few electrochemical (dis)charge cycles due to both losses in interfacial contact and increased diffusional barriers. The reported exchange NMR facilitates non-invasive and selective measurement of lithium-ion interfacial transport, providing insight that can guide the electrolyte-electrode interface design for future all-solid-state batteries.

High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self-Catalyzed Strategy toward Facile Synthesis.

PubMed

Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Liu, Zhihong; Cui, Guanglei; Feng, Jiwen

2017-11-01

It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self-catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte (C-PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li + and considerable ionic conductivity of 8.9 × 10 -5 S cm -1 at ambient temperature. Moreover, the LiFePO 4 /C-PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self-catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at leastmore » 5 mAh/cm.sup.2 at a C-rate of C/2.« less

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Triple-conducting layered perovskites as cathode materials for proton-conducting solid oxide fuel cells.

PubMed

Kim, Junyoung; Sengodan, Sivaprakash; Kwon, Goeun; Ding, Dong; Shin, Jeeyoung; Liu, Meilin; Kim, Guntae

2014-10-01

We report on an excellent anode-supported H(+) -SOFC material system using a triple conducting (H(+) /O(2-) /e(-) ) oxide (TCO) as a cathode material for H(+) -SOFCs. Generally, mixed ionic (O(2-) ) and electronic conductors (MIECs) have been selected as the cathode material of H(+) -SOFCs. In an H(+) -SOFC system, however, MIEC cathodes limit the electrochemically active sites to the interface between the proton conducting electrolyte and the cathode. New approaches to the tailoring of cathode materials for H(+) -SOFCs should therefore be considered. TCOs can effectively extend the electrochemically active sites from the interface between the cathode and the electrolyte to the entire surface of the cathode. The electrochemical performance of NBSCF/BZCYYb/BZCYYb-NiO shows excellent long term stability for 500 h at 1023 K with high power density of 1.61 W cm(-2) . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-Liquid Electrolyte as a Nanoion Modulator for Dendrite-Free Lithium Anodes.

PubMed

Wen, Kaihua; Wang, Yanlei; Chen, Shimou; Wang, Xi; Zhang, Suojiang; Archer, Lynden A

2018-06-20

Rechargeable lithium (Li) metal batteries are considered the most promising of Li-based energy storage technologies. However, tree-like dendrite produced by irregular Li + electrodeposition restricts it wide applications. Herein, based on a cation-microphase-regulation strategy, we create solid-liquid electrolytes (SLEs) by absorbing commercial liquid electrolytes into polyethylene glycol (PEG) engineered nanoporous Al 2 O 3 ceramic membranes. By means of molecular dynamics simulations and comprehensive experiments, we show that Li ions are regulated and promoted in the two microphases, the channel phase and nonchannel phase, respectively. The channel phase can achieve homogeneous Li + flux distribution by multiple mechanisms, including its uniform array of nanochannels and ability to suppress lateral dendrite growth by its high modulus. In the nonchannel phase, PEG chains swollen by electrolyte facilitate desolvation and fast conduction of Li + . As a result, the studied SLEs exhibit high ionic conductivity, low interfacial resistance, and the unique ability to stabilize deposition at the Li anode. By means of galvanostatic cycling studies in symmetric Li cells and Li/Li 4 Ti 5 O 12 cells, we further show that the materials open a path to Li metal batteries with excellent cycling performance.

A solid state actuator based on polypyrrole (PPy) and a solid electrolyte NBR working in air

NASA Astrophysics Data System (ADS)

Cho, Misuk; Nam, Jaedo; Choi, Hyouk Ryeol; Koo, Jachoon; Lee, Youngkwan

2005-05-01

The solid polymer electrolyte based conducting polymer actuator was presented. In the preparation of acutuator module, an ionic liquid impregnated a synthetic rubber (NBR) and PPy were used as a solid polymer electrolyte and conducting polymer, respectively. An ionic liquid, 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide (BMITFSI) is gradually dispersed into the NBR film and the conducting polymer, PPy was synthesized on the surface of NBR. The ionic conductivity of new type solid polymer electrolyte as a function of the immersion time was investigated. The cyclic voltammetry responsed and the redox switching dynamics of PEDOT in NBR matrix were studied. The displacement of the actuator was measured by laser beam.

Taichi-inspired rigid-flexible coupling cellulose-supported solid polymer electrolyte for high-performance lithium batteries

PubMed Central

Zhang, Jianjun; Yue, Liping; Hu, Pu; Liu, Zhihong; Qin, Bingsheng; Zhang, Bo; Wang, Qingfu; Ding, Guoliang; Zhang, Chuanjian; Zhou, Xinhong; Yao, Jianhua; Cui, Guanglei; Chen, Liquan

2014-01-01

Inspired by Taichi, we proposed rigid-flexible coupling concept and herein developed a highly promising solid polymer electrolyte comprised of poly (ethylene oxide), poly (cyano acrylate), lithium bis(oxalate)borate and robust cellulose nonwoven. Our investigation revealed that this new class solid polymer electrolyte possessed comprehensive properties in high mechanical integrity strength, sufficient ionic conductivity (3 × 10−4 S cm−1) at 60°C and improved dimensional thermostability (up to 160°C). In addition, the lithium iron phosphate (LiFePO4)/lithium (Li) cell using such solid polymer electrolyte displayed superior rate capacity (up to 6 C) and stable cycle performance at 80°C. Furthermore, the LiFePO4/Li battery could also operate very well even at an elevated temperature of 160°C, thus improving enhanced safety performance of lithium batteries. The use of this solid polymer electrolyte mitigates the safety risk and widens the operation temperature range of lithium batteries. Thus, this fascinating study demonstrates a proof of concept of the use of rigid-flexible coupling solid polymer electrolyte toward practical lithium battery applications with improved reliability and safety. PMID:25183416

Oxygen concentration sensor for an internal combustion engine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakajima, T.; Okada, Y.; Mieno, T.

1988-09-29

This patent describes an oxygen concentration sensor, comprising: an oxygen ion conductive solid electrolyte member forming a gas diffusion restricted region into which a measuring gas is introduced; a pair of electrodes sandwiching the solid electrolyte member; pump current supply means applying a pump voltage to the pair of electrodes through a current detection element to generate a pump current; and a heater element connected to the solid electrolyte member for heating the solid electrolyte member for heating the solid electrolyte member when a heater current is supplied from a heater current source; wherein the oxygen concentration sensor detects anmore » oxygen concentration in the measuring gas in terms of a current value of the pump current supplied through the current detection element and controls oxygen concentration in the gas diffusion restricted region by conducting oxygen ions through the solid electrolyte member in accordance to the flow of the pump current; and wherein the current detection element is connected to the electrode of the pair of electrodes facing the gas diffusion restricted region for insuring that the current value is representative of the pump current and possible leakage current from the heater current.« less

Computational Exploration of the Li-Electrode|Electrolyte Interface in the Presence of a Nanometer Thick Solid-Electrolyte Interphase Layer [Computational exploration of the Li-electrode|electrolyte interface complicated by a nanometer thin solid-electrolyte interphase (SEI) layer

DOE PAGES

Li, Yunsong; Leung, Kevin; Qi, Yue

2016-09-30

A nanometer thick passivation layer will spontaneously form on Li-metal in battery applications due to electrolyte reduction reactions. This passivation layer in rechargeable batteries must have “selective” transport properties: blocking electrons from attacking the electrolytes, while allowing Li + ion to pass through so the electrochemical reactions can continue. The classical description of the electrochemical reaction, Li + + e → Li 0, occurring at the Li-metal|electrolyte interface is now complicated by the passivation layer and will reply on the coupling of electronic and ionic degrees of freedom in the layer. We consider the passivation layer, called “solid electrolyte interphasemore » (SEI)”, as “the most important but the least understood in rechargeable Li-ion batteries,” partly due to the lack of understanding of its structure–property relationship. In predictive modeling, starting from the ab initio level, we find that it is an important tool to understand the nanoscale processes and materials properties governing the interfacial charge transfer reaction at the Li-metal|SEI|electrolyte interface. Here, we demonstrate pristine Li-metal surfaces indeed dissolve in organic carbonate electrolytes without the SEI layer. Based on joint modeling and experimental results, we point out that the well-known two-layer structure of SEI also exhibits two different Li + ion transport mechanisms. The SEI has a porous (organic) outer layer permeable to both Li + and anions (dissolved in electrolyte), and a dense (inorganic) inner layer facilitate only Li + transport. This two-layer/two-mechanism diffusion model suggests only the dense inorganic layer is effective at protecting Li-metal in electrolytes. This model suggests a strategy to deconvolute the structure–property relationships of the SEI by analyzing an idealized SEI composed of major components, such as Li 2CO 3, LiF, Li 2O, and their mixtures. After sorting out the Li+ ion diffusion carriers and their diffusion pathways, we design methods to accelerate the Li + ion conductivity by doping and by using heterogonous structure designs. We will predict the electron tunneling barriers and connect them with measurable first cycle irreversible capacity loss. We note that the SEI not only affects Li + and e – transport, but it can also impose a potential drop near the Li-metal|SEI interface. Our challenge is to fully describe the electrochemical reactions at the Li -metal|SEI|electrolyte interface. This will be the subject of ongoing efforts.« less

Computational Exploration of the Li-Electrode|Electrolyte Interface in the Presence of a Nanometer Thick Solid-Electrolyte Interphase Layer [Computational exploration of the Li-electrode|electrolyte interface complicated by a nanometer thin solid-electrolyte interphase (SEI) layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yunsong; Leung, Kevin; Qi, Yue

A nanometer thick passivation layer will spontaneously form on Li-metal in battery applications due to electrolyte reduction reactions. This passivation layer in rechargeable batteries must have “selective” transport properties: blocking electrons from attacking the electrolytes, while allowing Li + ion to pass through so the electrochemical reactions can continue. The classical description of the electrochemical reaction, Li + + e → Li 0, occurring at the Li-metal|electrolyte interface is now complicated by the passivation layer and will reply on the coupling of electronic and ionic degrees of freedom in the layer. We consider the passivation layer, called “solid electrolyte interphasemore » (SEI)”, as “the most important but the least understood in rechargeable Li-ion batteries,” partly due to the lack of understanding of its structure–property relationship. In predictive modeling, starting from the ab initio level, we find that it is an important tool to understand the nanoscale processes and materials properties governing the interfacial charge transfer reaction at the Li-metal|SEI|electrolyte interface. Here, we demonstrate pristine Li-metal surfaces indeed dissolve in organic carbonate electrolytes without the SEI layer. Based on joint modeling and experimental results, we point out that the well-known two-layer structure of SEI also exhibits two different Li + ion transport mechanisms. The SEI has a porous (organic) outer layer permeable to both Li + and anions (dissolved in electrolyte), and a dense (inorganic) inner layer facilitate only Li + transport. This two-layer/two-mechanism diffusion model suggests only the dense inorganic layer is effective at protecting Li-metal in electrolytes. This model suggests a strategy to deconvolute the structure–property relationships of the SEI by analyzing an idealized SEI composed of major components, such as Li 2CO 3, LiF, Li 2O, and their mixtures. After sorting out the Li+ ion diffusion carriers and their diffusion pathways, we design methods to accelerate the Li + ion conductivity by doping and by using heterogonous structure designs. We will predict the electron tunneling barriers and connect them with measurable first cycle irreversible capacity loss. We note that the SEI not only affects Li + and e – transport, but it can also impose a potential drop near the Li-metal|SEI interface. Our challenge is to fully describe the electrochemical reactions at the Li -metal|SEI|electrolyte interface. This will be the subject of ongoing efforts.« less

Creating Lithium-Ion Electrolytes with Biomimetic Ionic Channels in Metal-Organic Frameworks.

PubMed

Shen, Li; Wu, Hao Bin; Liu, Fang; Brosmer, Jonathan L; Shen, Gurong; Wang, Xiaofeng; Zink, Jeffrey I; Xiao, Qiangfeng; Cai, Mei; Wang, Ge; Lu, Yunfeng; Dunn, Bruce

2018-06-01

Solid-state electrolytes are the key to the development of lithium-based batteries with dramatically improved energy density and safety. Inspired by ionic channels in biological systems, a novel class of pseudo solid-state electrolytes with biomimetic ionic channels is reported herein. This is achieved by complexing the anions of an electrolyte to the open metal sites of metal-organic frameworks (MOFs), which transforms the MOF scaffolds into ionic-channel analogs with lithium-ion conduction and low activation energy. This work suggests the emergence of a new class of pseudo solid-state lithium-ion conducting electrolytes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-Liquid Lithium Electrolyte Nanocomposites Derived from Porous Molecular Cages.

PubMed

Petronico, Aaron; Moneypenny, Timothy P; Nicolau, Bruno G; Moore, Jeffrey S; Nuzzo, Ralph G; Gewirth, Andrew A

2018-06-20

We demonstrate that solid-liquid nanocomposites derived from porous organic cages are effective lithium ion electrolytes at room temperature. A solid-liquid electrolyte nanocomposite (SLEN) fabricated from a LiTFSI/DME electrolyte system and a porous organic cage exhibits ionic conductivity on the order of 1 × 10 -3 S cm -1 . With an experimentally measured activation barrier of 0.16 eV, this composite is characterized as a superionic conductor. Furthermore, the SLEN displays excellent oxidative stability up to 4.7 V vs Li/Li + . This simple three-component system enables the rational design of electrolytes from tunable discrete molecular architectures.

Lithium Polymer Electrolytes and Solid State NMR

NASA Technical Reports Server (NTRS)

Berkeley, Emily R.

2004-01-01

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Organosulfide-plasticized solid-electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Guoxing; Gao, Yue; He, Xin

Lithium metal is a promising anode candidate for the next-generation rechargeable battery due to its highest specific capacity (3860 mA h g -1) and lowest potential, but low Coulombic efficiency and formation of lithium dendrites hinder its practical application. Here, we report a self-formed flexible hybrid solid-electrolyte interphase layer through co-deposition of organosulfides/organopolysulfides and inorganic lithium salts using sulfur-containing polymers as an additive in the electrolyte. The organosulfides/organopolysulfides serve as “plasticizer” in the solid-electrolyte interphase layer to improve its mechanical flexibility and toughness. The as-formed robust solid-electrolyte interphase layers enable dendrite-free lithium deposition and significantly improve Coulombic efficiency (99% overmore » 400 cycles at a current density of 2mAcm -2). A lithium-sulfur battery based on this strategy exhibits long cycling life (1000 cycles) and good capacity retention. This study reveals an avenue to effectively fabricate stable solid-electrolyte interphase layer for solving the issues associated with lithium metal anodes.« less

Organosulfide-plasticized solid-electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries

DOE PAGES

Li, Guoxing; Gao, Yue; He, Xin; ...

2017-10-11

Lithium metal is a promising anode candidate for the next-generation rechargeable battery due to its highest specific capacity (3860 mA h g -1) and lowest potential, but low Coulombic efficiency and formation of lithium dendrites hinder its practical application. Here, we report a self-formed flexible hybrid solid-electrolyte interphase layer through co-deposition of organosulfides/organopolysulfides and inorganic lithium salts using sulfur-containing polymers as an additive in the electrolyte. The organosulfides/organopolysulfides serve as “plasticizer” in the solid-electrolyte interphase layer to improve its mechanical flexibility and toughness. The as-formed robust solid-electrolyte interphase layers enable dendrite-free lithium deposition and significantly improve Coulombic efficiency (99% overmore » 400 cycles at a current density of 2mAcm -2). A lithium-sulfur battery based on this strategy exhibits long cycling life (1000 cycles) and good capacity retention. This study reveals an avenue to effectively fabricate stable solid-electrolyte interphase layer for solving the issues associated with lithium metal anodes.« less

Rapid Thermal Annealing of Cathode-Garnet Interface toward High-Temperature Solid State Batteries.

PubMed

Liu, Boyang; Fu, Kun; Gong, Yunhui; Yang, Chunpeng; Yao, Yonggang; Wang, Yanbin; Wang, Chengwei; Kuang, Yudi; Pastel, Glenn; Xie, Hua; Wachsman, Eric D; Hu, Liangbing

2017-08-09

High-temperature batteries require the battery components to be thermally stable and function properly at high temperatures. Conventional batteries have high-temperature safety issues such as thermal runaway, which are mainly attributed to the properties of liquid organic electrolytes such as low boiling points and high flammability. In this work, we demonstrate a truly all-solid-state high-temperature battery using a thermally stable garnet solid-state electrolyte, a lithium metal anode, and a V 2 O 5 cathode, which can operate well at 100 °C. To address the high interfacial resistance between the solid electrolyte and cathode, a rapid thermal annealing method was developed to melt the cathode and form a continuous contact. The resulting interfacial resistance of the solid electrolyte and V 2 O 5 cathode was significantly decreased from 2.5 × 10 4 to 71 Ω·cm 2 at room temperature and from 170 to 31 Ω·cm 2 at 100 °C. Additionally, the diffusion resistance in the V 2 O 5 cathode significantly decreased as well. The demonstrated high-temperature solid-state full cell has an interfacial resistance of 45 Ω·cm 2 and 97% Coulombic efficiency cycling at 100 °C. This work provides a strategy to develop high-temperature all-solid-state batteries using garnet solid electrolytes and successfully addresses the high contact resistance between the V 2 O 5 cathode and garnet solid electrolyte without compromising battery safety or performance.

Electrochromic Behavior of Ionically Self-Assembled Thin Films

NASA Astrophysics Data System (ADS)

Janik, J. A.; Heflin, J. R.; Marciu, D.; Miller, M. B.; Davis, R. M.

2001-03-01

Ionically self-assembled monolayers (ISAMs), fabricated by alternate adsorption of cationic and anionic components, yield exceptionally homogeneous thin films with sub-nanometer control of the thickness and relative special location of the component materials. Using organic electrochromic materials such as polyaniline, we report studies of electrochromic responses in ISAM films. Reversible changes in the absorption spectrum are observed with the application of voltages on the order of 1.0 V. Measurements are made using both liquid electrolytes and in all-solid state devices incorporating solid polyelectrolytes such as poly(2-acylamido 2-methyl propane sulfonic acid) (PAMPS).

Enhanced ionic conductivity with Li{sub 7}O{sub 2}Br{sub 3} phase in Li{sub 3}OBr anti-perovskite solid electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jinlong, E-mail: jlzhu04@physics.unlv.edu, E-mail: yusheng.zhao@unlv.edu, E-mail: zhaoys@sustc.edu.cn; Li, Shuai; Zhang, Yi

Cubic anti-perovskites with general formula Li{sub 3}OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li{sub 3}OBr and layered Li{sub 7}O{sub 2}Br{sub 3,} by solid state reaction routes. The results indicate that with the phase fraction of Li{sub 7}O{sub 2}Br{sub 3} increasing to 44 wt.more » %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li{sub 3}OBr. Formation energy calculations revealed the meta-stable nature of Li{sub 7}O{sub 2}Br{sub 3}, which supports the great difficulty in producing phase-pure Li{sub 7}O{sub 2}Br{sub 3} at ambient pressure. Methods of obtaining phase-pure Li{sub 7}O{sub 2}Br{sub 3} will continue to be explored, including both high pressure and metathesis techniques.« less

Phosphorus Enrichment as a New Composition in the Solid Electrolyte Interphase of High-Voltage Cathodes and Its Effects on Battery Cycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Pengfei; Zheng, Jianming; Kuppan, Saravanan

2015-11-10

Immersion of a solid into liquid often leads to the modification of both the structure and chemistry of surface of the solid, which subsequently affects the chemical and physical properties of the system. For the case of the rechargeable lithium ion battery, such a surface modification is termed as solid electrolyte interphase (SEI) layer, which has been perceived to play critical role for the stable operation of the batteries. However, the structure and chemical composition of SEI layer and its spatial distribution and dependence on the battery operating condition remain unclear. By using aberration corrected scanning transmission electron microscopy coupledmore » with ultra-high sensitive energy dispersive x-ray spectroscopy, we probed the structure and chemistry of SEI layer on several high voltage cathodes. We show that layer-structured cathodes, when cycled at a high cut off voltage, can form a P-rich SEI layer on their surface, which is a direct evidence of Li-salt (LiPF6) decomposition. Our systematical investigations indicate such cathode/Li-salt side reaction shows strong dependence on structure of the cathode materials, operating voltage and temperature, indicating the feasibility of SEI engineering. These findings provide us valuable insights into the complex interface between the high-voltage cathode and the electrolyte.« less

Electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-01-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-09-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode and a semi-solid cathode. The semi-solid cathode includes a suspension of an active material of about 35% to about 75% by volume of an active material and about 0.5% to about 8% by volume of a conductive material in a non-aqueous liquid electrolyte. An ion-permeable membrane is disposed between the anode and the semi-solid cathode. The semi-solidmore » cathode has a thickness of about 250 .mu.m to about 2,000 .mu.m, and the electrochemical cell has an area specific capacity of at least about 7 mAh/cm.sup.2 at a C-rate of C/4. In some embodiments, the semi-solid cathode slurry has a mixing index of at least about 0.9.« less

Doping, Ionic Conductivity and Photothermal Stability of Functionalized DNA for Solar Energy Conversion and Electrochromic Applications

DTIC Science & Technology

2011-06-01

and coworkers 1,2,3,4 . They are renewable and biodegradable materials, recovered from waste in food industry (fruits, animal and fish meat waste) and...charges leads to the change of its absorption spectrum, or in other words to a change of its color . However in most cases the electrolyte used is in...electrodes (cf. Fig. 25). CeO2- TiO2 BK7 BK7 SOLID ELECTROLYTE ITO WO3 ITO Fig. 25. Structure of the used electrochromic cell 21 Figure 26

Plutonium recovery from spent reactor fuel by uranium displacement

DOEpatents

Ackerman, John P.

1992-01-01

A process for separating uranium values and transuranic values from fission products containing rare earth values when the values are contained together in a molten chloride salt electrolyte. A molten chloride salt electrolyte with a first ratio of plutonium chloride to uranium chloride is contacted with both a solid cathode and an anode having values of uranium and fission products including plutonium. A voltage is applied across the anode and cathode electrolytically to transfer uranium and plutonium from the anode to the electrolyte while uranium values in the electrolyte electrolytically deposit as uranium metal on the solid cathode in an amount equal to the uranium and plutonium transferred from the anode causing the electrolyte to have a second ratio of plutonium chloride to uranium chloride. Then the solid cathode with the uranium metal deposited thereon is removed and molten cadmium having uranium dissolved therein is brought into contact with the electrolyte resulting in chemical transfer of plutonium values from the electrolyte to the molten cadmium and transfer of uranium values from the molten cadmium to the electrolyte until the first ratio of plutonium chloride to uranium chloride is reestablished.

Stimuli Responsive Ionogels for Sensing Applications—An Overview

PubMed Central

Kavanagh, Andrew; Byrne, Robert; Diamond, Dermot; Fraser, Kevin J.

2012-01-01

This overview aims to summarize the existing potential of “Ionogels” as a platform to develop stimuli responsive materials. Ionogels are a class of materials that contain an Ionic Liquid (IL) confined within a polymer matrix. Recently defined as “a solid interconnected network spreading throughout a liquid phase”, the ionogel therefore combines the properties of both its solid and liquid components. ILs are low melting salts that exist as liquids composed entirely of cations and anions at or around 100 °C. Important physical properties of these liquids such as viscosity, density, melting point and conductivity can be altered to suit a purpose by choice of the cation/anion. Here we provide an overview to highlight the literature thus far, detailing the encapsulation of IL and responsive materials within these polymeric structures. Exciting applications in the areas of optical and electrochemical sensing, solid state electrolytes and actuating materials shall be discussed. PMID:24957961

Molecular dynamics simulations of Li transport between cathode crystals

NASA Astrophysics Data System (ADS)

Garofalini, S. H.

The molecular dynamics (MD) computer simulation technique has been used to study the effect of an amorphous intergranular film (IGF) present in a polycrystalline cathode on Li transport. The solid electrolyte is a model lithium silicate glass while the cathode is a nanocrystalline vanadia with an amorphous V 2O 5 IGF separating the crystals. Thin (˜1 to a few nanometer thick) IGFs are known to be present in most polycrystalline oxide materials. However, the role of such a film on Li transport in oxide cathodes has not been addressed. Current scanning probe microscopy (SPM) studies have shown that the orientation of the layered nanocrystalline vanadia crystals near the cathode/solid electrolyte interface is not optimized for Li ion transport. While the precise structure of the material between the crystals has not been identified, initially it can be initially considered as likely to be a thin non-crystalline (amorphous) film. This is based on the ubiquitous presence of such a structure in other polycrystalline oxides. Also, and with more relevance to the materials used in thin film batteries, an amorphous film can be expected to form between nanocrystals that crystallized from an amorphous matrix, as would be the case in a deposited thin film cathode. Consistent with simulations of Li transport in amorphous vanadia, the current simulations show that Li ions diffuse more rapidly into the amorphous intergranular thin film than into the layered vanadia with the (0 0 1) planes parallel to the cathode/electrolyte interface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graetz J.; Meng, Y.S.; McGilvray, T.

Oxides and their tailored structures are at the heart of electrochemical energy storage technologies and advances in understanding and controlling the dynamic behaviors in the complex oxides, particularly at the interfaces, during electrochemical processes will catalyze creative design concepts for new materials with enhanced and better-understood properties. Such knowledge is not accessible without new analytical tools. New innovative experimental techniques are needed for understanding the chemistry and structure of the bulk and interfaces, more importantly how they change with electrochemical processes in situ. Analytical Transmission Electron Microscopy (TEM) is used extensively to study electrode materials ex situ and is onemore » of the most powerful tools to obtain structural, morphological, and compositional information at nanometer scale by combining imaging, diffraction and spectroscopy, e.g., EDS (energy dispersive X-ray spectrometry) and Electron Energy Loss Spectrometry (EELS). Determining the composition/structure evolution upon electrochemical cycling at the bulk and interfaces can be addressed by new electron microscopy technique with which one can observe, at the nanometer scale and in situ, the dynamic phenomena in the electrode materials. In electrochemical systems, for instance in a lithium ion battery (LIB), materials operate under conditions that are far from equilibrium, so that the materials studied ex situ may not capture the processes that occur in situ in a working battery. In situ electrochemical operation in the ultra-high vacuum column of a TEM has been pursued by two major strategies. In one strategy, a 'nano-battery' can be fabricated from an all-solid-state thin film battery using a focused ion beam (FIB). The electrolyte is either polymer based or ceramic based without any liquid component. As shown in Fig. 1a, the interfaces between the active electrode material/electrolyte can be clearly observed with TEM imaging, in contrast to the composite electrodes/electrolyte interfaces in conventional lithium ion batteries, depicted in Fig.1b, where quantitative interface characterization is extremely difficult if not impossible. A second strategy involves organic electrolyte, though this approach more closely resembles the actual operation conditions of a LIB, the extreme volatility In Situ Analytical Electron Microscopy for Probing Nanoscale Electrochemistry by Ying Shirley Meng, Thomas McGilvray, Ming-Che Yang, Danijel Gostovic, Feng Wang, Dongli Zeng, Yimei Zhu, and Jason Graetz of the organic electrolytes present significant challenges for designing an in situ cell that is suitable for the vacuum environment of the TEM. Significant progress has been made in the past few years on the development of in situ electron microscopy for probing nanoscale electrochemistry. In 2008, Brazier et al. reported the first cross-section observation of an all solid-state lithium ion nano-battery by TEM. In this study the FIB was used to make a 'nano-battery,' from an all solid-state battery prepared by pulsed laser deposition (PLD). In situ TEM observations were not possible at that time due to several key challenges such as the lack of a suitable biasing sample holder and vacuum transfer of sample. In 2010, Yamamoto et al. successfully observed changes of electric potential in an all-solid-state lithium ion battery in situ with electron holography (EH). The 2D potential distribution resulting from movement of lithium ions near the positive-electrode/electrolyte interface was quantified. More recently Huang et al. and Wang et al. reported the in situ observations of the electrochemical lithiation of a single SnO{sub 2} nanowire electrode in two different in situ setups. In their approach, a vacuum compatible ionic liquid is used as the electrolyte, eliminating the need for complicated membrane sealing to prevent the evaporation of carbonate based organic electrolyte into the TEM column. One main limitation of this approach is that EELS spectral imaging is not possible due to the high plasmon signal of the ionic liquid. To this end, we have developed a novel in situ instrumental system combining analytical electron microscopy with advanced spectroscopy to probe the dynamic phenomena in an all solid-state nano-battery. In situ electron microscopy is a versatile technique that yields insights into challenging questions that could not be obtained using other techniques. However, in order to fully exploit the capabilities, a very carefully thought-out plan of action is essential. It is important to recognize that this is not just a simple characterization tool, but a collection of tools that make up a complete experimental set-up: the choice of FIB operation conditions, specimen holder for biasing, grid materials and design as well as microscope environment must be thoroughly considered before performing an experiment.« less

Self‐Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery

PubMed Central

Wu, Feng; Chen, Nan; Zhu, Qizhen; Tan, Guoqiang; Li, Li

2016-01-01

The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator‐based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable “nanogelator” that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid‐like apparent ionic conductivity of 2.93 × 10−3 S cm−1 at room temperature. The results show that the nanogelator, which possess self‐regulating ability, is able to immobilize imidazolium‐, pyrrolidinium‐, or piperidinium‐based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti‐nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes. PMID:27774385

Self-Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery.

PubMed

Wu, Feng; Chen, Nan; Chen, Renjie; Zhu, Qizhen; Tan, Guoqiang; Li, Li

2016-01-01

The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator-based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable "nanogelator" that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid-like apparent ionic conductivity of 2.93 × 10 -3 S cm -1 at room temperature. The results show that the nanogelator, which possess self-regulating ability, is able to immobilize imidazolium-, pyrrolidinium-, or piperidinium-based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti-nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes.

An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes

PubMed Central

Zhao, Chen-Zi; Zhang, Xue-Qiang; Cheng, Xin-Bing; Zhang, Rui; Xu, Rui; Chen, Peng-Yu; Peng, Hong-Jie; Huang, Jia-Qi

2017-01-01

Lithium metal is strongly regarded as a promising electrode material in next-generation rechargeable batteries due to its extremely high theoretical specific capacity and lowest reduction potential. However, the safety issue and short lifespan induced by uncontrolled dendrite growth have hindered the practical applications of lithium metal anodes. Hence, we propose a flexible anion-immobilized ceramic–polymer composite electrolyte to inhibit lithium dendrites and construct safe batteries. Anions in the composite electrolyte are tethered by a polymer matrix and ceramic fillers, inducing a uniform distribution of space charges and lithium ions that contributes to a dendrite-free lithium deposition. The dissociation of anions and lithium ions also helps to reduce the polymer crystallinity, rendering stable and fast transportation of lithium ions. Ceramic fillers in the electrolyte extend the electrochemically stable window to as wide as 5.5 V and provide a barrier to short circuiting for realizing safe batteries at elevated temperature. The anion-immobilized electrolyte can be applied in all–solid-state batteries and exhibits a small polarization of 15 mV. Cooperated with LiFePO4 and LiNi0.5Co0.2Mn0.3O2 cathodes, the all–solid-state lithium metal batteries render excellent specific capacities of above 150 mAh⋅g−1 and well withstand mechanical bending. These results reveal a promising opportunity for safe and flexible next-generation lithium metal batteries. PMID:28973945

Interfacial Reactivity Benchmarking of the Sodium Ion Conductors Na3PS4 and Sodium β-Alumina for Protected Sodium Metal Anodes and Sodium All-Solid-State Batteries.

PubMed

Wenzel, Sebastian; Leichtweiss, Thomas; Weber, Dominik A; Sann, Joachim; Zeier, Wolfgang G; Janek, Jürgen

2016-10-05

The interfacial stability of solid electrolytes at the electrodes is crucial for an application of all-solid-state batteries and protected electrodes. For instance, undesired reactions between sodium metal electrodes and the solid electrolyte form charge transfer hindering interphases. Due to the resulting large interfacial resistance, the charge transfer kinetics are altered and the overvoltage increases, making the interfacial stability of electrolytes the limiting factor in these systems. Driven by the promising ionic conductivities of Na 3 PS 4 , here we explore the stability and viability of Na 3 PS 4 as a solid electrolyte against metallic Na and compare it to that of Na-β″-Al 2 O 3 (sodium β-alumina). As expected, Na-β″-Al 2 O 3 is stable against sodium, whereas Na 3 PS 4 decomposes with an increasing overall resistance, making Na-β″-Al 2 O 3 the electrolyte of choice for protected sodium anodes and all-solid-state batteries.

Printable organic and inorganic materials for flexible electrochemical devices

NASA Astrophysics Data System (ADS)

Wojcik, Pawel Jerzy

The growing demand of consumer printed electronics such as smart cards, smart packaging, automotive displays, electronic paper and others led to the increased interest in fully printed electrochemical devices. These components are expected to be developed based on printed thin films derived from cheap and widely accessible compounds. This dissertation presents the long stretch of technical research that was performed to realize printed energy efficient concepts such as electrochromic displays and smart-windows. Within this broad theme, the presented study had a number of specific objectives, however, the overall aim was to develop low-cost material systems (i.e. printable mixtures) at a lab-scale, which would be compatible with large-scale roll-to-roll processing. Presented results concern three main topics: (i) dual-phase inorganic electrochromic material processed at low temperature, (ii) enhancement in electrochromic performance via metaloxide nanoparticles engineering, and (iii) highly conductive and mechanically stable solid-state electrolyte. First two topics are related to crystallographic structure of metal-oxide films derived from sol-gel precursor, which is shown to be critical for electrochemical performance. The proposed method of microstructure control enables development of electrochromic films which outperform their amorphous or nanocrystalline analogues presented in the state-of-the-art due to their superior chemical and physical properties. Developed materials and processes resulted in electrochemical devices exhibiting optical density on the level of 0.82 and switching time shorter than 3 seconds, reaching performance at practical level. Third topic concerns a new concept of solid state electrolyte based on plastic crystal doped with lithium salt, dispersed in a thermosetting polymer resin network. This soft matter printable electrolyte meets requirements for electrochromic applications, exhibiting ionic conductivities of 10. -6 - 10. -4 S cm-1 at ambient temperature, Young'sModulus in the range of 0.1 - 1.4 MPa and operational temperature up to 115°C. In order to extract information from massive computational data, model developed material systems and optimize composition, an efficient mathematical methodology based on statistical techniques was applied. This approach significantly reduces the number of experiments to be realized, while maintaining a high accuracy of the analysis. Using this approach the number of experiments has been reduced from 162 down to 30 in case of dual-phase electrochromic films, and from 729 down to 28 in study on solid-state electrolyte (when comparing to classical three-level full factorial approach). Coupling of statistical methods with formulation of electrochemically active materials shows the potential to maximize the capabilities of these systems.

Fabrication, testing and simulation of all solid state three dimensional Li-ion batteries

DOE PAGES

Talin, Albert Alec; Ruzmetov, Dmitry; Kolmakov, Andrei; ...

2016-11-10

Realization of safe, long cycle life and simple to package solid-state rechargeable batteries with high energy and power density has been a long-standing goal of the energy storage community. [1,2] Much of the research activity has been focused on developing new solid electrolytes with high Li ionic conductivity. In addition, LiPON, the only solid electrolyte currently used in commercial thin film solid state Li-ion batteris (SSLIBs), has a conductivity of ~10 -6 S/cm, compared to ~0.01 S/cm typically observed for liquid organic electrolytes [3].

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries.

PubMed

Hayashi, Akitoshi; Noi, Kousuke; Sakuda, Atsushi; Tatsumisago, Masahiro

2012-05-22

Innovative rechargeable batteries that can effectively store renewable energy, such as solar and wind power, urgently need to be developed to reduce greenhouse gas emissions. All-solid-state batteries with inorganic solid electrolytes and electrodes are promising power sources for a wide range of applications because of their safety, long-cycle lives and versatile geometries. Rechargeable sodium batteries are more suitable than lithium-ion batteries, because they use abundant and ubiquitous sodium sources. Solid electrolytes are critical for realizing all-solid-state sodium batteries. Here we show that stabilization of a high-temperature phase by crystallization from the glassy state dramatically enhances the Na(+) ion conductivity. An ambient temperature conductivity of over 10(-4) S cm(-1) was obtained in a glass-ceramic electrolyte, in which a cubic Na(3)PS(4) crystal with superionic conductivity was first realized. All-solid-state sodium batteries, with a powder-compressed Na(3)PS(4) electrolyte, functioned as a rechargeable battery at room temperature.

High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self‐Catalyzed Strategy toward Facile Synthesis

PubMed Central

Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Feng, Jiwen

2017-01-01

Abstract It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self‐catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte (C‐PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li+ and considerable ionic conductivity of 8.9 × 10−5 S cm−1 at ambient temperature. Moreover, the LiFePO4/C‐PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self‐catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes. PMID:29201612

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors.

PubMed

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-04-07

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br - in PIL-M-(Br) and TFSI - in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br - and TFSI - , respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g - ¹, 40 and 48 kW·kg - ¹, and 107 and 59.9 Wh·kg - ¹ were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively.

Reciprocated suppression of polymer crystallization toward improved solid polymer electrolytes: Higher ion conductivity and tunable mechanical properties

DOE PAGES

Bi, Sheng; Sun, Che-Nan; Zawodzinski, Thomas A.; ...

2015-08-06

Solid polymer electrolytes based on lithium bis(trifluoromethanesulfonyl) imide and polymer matrix were extensively studied in the past due to their excellent potential in a broad range of energy related applications. Poly(vinylidene fluoride) (PVDF) and polyethylene oxide (PEO) are among the most examined polymer candidates as solid polymer electrolyte matrix. In this paper, we study the effect of reciprocated suppression of polymer crystallization in PVDF/PEO binary matrix on ion transport and mechanical properties of the resultant solid polymer electrolytes. With electron and X-ray diffractions as well as energy filtered transmission electron microscopy, we identify and examine the appropriate blending composition thatmore » is responsible for the diminishment of both PVDF and PEO crystallites. Laslty, a three-fold conductivity enhancement is achieved along with a highly tunable elastic modulus ranging from 20 to 200 MPa, which is expected to contribute toward future designs of solid polymer electrolytes with high room-temperature ion conductivities and mechanical flexibility.« less

Novel Mg-Doped SrMoO3 Perovskites Designed as Anode Materials for Solid Oxide Fuel Cells

PubMed Central

Cascos, Vanessa; Alonso, José Antonio; Fernández-Díaz, María Teresa

2016-01-01

SrMo1−xMxO3−δ (M = Fe and Cr, x = 0.1 and 0.2) oxides have been recently described as excellent anode materials for solid oxide fuel cells at intermediate temperatures (IT-SOFC) with LSGM as the electrolyte. In this work, we have improved their properties by doping with aliovalent Mg ions at the B-site of the parent SrMoO3 perovskite. SrMo1−xMgxO3−δ (x = 0.1, 0.2) oxides have been prepared, characterized and tested as anode materials in single solid-oxide fuel cells, yielding output powers near 900 mW/cm−2 at 850 °C using pure H2 as fuel. We have studied its crystal structure with an “in situ” neutron power diffraction (NPD) experiment at temperatures as high as 800 °C, emulating the working conditions of an SOFC. Adequately high oxygen deficiencies, observed by NPD, together with elevated disk-shaped anisotropic displacement factors suggest a high ionic conductivity at the working temperatures. Furthermore, thermal expansion measurements, chemical compatibility with the LSGM electrolyte, electronic conductivity and reversibility upon cycling in oxidizing-reducing atmospheres have been carried out to find out the correlation between the excellent performance as an anode and the structural features. PMID:28773708

Further optimization of barium cerate properties via co-doping strategy for potential application as proton-conducting solid oxide fuel cell electrolyte

NASA Astrophysics Data System (ADS)

Wang, Shuai; Shen, Jianxing; Zhu, Zhiwen; Wang, Zhihao; Cao, Yanxin; Guan, Xiaoli; Wang, Yueyue; Wei, Zhaoling; Chen, Meina

2018-05-01

Yttrium-doped BaCeO3 is one of the most promising electrolyte candidates for solid oxide fuel cells because of its high ionic conductivity. Nd and Y co-doped BaCeO3 strategy is adopted for the further optimization of Y-doped BaCeO3 electrolyte properties. X-ray diffraction results indicate that the structure of BaCe0.8Y0.2-xNdxO3-δ (x = 0, 0.05, 0.1, 0.15) with orthorhombic perovskite phase becomes more symmetric with increasing Nd concentration. The scanning electron microscope observation demonstrates that the densification and grain size of the sintered pellets significantly enhance with the increase of Nd doping level. Whether in dry and humid hydrogen or air, the increase of Nd dopant firstly increases the conductivities of BaCe0.8Y0.2-xNdxO3-δ (x = 0, 0.05, 0.1, 0.15) and then decrease them after reaching the peak value at x = 0.05. Electrochemical impedance spectra at 350 °C can distinguish clearly the contribution of grain and grain boundary to total conductivity and the highest conductivity of BaCe0.8Y0.15Nd0.05O3-δ ascribes to the decrease in bulk and grain boundary resistances due to the synergistic effect of Nd and Y doping. The anode-supported single cell with BaCe0.8Y0.15Nd0.05O3-δ electrolyte shows an encouraging peak power density of 660 mW cm-2 at 700 °C, suggesting that BaCe0.8Y0.15Nd0.05O3-δ is a potential electrolyte material for the highly-efficient proton-conducting solid oxide fuel cell.

Vertically-aligned Mn(OH) 2 nanosheet films for flexible all-solid-state electrochemical supercapacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ziyuan; Gong, Jiangfeng; Tang, Chunmei

We report that the arrangement of the electrode materials is a significant contributor for constructing high performance supercapacitor. Here, vertically-aligned Mn(OH) 2 nanosheet thin films were synthesized by cathodic electrodeposition technique on flexible Au coated polyethylene terephthalate substrates. Morphologies, microstructures, chemical compositions and valence state of the nanosheet films were characterized systematically. It shows that the nanosheets arranged vertically to the substrate, forming a porous nanowall structures and creating large open framework, which greatly facilitate the adsorption or diffusion of electrolyte ions for faradaic redox reaction. Electrochemical tests of the films show the specific capacitance as high as 240.2 Fmore » g -1 at 1.0 A g -1. The films were employed to assemble symmetric all-solid-state supercapacitors with LiCl/PVA gel severed as solid electrolyte. Finally, the solid devices exhibit high volumetric capacitance of 39.3 mF cm -3 at the current density 0.3 mA cm -3 with robust cycling stability. The superior performance is attributed to the vertically-aligned configuration.« less

Vertically-aligned Mn(OH) 2 nanosheet films for flexible all-solid-state electrochemical supercapacitors

DOE PAGES

Yang, Ziyuan; Gong, Jiangfeng; Tang, Chunmei; ...

2017-08-28

We report that the arrangement of the electrode materials is a significant contributor for constructing high performance supercapacitor. Here, vertically-aligned Mn(OH) 2 nanosheet thin films were synthesized by cathodic electrodeposition technique on flexible Au coated polyethylene terephthalate substrates. Morphologies, microstructures, chemical compositions and valence state of the nanosheet films were characterized systematically. It shows that the nanosheets arranged vertically to the substrate, forming a porous nanowall structures and creating large open framework, which greatly facilitate the adsorption or diffusion of electrolyte ions for faradaic redox reaction. Electrochemical tests of the films show the specific capacitance as high as 240.2 Fmore » g -1 at 1.0 A g -1. The films were employed to assemble symmetric all-solid-state supercapacitors with LiCl/PVA gel severed as solid electrolyte. Finally, the solid devices exhibit high volumetric capacitance of 39.3 mF cm -3 at the current density 0.3 mA cm -3 with robust cycling stability. The superior performance is attributed to the vertically-aligned configuration.« less

Next-Generation Electrochemical Energy Materials for Intermediate Temperature Molten Oxide Fuel Cells and Ion Transport Molten Oxide Membranes.

PubMed

Belousov, Valery V

2017-02-21

High temperature electrochemical devices such as solid oxide fuel cells (SOFCs) and oxygen separators based on ceramic materials are used for efficient energy conversion. These devices generally operate in the temperature range of 800-1000 °C. The high operating temperatures lead to accelerated degradation of the SOFC and oxygen separator materials. To solve this problem, the operating temperatures of these electrochemical devices must be lowered. However, lowering the temperature is accompanied by decreasing the ionic conductivity of fuel cell electrolyte and oxygen separator membrane. Therefore, there is a need to search for alternative electrolyte and membrane materials that have high ionic conductivity at lower temperatures. A great many opportunities exist for molten oxides as electrochemical energy materials. Because of their unique electrochemical properties, the molten oxide innovations can offer significant benefits for improving energy efficiency. In particular, the newly developed electrochemical molten oxide materials show high ionic conductivities at intermediate temperatures (600-800 °C) and could be used in molten oxide fuel cells (MOFCs) and molten oxide membranes (MOMs). The molten oxide materials containing both solid grains and liquid channels at the grain boundaries have advantages compared to the ceramic materials. For example, the molten oxide materials are ductile, which solves a problem of thermal incompatibility (difference in coefficient of thermal expansion, CTE). Besides, the outstanding oxygen selectivity of MOM materials allows us to separate ultrahigh purity oxygen from air. For their part, the MOFC electrolytes show the highest ionic conductivity at intermediate temperatures. To evaluate the potential of molten oxide materials for technological applications, the relationship between the microstructure of these materials and their transport and mechanical properties must be revealed. This Account summarizes the latest results on oxygen ion transport in potential MOM materials and MOFC electrolytes. In addition, we consider the rapid oxygen transport in a molten oxide scale formed on a metal surface during catastrophic oxidation and show that the same transport could be used beneficially in MOMs and MOFCs. A polymer model explaining the oxygen transport in molten oxides is also considered. Understanding the oxygen transport mechanisms in oxide melts is important for the development of new generation energy materials, which will contribute to more efficient operation of electrochemical devices at intermediate temperatures. Here we highlight the progress made in developing this understanding. We also show the latest advances made in search of alternative molten oxide materials having high mixed ion electronic and ionic conductivities for use in MOMs and MOFCs, respectively. Prospects for further research are presented.

General method to predict voltage-dependent ionic conduction in a solid electrolyte coating on electrodes

NASA Astrophysics Data System (ADS)

Pan, Jie; Cheng, Yang-Tse; Qi, Yue

2015-04-01

Understanding the ionic conduction in solid electrolytes in contact with electrodes is vitally important to many applications, such as lithium ion batteries. The problem is complex because both the internal properties of the materials (e.g., electronic structure) and the characteristics of the externally contacting phases (e.g., voltage of the electrode) affect defect formation and transport. In this paper, we developed a method based on density functional theory to study the physics of defects in a solid electrolyte in equilibrium with an external environment. This method was then applied to predict the ionic conduction in lithium fluoride (LiF), in contact with different electrodes which serve as reservoirs with adjustable Li chemical potential (μLi) for defect formation. LiF was chosen because it is a major component in the solid electrolyte interphase (SEI) formed on lithium ion battery electrodes. Seventeen possible native defects with their relevant charge states in LiF were investigated to determine the dominant defect types on various electrodes. The diffusion barrier of dominant defects was calculated by the climbed nudged elastic band method. The ionic conductivity was then obtained from the concentration and mobility of defects using the Nernst-Einstein relationship. Three regions for defect formation were identified as a function of μLi: (1) intrinsic, (2) transitional, and (3) p -type region. In the intrinsic region (high μLi, typical for LiF on the negative electrode), the main defects are Schottky pairs and in the p -type region (low μLi, typical for LiF on the positive electrode) are Li ion vacancies. The ionic conductivity is calculated to be approximately 10-31Scm-1 when LiF is in contact with a negative electrode but it can increase to 10-12Scm-1 on a positive electrode. This insight suggests that divalent cation (e.g., Mg2+) doping is necessary to improve Li ion transport through the engineered LiF coating, especially for LiF on negative electrodes. Our results provide an understanding of the influence of the environment on defect formation and demonstrate a linkage between defect concentration in a solid electrolyte and the voltage of the electrode.

Liquid-like ionic conduction in solid lithium and sodium monocarba- closo-decaborates near or at room temperature

DOE PAGES

Tang, Wan Si; Matsuo, Motoaki; Wu, Hui; ...

2016-02-05

Both LiCB 9H 10 and NaCB 9H 10 exhibit liquid-like cationic conductivities (≥0.03 S cm –1) in their disordered hexagonal phases near or at room temperature. Furthermore, these unprecedented conductivities and favorable stabilities enabled by the large pseudoaromatic polyhedral anions render these materials in their pristine or further modified forms as promising solid electrolytes in next-generation, power devices.

Computational and Experimental Investigations of Na-Ion Conduction in Cubic Na 3PSe 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bo, Shou -Hang; Wang, Yan; Kim, Jae Chul

All-solid-state Na-ion batteries that operate at or close to room temperature are a promising next-generation battery technology with enhanced safety and reduced manufacturing cost. An indispensable component of this technology is the solid-state electrolyte that allows rapid shuttling of the mobile cation (i.e., Na +) between the cathode and anode. However, there are very few fast Na-ion conductors with ionic conductivity approaching that of the liquid counterparts (i.e., 1 mS cm –1). In this work, we present the synthesis and characterization of a fast Na-ion conductor, cubic Na 3PSe 4. This material possesses a room-temperature ionic conductivity exceeding 0.1 mSmore » cm –1 and does not require high-temperature sintering to minimize grain boundary resistance, making it a promising solid-state electrolyte candidate for all-solid-state Na-ion battery applications. On the basis of density functional theory, nudged elastic band, and molecular dynamics investigations, we demonstrate that the framework of cubic Na 3PSe 4 only permits rapid Na + diffusion with the presence of defects, and that the formation of the Na vacancy (charge-balanced by slight Se 2– oxidation) is more energetically favorable among the various defects considered. This finding provides important guidelines to further improve Na-ion conductivity in this class of materials.« less

Stabilization of superionic α-Agl at room temperature in a glass matrix

NASA Astrophysics Data System (ADS)

Tatsumisago, Masahiro; Shinkuma, Yoshikane; Minami, Tsutomu

1991-11-01

SINCE the discovery1 that the high-temperature phase of silver iodide (α-AgI) has an ionic conductivity comparable to that of the best liquid electrolytes, solid electrolytes have attracted wide interest. Possible applications of these materials range from solid-state batteries to electrochromic displays and sensors2. Although α-AgI displays conductivities of more than 10 S cm-1 (ref. 3), owing to the almost liquid-like mobility of Ag+ ions, the crystal transforms below 147 °C to the β-phase with a conductivity of only ~10-5 S cm-1 at room temperature. Efforts to achieve good conductivities at lower temperatures have focused on the addition of a second component to AgI to form solid solutions or new compounds such as RbAg4I5 and Ag2HgI4 (refs 4-7). Here we report our success in depressing the α-->β transformation temperature so as to stabilize α-AgI itself at room temperature. We use a melt-quenching technique to prepare crystallites of α-AgI frozen into a silver borate glass matrix. The quenched material showed diffraction peaks characteristic of α-AgI and displayed ionic conductivities of about 10-1 S cm-1. Further development of these glass/crystal composites may make the high ionic conductivity of α-AgI available for room-temperature solid-state applications.

Computational and Experimental Investigations of Na-Ion Conduction in Cubic Na 3PSe 4

DOE PAGES

Bo, Shou -Hang; Wang, Yan; Kim, Jae Chul; ...

2015-11-17

All-solid-state Na-ion batteries that operate at or close to room temperature are a promising next-generation battery technology with enhanced safety and reduced manufacturing cost. An indispensable component of this technology is the solid-state electrolyte that allows rapid shuttling of the mobile cation (i.e., Na +) between the cathode and anode. However, there are very few fast Na-ion conductors with ionic conductivity approaching that of the liquid counterparts (i.e., 1 mS cm –1). In this work, we present the synthesis and characterization of a fast Na-ion conductor, cubic Na 3PSe 4. This material possesses a room-temperature ionic conductivity exceeding 0.1 mSmore » cm –1 and does not require high-temperature sintering to minimize grain boundary resistance, making it a promising solid-state electrolyte candidate for all-solid-state Na-ion battery applications. On the basis of density functional theory, nudged elastic band, and molecular dynamics investigations, we demonstrate that the framework of cubic Na 3PSe 4 only permits rapid Na + diffusion with the presence of defects, and that the formation of the Na vacancy (charge-balanced by slight Se 2– oxidation) is more energetically favorable among the various defects considered. This finding provides important guidelines to further improve Na-ion conductivity in this class of materials.« less

In Situ Atomic-Scale Observation of Electrochemical Delithiation Induced Structure Evolution of LiCoO2 Cathode in a Working All-Solid-State Battery.

PubMed

Gong, Yue; Zhang, Jienan; Jiang, Liwei; Shi, Jin-An; Zhang, Qinghua; Yang, Zhenzhong; Zou, Dongli; Wang, Jiangyong; Yu, Xiqian; Xiao, Ruijuan; Hu, Yong-Sheng; Gu, Lin; Li, Hong; Chen, Liquan

2017-03-29

We report a method for in situ atomic-scale observation of electrochemical delithiation in a working all-solid-state battery using a state-of-the-art chip based in situ transmission electron microscopy (TEM) holder and focused ion beam milling to prepare an all-solid-state lithium-ion battery sample. A battery consisting of LiCoO 2 cathode, LLZO solid state electrolyte and gold anode was constructed, delithiated and observed in an aberration corrected scanning transmission electron microscope at atomic scale. We found that the pristine single crystal LiCoO 2 became nanosized polycrystal connected by coherent twin boundaries and antiphase domain boundaries after high voltage delithiation. This is different from liquid electrolyte batteries, where a series of phase transitions take place at LiCoO 2 cathode during delithiation. Both grain boundaries become more energy favorable along with extraction of lithium ions through theoretical calculation. We also proposed a lithium migration pathway before and after polycrystallization. This new methodology could stimulate atomic scale in situ scanning/TEM studies of battery materials and provide important mechanistic insight for designing better all-solid-state battery.

Electric double-layer capacitor based on an ionic clathrate hydrate.

PubMed

Lee, Wonhee; Kwon, Minchul; Park, Seongmin; Lim, Dongwook; Cha, Jong-Ho; Lee, Huen

2013-07-01

Herein, we suggest a new approach to an electric double-layer capacitor (EDLC) that is based on a proton-conducting ionic clathrate hydrate (ICH). The ice-like structures of clathrate hydrates, which are comprised of host water molecules and guest ions, make them suitable for applications in EDLC electrolytes, owing to their high proton conductivities and thermal stabilities. The carbon materials in the ICH Me4NOH⋅5 H2O show a high specific capacitance, reversible charge-discharge behavior, and a long cycle life. The ionic-hydrate complex provides the following advantages in comparison with conventional aqueous and polymer electrolytes: 1) The ICH does not cause leakage problems under normal EDLC operating conditions. 2) The hydrate material can be utilized itself, without requiring any pre-treatments or activation for proton conduction, thus shortening the preparation procedure of the EDLC. 3) The crystallization of the ICH makes it possible to tailor practical EDLC dimensions because of its fluidity as a liquid hydrate. 4) The hydrate solid electrolyte exhibits more-favorable electrochemical stability than aqueous and polymer electrolytes. Therefore, ICH materials are expected to find practical applications in versatile energy devices that incorporate electrochemical systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-state supercapacitors with rationally designed heterogeneous electrodes fabricated by large area spray processing for wearable energy storage applications.

PubMed

Huang, Chun; Zhang, Jin; Young, Neil P; Snaith, Henry J; Grant, Patrick S

2016-05-10

Supercapacitors are in demand for short-term electrical charge and discharge applications. Unlike conventional supercapacitors, solid-state versions have no liquid electrolyte and do not require robust, rigid packaging for containment. Consequently they can be thinner, lighter and more flexible. However, solid-state supercapacitors suffer from lower power density and where new materials have been developed to improve performance, there remains a gap between promising laboratory results that usually require nano-structured materials and fine-scale processing approaches, and current manufacturing technology that operates at large scale. We demonstrate a new, scalable capability to produce discrete, multi-layered electrodes with a different material and/or morphology in each layer, and where each layer plays a different, critical role in enhancing the dynamics of charge/discharge. This layered structure allows efficient utilisation of each material and enables conservative use of hard-to-obtain materials. The layered electrode shows amongst the highest combinations of energy and power densities for solid-state supercapacitors. Our functional design and spray manufacturing approach to heterogeneous electrodes provide a new way forward for improved energy storage devices.

Current status of solid-state lithium batteries employing solid redox polymerization cathodes

NASA Astrophysics Data System (ADS)

Visco, S. J.; Doeff, M. M.; Dejonghe, L. C.

1991-03-01

The rapidly growing demand for secondary batteries having high specific energy and power has naturally led to increased efforts in lithium battery technology. Still, the increased safety risks associated with high energy density systems has tempered the enthusiasm of proponents of such systems for use in the consumer marketplace. The inherent advantages of all-solid-state batteries in regards to safety and reliability are strong factors in advocating their introduction to the marketplace. However, the low ionic conductivity of solid electrolytes relative to nonaqueous liquid electrolytes implies low power densities for solid state systems operating at ambient temperatures. Recent advances in polymer electrolytes have led to the introduction of solid electrolytes having conductivities in the range of 10(exp -4)/ohm cm at room temperature; this is still two orders of magnitude lower than liquid electrolytes. Although these improved ambient conductivities put solid state batteries in the realm of practical devices, it is clear that solid state batteries using such polymeric separators will be thin film devices. Fortunately, thin film fabrication techniques are well established in the plastics and paper industry, and present the possibility of continuous web-form manufacturing. This style of battery manufacture should make solid polymer batteries very cost-competitive with conventional secondary cells. In addition, the greater geometric flexibility of thin film solid state cells should provide benefits in terms of the end-use form factor in device design. This work discusses the status of solid redox polymerization cathodes.

Thermal power transfer system using applied potential difference to sustain operating pressure difference

NASA Technical Reports Server (NTRS)

Bhandari, Pradeep (Inventor); Fujita, Toshio (Inventor)

1991-01-01

A thermal power transfer system using a phase change liquid gas fluid in a closed loop configuration has a heat exchanger member connected to a gas conduit for inputting thermal energy into the fluid. The pressure in the gas conduit is higher than a liquid conduit that is connected to a heat exchanger member for outputting thermal energy. A solid electrolyte member acts as a barrier between the gas conduit and the liquid conduit adjacent to a solid electrolyte member. The solid electrolyte member has the capacity of transmitting ions of a fluid through the electrolyte member. The ions can be recombined with electrons with the assistance of a porous electrode. An electrical field is applied across the solid electrolyte member to force the ions of the fluid from a lower pressure liquid conduit to the higher pressure gas conduit.

Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

PubMed Central

Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

2017-01-01

A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm−1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications. PMID:28067301

Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

NASA Astrophysics Data System (ADS)

Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

2017-01-01

A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm-1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications.

Experimental Evaluation of the Synthetic Solid Electrolyte Interface (SSEI) Concept for the Primary Ca-SOCl2 Battery System

DTIC Science & Technology

1988-12-01

coatings based on the Ca(Sr,Y)- Ge-S system can serve as an effective SSEI for Ca anodes in Ca-SOC12 primary cells using 1 M Ca(AlCl4 )2 as the electrolyte...I iy - LFI. CDY 4 EXPERIMENTAL EVALUATION OF THE SYNTHETIC SOLID ELECTROLYTE INTERFACE ( SSEI ) CONCEPT FOR THE PRIMARY Ca-SOC1 2 BA LERY SYSTEM...apply the concept of a synthetic solid electrolyte interface ( SSEI ) to overcome the problem of Ca corro- sion in Ca-SOC 2 primary cells. / To this end

Nanoporous adsorption effect on altering Li+ diffusion pathway by a highly ordered porous electrolyte additive for high rate all-solid-state lithium metal batteries.

PubMed

Li, Wenwen; Zhang, Sanpei; Wang, Bangrun; Gu, Sui; Xu, Dong; Wang, Jianing; Chen, Chunhua; Wen, Zhaoyin

2018-06-19

Solid polymer electrolytes (SPEs) have shown extraordinary promise for all-solid-state lithium metal batteries with high energy density and flexibility but are mainly limited by the low ionic conductivity and their poor stability with lithium metal anode. In this work, we propose a highly ordered porous electrolyte additive derived from SSZ-13 for high-rate all-solid-state lithium metal batteries. The nanoporous adsorption effect provided by the highly ordered porous nanoparticles in the poly (ethylene oxide) (PEO) electrolyte are found to significantly improve the Li + conductivity (1.91×10 -3 S cm -1 at 60°C, 4.43×10 -5 S cm -1 at 20°C) and widen the electrochemical stability window to 4.7 V vs Li + /Li. Meanwhile, the designed PEO-based electrolyte demonstrates enhanced stability with the lithium metal anode. Through systematically increasing Li + diffusion, widening the electrochemical stability window and enhancing the stability of the SSZ-CPE electrolyte, the LiFePO4/SSZ-CPE/Li cell is optimized to deliver high-rate capability and stable cycling performance, which demonstrates great potential for all-solid-state energy storage application.

Nickel/metal hydride secondary batteries using an alkaline solid polymer electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vassal, N.; Salmon, E.; Fauvarque, J.F.

1999-01-01

Sealed alkaline solid polymer electrolyte nickel/metal hydride laboratory cells have been constructed and tested to evaluate their properties. Studies of the cycle life, self-discharge, and behavior of cells at different temperatures were carried out. The first results on the electrochemical behavior of an alkaline solid polymer electrolyte [based on poly(ethylene oxide), potassium hydroxide, and water] medium are presented here and show good reversibility of this all-solid-state system for more than 500 cycles, without significant loss of capacity and with a reasonable average discharge efficiency (close to 80%). The temperature-dependence study allowed the determination of optimum operating conditions between 0 andmore » 40 C. Characteristics of the solid polymer electrolyte based Ni/MH cells are compared to those of several other rechargeable battery systems.« less

Monitoring the Electrochemical Processes in the Lithium–Air Battery by Solid State NMR Spectroscopy

PubMed Central

2013-01-01

A multi-nuclear solid-state NMR approach is employed to investigate the lithium–air battery, to monitor the evolution of the electrochemical products formed during cycling, and to gain insight into processes affecting capacity fading. While lithium peroxide is identified by 17O solid state NMR (ssNMR) as the predominant product in the first discharge in 1,2-dimethoxyethane (DME) based electrolytes, it reacts with the carbon cathode surface to form carbonate during the charging process. 13C ssNMR provides evidence for carbonate formation on the surface of the carbon cathode, the carbonate being removed at high charging voltages in the first cycle, but accumulating in later cycles. Small amounts of lithium hydroxide and formate are also detected in discharged cathodes and while the hydroxide formation is reversible, the formate persists and accumulates in the cathode upon further cycling. The results indicate that the rechargeability of the battery is limited by both the electrolyte and the carbon cathode stability. The utility of ssNMR spectroscopy in directly detecting product formation and decomposition within the battery is demonstrated, a necessary step in the assessment of new electrolytes, catalysts, and cathode materials for the development of a viable lithium–oxygen battery. PMID:24489976

Simulation of electrochemical behavior in Lithium ion battery during discharge process.

PubMed

Chen, Yong; Huo, Weiwei; Lin, Muyi; Zhao, Li

2018-01-01

An electrochemical Lithium ion battery model was built taking into account the electrochemical reactions. The polarization was divided into parts which were related to the solid phase and the electrolyte mass transport of species, and the electrochemical reactions. The influence factors on battery polarization were studied, including the active material particle radius and the electrolyte salt concentration. The results showed that diffusion polarization exist in the positive and negative electrodes, and diffusion polarization increase with the conducting of the discharge process. The physicochemical parameters of the Lithium ion battery had the huge effect on cell voltage via polarization. The simulation data show that the polarization voltage has close relationship with active material particle size, discharging rate and ambient temperature.

Simulation of electrochemical behavior in Lithium ion battery during discharge process

PubMed Central

Chen, Yong; Lin, Muyi; Zhao, Li

2018-01-01

An electrochemical Lithium ion battery model was built taking into account the electrochemical reactions. The polarization was divided into parts which were related to the solid phase and the electrolyte mass transport of species, and the electrochemical reactions. The influence factors on battery polarization were studied, including the active material particle radius and the electrolyte salt concentration. The results showed that diffusion polarization exist in the positive and negative electrodes, and diffusion polarization increase with the conducting of the discharge process. The physicochemical parameters of the Lithium ion battery had the huge effect on cell voltage via polarization. The simulation data show that the polarization voltage has close relationship with active material particle size, discharging rate and ambient temperature. PMID:29293535

A facile synthesis of high quality nanostructured CeO2 and Gd2O3-doped CeO2 solid electrolytes for improved electrochemical performance.

PubMed

Kuo, Yu-Lin; Su, Yu-Ming; Chou, Hung-Lung

2015-06-07

This study describes the use of a composite nitrate salt solution as a precursor to synthesize CeO2 and Gd2O3-doped CeO2 (GDC) nanoparticles (NPs) using an atmospheric pressure plasma jet (APPJ). The microstructures of CeO2 and GDC NPs were found to be cubical and spherical shaped nanocrystallites with average particle sizes of 10.5 and 6.7 nm, respectively. Reactive oxygen species, detected by optical emission spectroscopy (OES), are believed to be the major oxidative agents for the formation of oxide materials in the APPJ process. Based on the material characterization and OES observations, the study effectively demonstrated the feasibility of preparing well-crystallized GDC NPs by the APPJ system as well as the gas-to-particle mechanism. Notably, the Bader charge of CeO2 and Ce0.9Gd0.1O2 characterized by density function theory (DFT) simulation and AC impedance measurements shows that Gd helps in increasing the charge on Ce0.9Gd0.1O2 NPs, thus improving their conductivity and making them candidate materials for electrolytes in solid oxide fuel cells.

Performance improvement of gel- and solid-state dye-sensitized solar cells by utilization the blending effect of poly (vinylidene fluoride-co-hexafluropropylene) and poly (acrylonitrile-co-vinyl acetate) co-polymers

NASA Astrophysics Data System (ADS)

Venkatesan, Shanmugam; Obadja, Nesia; Chang, Ting-Wei; Chen, Li-Tung; Lee, Yuh-Lang

2014-12-01

Poly (vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) and poly (acrylonitrile-co-vinyl acetate) (PAN-VA) are used as gelator to prepare gel- and solid-state polymer electrolytes for dye sensitized solar cells (DSSCs) applications. The electrolytes prepared using PVDF-HFP have higher conductivities than those prepared using PAN-VA. In blended polymers, the conductivities of the electrolytes increase with increasing composition of PVDF-HFP; at 75% PVDF-HFP, conductivity of the blended polymer surpassed that of pure polymers. It is also found that the viscosity of the electrolyte prepared by PAN-VA (1.2 kPaS) is much lower than that by PVDF-HFP (11 kPaS). Therefore, increasing PAN-VA composition can decrease the viscosity of the electrolyte, improving the penetration of electrolytes in the TiO2 matrix. By controlling the ratio of PVDF-HFP/PAN-VA, the conductivity and viscosity of the electrolyte can be regulated and an optimal ratio based on the conversion efficiency of the gel- and solid state DSSCs is obtained at the ratio of 3/1. The highest efficiency achieved by the gel- and solid-state cells using the blending polymers are 6.3% and 4.88%, respectively, which are higher than those prepared using pure polymers (5.53% and 4.56%, respectively). The introduction of TiO2 fillers to the solid electrolyte can further increase the cell efficiency to 5.34%.

Highly Conductive Solid-State Hybrid Electrolytes Operating at Subzero Temperatures.

PubMed

Kwon, Taeyoung; Choi, Ilyoung; Park, Moon Jeong

2017-07-19

We report a unique, highly conductive, dendrite-inhibited, solid-state polymer electrolyte platform that demonstrates excellent battery performance at subzero temperatures. A design based on functionalized inorganic nanoparticles with interconnected mesopores that contain surface nitrile groups is the key to this development. Solid-state hybrid polymer electrolytes based on succinonitrile (SN) electrolytes and porous nanoparticles were fabricated via a simple UV-curing process. SN electrolytes were effectively confined within the mesopores. This stimulated favorable interactions with lithium ions, reduced leakage of SN electrolytes over time, and improved mechanical strength of membranes. Inhibition of lithium dendrite growth and improved electrochemical stability up to 5.2 V were also demonstrated. The hybrid electrolytes exhibited high ionic conductivities of 2 × 10 -3 S cm -1 at room temperature and >10 -4 S cm -1 at subzero temperatures, leading to stable and improved battery performance at subzero temperatures. Li cells made with lithium titanate anodes exhibited stable discharge capacities of 151 mAh g -1 at temperatures below -10 °C. This corresponds to 92% of the capacity achieved at room temperature (164 mAh g -1 ). Our work represents a significant advance in solid-state polymer electrolyte technology and far exceeds the performance available with conventional polymeric battery separators.

Plutonium recovery from spent reactor fuel by uranium displacement

DOEpatents

Ackerman, J.P.

1992-03-17

A process is described for separating uranium values and transuranic values from fission products containing rare earth values when the values are contained together in a molten chloride salt electrolyte. A molten chloride salt electrolyte with a first ratio of plutonium chloride to uranium chloride is contacted with both a solid cathode and an anode having values of uranium and fission products including plutonium. A voltage is applied across the anode and cathode electrolytically to transfer uranium and plutonium from the anode to the electrolyte while uranium values in the electrolyte electrolytically deposit as uranium metal on the solid cathode in an amount equal to the uranium and plutonium transferred from the anode causing the electrolyte to have a second ratio of plutonium chloride to uranium chloride. Then the solid cathode with the uranium metal deposited thereon is removed and molten cadmium having uranium dissolved therein is brought into contact with the electrolyte resulting in chemical transfer of plutonium values from the electrolyte to the molten cadmium and transfer of uranium values from the molten cadmium to the electrolyte until the first ratio of plutonium chloride to uranium chloride is reestablished.

Design and synthesis of a crystalline LiPON electrolyte

NASA Astrophysics Data System (ADS)

Holzwarth, N. A. W.; Senevirathne, Keerthi; Day, Cynthia S.; Lachgar, Abdessadek; Gross, Michael D.

2013-03-01

In the course of a computation study of the broad class of lithium phosphorus oxy-nitride materials of interest for solid electrolyte applications, Du and Holzwarth, [2] recently predicted a stable crystalline material with the stoichiometry Li2PO2N. The present paper reports the experimental preparation of the material using high temperature solid state synthesis and reports the results of experimental and calculational characterization studies. The so-named SD -Li2PO2N crystal structure has the orthorhombic space group Cmc21 with lattice constants a=9.0692(4) Å, b=5.3999(2) Å, and c=4.6856(2) Å. The structure is similar but not identical to the predicted structure, characterized by parallel arrangements of anionic phosphorus oxy-nitride chains having planar P -N -P -N backbones. Nitrogen 2p π states contribute to the strong bonding and to the chemical and thermal stablility of the material in air up to 600° C and in vacuum up to 1050° C. The measured Arrhenius activation energy for ionic conductivity is 0.6 eV which is comparable to computed vacancy migration energies in the presence of a significant population of Li+ ion vacancies. Supported by NSF grant DMR-1105485 and by a grnat from the Wake Forest University Center for Energy, Environment, and Sustainability.

All Solid State Rechargeable Lithium Batteries using Block Copolymers

NASA Astrophysics Data System (ADS)

Hallinan, Daniel; Balsara, Nitash

2011-03-01

The growing need for alternative energy and increased demand for mobile technology require higher density energy storage. Existing battery technologies, such as lithium ion, are limited by theoretical energy density as well as safety issues. Other battery chemistries are promising options for dramatically increasing energy density. Safety can be improved by replacing the flammable, reactive liquids used in existing lithium-ion battery electrolytes with polymer electrolytes. Block copolymers are uniquely suited for this task because ionic conductivity and mechanical strength, both important properties in battery formulation, can be independently controlled. In this study, lithium batteries were assembled using lithium metal as negative electrode, polystyrene-b-poly(ethylene oxide) copolymer with lithium salt as electrolyte, and a positive electrode. The positive electrode consisted of polymer electrolyte for ion conduction, carbon for electron conduction, and an active material. Batteries were charged and discharged over many cycles. The battery cycling results were compared to a conventional battery chemistry.

Tris(trimethylsilyl) Phosphite as an Efficient Electrolyte Additive To Improve the Surface Stability of Graphite Anodes.

PubMed

Yim, Taeeun; Han, Young-Kyu

2017-09-27

Tris(trimethylsilyl) phosphite (TMSP) has received considerable attention as a functional additive for various cathode materials in lithium-ion batteries, but the effect of TMSP on the surface stability of a graphite anode has not been studied. Herein, we demonstrate that TMSP serves as an effective solid electrolyte interphase (SEI)-forming additive for graphite anodes in lithium-ion batteries (LIBs). TMSP forms SEI layers by chemical reactions between TMSP and a reductively decomposed ethylene carbonate (EC) anion, which is strikingly different from the widely known mechanism of the SEI-forming additives. TMSP is stable under cathodic polarization, but it reacts chemically with radical anion intermediates derived from the electrochemical reduction of the carbonate solvents to generate a stable SEI layer. These TMSP-derived SEI layers improve the interfacial stability of the graphite anode, resulting in a retention of 96.8% and a high Coulombic efficiency of 95.2%. We suggest the use of TMSP as a functional additive that effectively stabilizes solid electrolyte interfaces of both the anode and cathode in lithium-ion batteries.

3-V Solid-State Flexible Supercapacitors with Ionic-Liquid-Based Polymer Gel Electrolyte for AC Line Filtering.

PubMed

Kang, Yu Jin; Yoo, Yongju; Kim, Woong

2016-06-08

State-of-the-art solid-state flexible supercapacitors with sufficiently fast response speed for AC line filtering application suffer from limited energy density. One of the main causes of the low energy density is the low cell voltage (1 V), which is limited by aqueous-solution-based gel electrolytes. In this work, we demonstrate for the first time a 3-V flexible supercapacitor for AC line filtering based on an ionic-liquid-based polymer gel electrolyte and carbon nanotube electrode material. The flexible supercapacitor exhibits an areal energy density that is more than 20 times higher than that of the previously demonstrated 1-V flexible supercapacitor (0.66 vs 0.03 μWh/cm(2)) while maintaining excellent capacitive behavior at 120 Hz. The supercapacitor shows a maximum areal power density of 1.5 W/cm(2) and a time constant of 1 ms. The improvement of the cell voltage while maintaining the fast-response capability greatly improves the potential of supercapacitors for high-frequency applications in wearable and/or portable electronics.

Solid-state supercapacitors with ionic liquid gel polymer electrolyte based on poly (3, 4-ethylenedioxythiophene), carbon nanotubes, and metal oxides nanocomposites for electrical energy storage

NASA Astrophysics Data System (ADS)

Obeidat, Amr M.

Clean and renewable energy systems have emerged as an important area of research having diverse and significant new applications. These systems utilize different energy storage methods such as the batteries and supercapacitors. Supercapacitors are electrochemical energy storage devices that are designed to bridge the gap between batteries and conventional capacitors. Supercapacitors which store electrical energy by electrical double layer capacitance are based on large surface area structured carbons. The materials systems in which the Faradaic reversible redox reactions store electrical energy are the transition metal oxides and electronically conducting polymers. Among the different types of conducting polymers, poly (3, 4- ethylenedioxythiophene) (PEDOT) is extensively investigated owing to its chemical and mechanical stability. Due to instability of aqueous electrolytes at high voltages and toxicity of organic electrolytes, potential of supercapacitors has not been fully exploited. A novel aspect of this work is in utilizing the ionic liquid gel polymer electrolyte to design solid-state supercapacitors for energy storage. Various electrochemical systems were investigated including graphene, PEDOT, PEDOT-carbon nanotubes, PEDOT-manganese oxide, and PEDOT-iron oxide nanocomposites. The electrochemical performance of solid-state supercapacitor devices was evaluated based on cyclic voltammetry (CV), charge-discharge (CD), prolonged cyclic tests, and electrochemical impedance spectroscopy (EIS) techniques. Raman spectroscopy technique was also utilized to analyze the bonding structure of the electrode materials. The graphene solid-state supercapacitor system displayed areal capacitance density of 141.83 mF cm-2 based on high potential window up to 4V. The PEDOT solid-state supercapacitor system was synthesized in acetonitrile and aqueous mediums achieving areal capacitance density of 219.17 mF cm-2. The hybrid structure of solid-state supercapacitors was also studied in solid-state design based on PEDOT and graphene electrodes that produced areal capacitance density of 198.26 mF cm-2. Symmetrical PEDOT-manganese oxide nanocomposites were synthesized by co-deposition and dip-coating techniques to fabricate solid-state supercapacitor systems achieving areal capacitance density of 122.08 mF cm-2 credited to the PEDOT-MnO2 supercapacitor that was synthesized by dipping the PEDOT electrode in pure KMnO4 solution. The electrochemical performance of PEDOT-carbon nanotube solid-state supercapacitors was also investigated in both acetonitrile and aqueous medium showing good dispersion characteristics with optimum CNT content of 1 mg. The PEDOT-CNT solid-state supercapacitor system synthesized in acetonitrile displayed areal capacitance density of 297.43 mF cm-2. PEDOT-Fe2O3 nanocomposites were synthesized by single-step co-deposition techniques, and these were used to fabricate solid-state supercapacitors achieving areal capacitance density of 96.89 mF cm-2. Furthermore, some of these thin flexible solid-state supercapacitors were integrated with solar cells for direct storage of solar electricity, which proved to be promising as autonomous power source for flexible and wearable electronics. This dissertation describes the electrode synthesis, design and properties of solid-state supercapacitors, and their electrochemical performance in the storage of electrical energy.

Application of atmospheric-pressure plasma jet processed carbon nanotubes to liquid and quasi-solid-state gel electrolyte supercapacitors

NASA Astrophysics Data System (ADS)

Kuok, Fei-Hong; Kan, Ken-Yuan; Yu, Ing-Song; Chen, Chieh-Wen; Hsu, Cheng-Che; Cheng, I.-Chun; Chen, Jian-Zhang

2017-12-01

We use a dc-pulse nitrogen atmospheric-pressure plasma jet (APPJ) to calcine carbon nanotubes (CNTs) pastes that are screen-printed on carbon cloth. 30-s APPJ treatment can efficiently oxidize and vaporize the organic binders, thereby forming porous structures. As indicated by X-ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA), the oxygen content decreases after APPJ treatment owing to the oxidation and vaporization of ethyl cellulose, terpineol, and ethanol. Nitrogen doping was introduced to the materials by the nitrogen APPJ. APPJ-calcination improves the wettability of the CNTs printed on carbon cloth, as evidenced by water contact angle measurement. Raman spectroscopy indicates that reactive species of nitrogen APPJ react violently with CNTs in only 30-s APPJ processing time and introduce defects and/or surface functional groups on CNTs. Carbon cloths with calcined CNT layers are used as electrodes for liquid and quasi-solid-state electrolyte supercapacitors. Under a cyclic voltammetry test with a 2 mV/s potential scan rate, the specific capacitance is 73.84 F/g (areal capacitance = 5.89 mF/cm2) with a 2 M KCl electrolyte and 66.47 F/g (areal capacitance = 6.10 mF/cm2) with a H2SO4/polyvinyl alcohol (PVA) gel electrolyte.

Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid.

PubMed

Yang, Chunpeng; Fu, Kun; Zhang, Ying; Hitz, Emily; Hu, Liangbing

2017-09-01

High-energy lithium-metal batteries are among the most promising candidates for next-generation energy storage systems. With a high specific capacity and a low reduction potential, the Li-metal anode has attracted extensive interest for decades. Dendritic Li formation, uncontrolled interfacial reactions, and huge volume effect are major hurdles to the commercial application of Li-metal anodes. Recent studies have shown that the performance and safety of Li-metal anodes can be significantly improved via organic electrolyte modification, Li-metal interface protection, Li-electrode framework design, separator coating, and so on. Superior to the liquid electrolytes, solid-state electrolytes are considered able to inhibit problematic Li dendrites and build safe solid Li-metal batteries. Inspired by the bright prospects of solid Li-metal batteries, increasing efforts have been devoted to overcoming the obstacles of solid Li-metal batteries, such as low ionic conductivity of the electrolyte and Li-electrolyte interfacial problems. Here, the approaches to protect Li-metal anodes from liquid batteries to solid-state batteries are outlined and analyzed in detail. Perspectives regarding the strategies for developing Li-metal anodes are discussed to facilitate the practical application of Li-metal batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

DOE PAGES

Yu, Seungho; Schmidt, Robert D.; Garcia-mendez, Regina; ...

2015-12-16

The oxide known as LLZO, with nominal composition Li 7La 3Zr 2O 12, is a promising solid electrolyte for Li-based batteries due to its high Li-ion conductivity and chemical stability with respect to lithium. Solid electrolytes may also enable the use of metallic Li anodes by serving as a physical barrier that suppresses dendrite initiation and propagation during cycling. Prior linear elasticity models of the Li electrode/solid electrolyte interface suggest that the stability of this interface is highly dependent on the elastic properties of the solid separator. For example, dendritic suppression is predicted to be enhanced as the electrolyte smore » shear modulus increases. In the present study a combination of first-principles calculations, acoustic impulse excitation measurements, and nanoindentation experiments are used to determine the elastic constants and moduli for highconductivity LLZO compositions based on Al and Ta doping. The calculated and measured isotropic shear moduli are in good agreement and fall within the range of 56-61 GPa. These values are an order of magnitude larger than that for Li metal and far exceed the minimum value ( 8.5 GPa) believed to be necessary to suppress dendrite initiation. These data suggest that LLZO exhibits sufficient stiffness to warrant additional development as a solid electrolyte for Li batteries.« less

Solid oxide fuel cells with bi-layered electrolyte structure

NASA Astrophysics Data System (ADS)

Zhang, Xinge; Robertson, Mark; Decès-Petit, Cyrille; Xie, Yongsong; Hui, Rob; Qu, Wei; Kesler, Olivera; Maric, Radenka; Ghosh, Dave

In this work, we have developed solid oxide fuel cells with a bi-layered electrolyte of 2 μm SSZ and 4 μm SDC using tape casting, screen printing, and co-firing processes. The cell reached power densities of 0.54 W cm -2 at 650 °C and 0.85 W cm -2 at 700 °C, with open circuit voltage (OCV) values larger than 1.02 V. The electrical leaking between anode and cathode through an SDC electrolyte has been blocked in the bi-layered electrolyte structure. However, both the electrolyte resistance (R el) and electrode polarization resistance (R p,a+c) increased in comparison to cells with single-layered SDC electrolytes. The formation of a solid solution of (Ce, Zr)O 2- x during sintering process and the flaws in the bi-layered electrolyte structure seem to be the main causes for the increase in the R el value (0.32 Ω cm 2) at 650 °C, which is almost one order of magnitude higher than the calculated value.

Synthesis, structural and electrical studies of Ba1-xSrxCe0.65Zr0.25Pr0.1O3-δ electrolyte materials for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Madhuri Sailaja, J.; Murali, N.; Margarette, S. J.; Mammo, Tulu Wegayehu; Veeraiah, V.

2018-03-01

This paper is discussed Sr doping effect on the microstructure, chemical stability and conductivity of Ba1-xSrxCe0.65Zr0.25Pr0.1O3-δ (0 ≤ x ≤ 0.2) electrolyte prepared by sol-gel method. The lattice constants and unit cell volumes are found to decrease as Sr atomic percentage increased in accordance with the Vegard law, confirming the formation of solid solution with orthorhombic structure. Among them all the synthesized samples are showed a conductivity with different atmosphere values at 500 °C. Ba0.92Sr0.08Ce0.65Zr0.25Pr0.1O3-δ recorded highest conductivity with a value of 3.3 × 10-6 S/cm (dry air) & 3.41 × 10-6 S/cm (wet air with 3% relative humidity) at 500 °C due to its smaller lattice volume, larger grain size and lower activation energy that led to excessive increase in conductivity. All pellets exhibited good chemical stability when exposed to air and H2O atmospheres. This study elucidates that the composition will be a promising electrolyte material for use as SOFC at intermediate temperatures if Sr doping is limited to small amounts.

Synthesis of POSS-based ionic conductors with low glass transition temperatures for efficient solid-state dye-sensitized solar cells.

PubMed

Zhang, Wei; Wang, Zhong-Sheng

2014-07-09

Replacing liquid-state electrolytes with solid-state electrolytes has been proven to be an effective way to improve the durability of dye-sensitized solar cells (DSSCs). We report herein the synthesis of amorphous ionic conductors based on polyhedral oligomeric silsesquioxane (POSS) with low glass transition temperatures for solid-state DSSCs. As the ionic conductor is amorphous and in the elastomeric state at the operating temperature of DSSCs, good pore filling in the TiO2 film and good interfacial contact between the solid-state electrolyte and the TiO2 film can be guaranteed. When the POSS-based ionic conductor containing an allyl group is doped with only iodine as the solid-state electrolyte without any other additives, power conversion efficiency of 6.29% has been achieved with good long-term stability under one-sun soaking for 1000 h.

Na3.4Zr1.8Mg0.2Si2PO12 filled poly(ethylene oxide)/Na(CF3SO2)2N as flexible composite polymer electrolyte for solid-state sodium batteries

NASA Astrophysics Data System (ADS)

Zhang, Zhizhen; Xu, Kaiqi; Rong, Xiaohui; Hu, Yong-Sheng; Li, Hong; Huang, Xuejie; Chen, Liquan

2017-12-01

Solid electrolytes with high ionic conductivity and excellent electrochemical stability are of prime significance to enable the application of solid-state batteries in energy storage and conversion. In this study, solid composite polymer electrolytes (CPEs) based on sodium bis(trifluorosulfonyl) imide (NaTFSI) and poly (ethylene oxide) (PEO) incorporated with active ceramic filler (NASICON) are reported for the first time. With the addition of NASICON fillers, the thermal stability and electrochemical stability of the CPEs are improved. A high conductivity of 2.8 mS/cm (at 80 °C) is readily achieved when the content of the NASICON filler in the composite polymer reaches 50 wt%. Furthermore, Na3V2(PO4)3/CPE/Na solid-state batteries using this composite electrolyte display good rate and excellent cycle performance.

Small quaternary alkyl phosphonium bis(fluorosulfonyl)imide ionic liquid electrolytes for sodium-ion batteries with P2- and O3-Na2/3[Fe2/3Mn1/3]O2 cathode material

NASA Astrophysics Data System (ADS)

Hilder, Matthias; Howlett, Patrick C.; Saurel, Damien; Gonzalo, Elena; Armand, Michel; Rojo, Teófilo; Macfarlane, Douglas R.; Forsyth, Maria

2017-05-01

A saturated solution of 2.3 M sodium bis(fluorosulfonyl)imide in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide ionic liquid shows a high conductivity (0.94 mScm-1 at 50 °C), low ion association, and a wide operational temperature window (-71 °C-305 °C) making it a promising electrolyte for sodium battery applications. Cycling with P2- and O3-Na2/3[Fe2/3Mn1/3]O2 cathode display excellent performance at 50 °C outperforming conventional organic solvent based electrolytes in terms of capacities (at C/10) and long term cycle stability (at C/2). Post analysis of the electrolyte shows no measurable changes while the sodium metal anode and the cathode surface shows the presence of electrolyte specific elements after cycling, suggesting the formation of a stabilizing solid electrolyte interface. Additionally, cycling changes the topography and particle morphology of the cathode. Thus, the electrolyte properties and cell performance match or outperform previously reported results with the additional benefit of replacing the hazardous and flammable organic solvent solutions commonly employed.

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors

PubMed Central

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-01-01

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br) and TFSI− in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively. PMID:29642456

The effect of diamond-like carbon coating on LiNi0.8Co0.15Al0.05O2 particles for all solid-state lithium-ion batteries based on Li2S-P2S5 glass-ceramics

NASA Astrophysics Data System (ADS)

Visbal, Heidy; Aihara, Yuichi; Ito, Seitaro; Watanabe, Taku; Park, Youngsin; Doo, Seokgwang

2016-05-01

There have been several reports on improvements of the performance of all solid-state battery using lithium metal oxide coatings on the cathode active material. However, the mechanism of the performance improvement remains unclear. To better understand the effect of the surface coating, we studied the impact of diamond-like carbon (DLC) coating on LiNi0.8Co0.15Al0.05O2 (NCA) by chemical vapor deposition (CVD). The DLC coated NCA showed good cycle ability and rate performance. This result is further supported by reduction of the interfacial resistance of the cathode and electrolyte observed in impedance spectroscopy. The DLC layer was analyzed by transmission electron microscopy electron energy loss spectroscopy (TEM-EELS). After 100 cycles the sample was analyzed by X-ray photo spectroscopy (XPS), and Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). These analyses showed that the thickness of the coating layer was around 4 nm on average, acting to hinder the side reactions between the cathode particle and the solid electrolyte. The results of this study will provide useful insights for understanding the nature of the buffer layer for the cathode materials.

Study, selection, and preparation of solid cationic conductors

NASA Technical Reports Server (NTRS)

Roth, W. L.; Mitoff, S. P.; King, R. N.

1972-01-01

Crystal chemical principles and transport theory were used to predict structures and specific compounds which might find application as solid electrolytes in rechargeable high energy and high power density batteries operating at temperatures less than 200 C. More than twenty compounds were synthesized or obtained and screened by nuclear magnetic resonance and conductivity. Many were densified by sintering or hot pressing. Encouraging results were obtained for nine of these materials but none have yet been good ionic conductors at low temperature.

Space charge induced surface stresses: implications in ceria and other ionic solids.

PubMed

Sheldon, Brian W; Shenoy, Vivek B

2011-05-27

Volume changes associated with point defects in space charge layers can produce strains that substantially alter thermodynamic equilibrium near surfaces in ionic solids. For example, near-surface compressive stresses exceeding -10 GPa are predicted for ceria. The magnitude of this effect is consistent with anomalous lattice parameter increases that occur in ceria nanoparticles. These stresses should significantly alter defect concentrations and key transport properties in a wide range of materials (e.g., ceria electrolytes in fuel cells). © 2011 American Physical Society

Ceramic Electrolyte Membrane Technology: Enabling Revolutionary Electrochemical Energy Storage

DTIC Science & Technology

2015-10-05

ion batteries . Solid-state Li- ion batteries could significantly improve safety and eliminate the need for complex...advancing ceramic electrolyte technology for use in solid-state Li- ion batteries . Solid-state Li- ion batteries could significantly improve safety and...technology for use in solid-state Li- ion batteries and high specific energy Li-S and Li- air batteries . Solid-state Li- ion batteries could

Production of an ion-exchange membrane-catalytic electrode bonded material for electrolytic cells

NASA Technical Reports Server (NTRS)

Takenaka, H.; Torikai, E.

1986-01-01

A good bond is achieved by placing a metal salt in solution on one side of a membrane and a reducing agent on the other side so that the reducing agent penetrates the membrane and reduces the metal. Thus, a solution containing Pt, Rh, etc., is placed on one side of the membrane and a reducing agent such as NaBH, is placed on the other side. The bonded metal layer obtained is superior in catalytic activity and is suitable as an electrode in a cell such as for solid polymer electrolyte water electrolysis.

Ion implantation of highly corrosive electrolyte battery components

DOEpatents

Muller, R.H.; Zhang, S.

1997-01-14

A method of producing corrosion resistant electrodes and other surfaces in corrosive batteries using ion implantation is described. Solid electrically conductive material is used as the ion implantation source. Battery electrode grids, especially anode grids, can be produced with greatly increased corrosion resistance for use in lead acid, molten salt, and sodium sulfur. 6 figs.

Ion implantation of highly corrosive electrolyte battery components

DOEpatents

Muller, Rolf H.; Zhang, Shengtao

1997-01-01

A method of producing corrosion resistant electrodes and other surfaces in corrosive batteries using ion implantation is described. Solid electrically conductive material is used as the ion implantation source. Battery electrode grids, especially anode grids, can be produced with greatly increased corrosion resistance for use in lead acid, molten salt, end sodium sulfur.

3-Dimensional Computational Fluid Dynamics Modeling of Solid Oxide Fuel Cell Using Different Fuels

DTIC Science & Technology

2011-01-01

major types of fuel cells in practice are listed below: Polymer Electrolyte Membrane Fuel Cell ( PEMFC ) Alkaline Fuel cell (AFC) Phosphoric Acid...Material Operating Temperature (oC) Efficiency (%) PEMFC H2, Methanol, Formic Acid Hydrated Organic Polymer < 90 40-50 AFC Pure H2 Aqueous

Performance of Solid Oxide Fuel Cell With La and Cr Co-doped SrTiO3 as Anode.

PubMed

Yi, Fenyun; Chen, Hongyu; Li, He

2014-06-01

The La 0.3 Sr 0.55 Ti 0.9 Cr 0.1 O 3-δ (LSTC10) anode material was synthesized by citric acid-nitrate process. The yttria-stabilized zirconia (YSZ) electrolyte-supported cell was fabricated by screen printing method using LSTC10 as anode and (La 0.75 Sr 0.25 ) 0.95 MnO 3-δ (LSM) as cathode. The electrochemical performance of cell was tested by using dry hydrogen as fuel and air as oxidant in the temperature range of 800-900 °C. At 900 °C, the open circuit voltage (OCV) and the maximum power density of cell are 1.08 V and 13.0 mW·cm -2 , respectively. The microstructures of cell after performance testing were investigated by scanning electron microscope (SEM). The results show that the anode and cathode films are porous and closely attached to the YSZ electrolyte. LSTC10 is believed to be a kind of potential solid oxide fuel cell (SOFC) anode material.

Bayesian-Driven First-Principles Calculations for Accelerating Exploration of Fast Ion Conductors for Rechargeable Battery Application.

PubMed

Jalem, Randy; Kanamori, Kenta; Takeuchi, Ichiro; Nakayama, Masanobu; Yamasaki, Hisatsugu; Saito, Toshiya

2018-04-11

Safe and robust batteries are urgently requested today for power sources of electric vehicles. Thus, a growing interest has been noted for fabricating those with solid electrolytes. Materials search by density functional theory (DFT) methods offers great promise for finding new solid electrolytes but the evaluation is known to be computationally expensive, particularly on ion migration property. In this work, we proposed a Bayesian-optimization-driven DFT-based approach to efficiently screen for compounds with low ion migration energies ([Formula: see text]. We demonstrated this on 318 tavorite-type Li- and Na-containing compounds. We found that the scheme only requires ~30% of the total DFT-[Formula: see text] evaluations on the average to recover the optimal compound ~90% of the time. Its recovery performance for desired compounds in the tavorite search space is ~2× more than random search (i.e., for [Formula: see text] < 0.3 eV). Our approach offers a promising way for addressing computational bottlenecks in large-scale material screening for fast ionic conductors.

Symposium on High Power, Ambient Temperature Lithium Batteries, 180th Meeting of the Electrochemical Society, Phoenix, AZ, Oct. 13-17, 1991, Proceedings

NASA Technical Reports Server (NTRS)

Clark, W. D. K. (Editor); Halpert, Gerald (Editor)

1992-01-01

Papers presented in these proceedings are on the state of the art in high-power lithium batteries, a design analysis of high-power Li-TiS2 battery, the performance and safety features of spiral wound lithium/thionyl chloride cells, the feasibility of a superhigh energy density battery of the Li/BrF3 electrochemical system, and an enhanced redox process of disulfide compounds and their application in high energy storage. Attention is also given to the structure and charge-discharge characteristics of mesophase-pitch based carbons, a study of carbons and graphites as anodes for lithium rechargeable cells, Li metal-free rechargeable Li(1+x)Mn2O4/carbon cells, and rechargeable lithium batteries using V6O13/V5O5 as the positive electrode material. Other papers discuss the electrochemical stability of organic electrolytes in contact with solid inorganic cathode materials, the electrochemical behavior of methyl formate solutions, and the interface between a solid polymer electrolyte and lithium anode.

Japan's Sunshine Project

NASA Astrophysics Data System (ADS)

1992-07-01

A summary report is given on the results of hydrogen energy research and development achieved during 1991 under the Sunshine Project. In hydrogen manufacturing, regenerative cells that can also generate power as fuel cells were discussed by using solid macromolecular electrolytic films for the case where no electrolysis is carried out with water electrolysis. Yttria stabilized zirconia (YSZ), an oxide solid electrolyte was used for the basic research on high-temperature steam electrolysis. Compositions of hydrogen storage alloys and their deterioration mechanisms were investigated to develop hydrogen transportation and storage technologies. High-density hydrides were searched, and fluidization due to paraffin was discussed. Electrode materials and forming technologies were discussed to develop a hydrogen to power conversion system using hydrogen storage alloys as reversible electrodes. Hydrogen-oxygen combustion was studied in terms of reactive theories, and so was the control of ignition and combustion using ultraviolet ray ignition plasma. Studies were made on hydrogen brittlement in welds on materials in hydrogen utilization and its preventive measures. Surveys were given on technical movements and development problems in high-efficiency, pollution-free hydrogen combustion turbines.

Polyphosphazene Solid Electrolytes.

DTIC Science & Technology

1984-10-01

soL..I’IIN ’ . LAV A - .:.u.s 009 ’-" 4. T .. T. edSutoe .TVCO EO T EI O Polyphosphazene Solid Electrolytes Interim Technical Repor 6. PEAFORMING RG ...Y. T.; Whitmore , D. H. Solid State Ionics 1982, 7, 129. (10) Bauerle, J. E. J. Phys. Chem. Solids 1969, 30, 2657. (11) MacDonald, J. R. J. Chem. Phys

Composite electrolytes of polyethylene oxides/garnets interfacially wetted by ionic liquid for room-temperature solid-state lithium battery

NASA Astrophysics Data System (ADS)

Huo, Hanyu; Zhao, Ning; Sun, Jiyang; Du, Fuming; Li, Yiqiu; Guo, Xiangxin

2017-12-01

Paramount attention has been paid on solid polymer electrolytes due to their potential in enhancement of energy density as well as improvement of safety. Herein, the composite electrolytes consisting of Li-salt-free polyethylene oxides and 200 nm-sized Li6.4La3Zr1.4Ta0.6O12 particles interfacially wetted by [BMIM]TF2N of 1.8 μL cm-2 have been prepared. Such wetted ionic liquid remains the solid state of membrane electrolytes and decreases the interface impedance between the electrodes and the electrolytes. There is no release of the liquid phase from the PEO matrix when the pressure of 5.0 × 104 Pa being applied for 24 h. The interfacially wetted membrane electrolytes show the conductivity of 2.2 × 10-4 S cm-1 at 20 °C, which is one order of magnitude greater than that of the membranes without the wetted ionic liquids. The conduction mechanism is related to a large number of lithium ions releasing from Li6.4La3Zr1.4Ta0.6O12 particles and the improved conductive paths along the ion-liquid-wetted interfaces between the polymer matrix and ceramic grains. When the membranes being used in the solid-state LiFePO4/Li and LiFe0.15Mn0.85PO4/Li cells at 25 °C, the excellent rate capability and superior cycle stability has been shown. The results provide a new prospect for solid polymer electrolytes used for room-temperature solid-state lithium batteries.

Solid electrolytes

DOEpatents

Abraham, Kuzhikalail M.; Alamgir, Mohamed

1993-06-15

This invention pertains to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized (encapsulated) in a solid organic polymer matrix. In particular, this invention relates to solid polymer electrolytes derived by immobilizing complexes (solvates) formed between a Li salt such as LiAsF.sub.6, LiCF.sub.3 SO.sub.3 or LiClO.sub.4 and a mixture of aprotic organic solvents having high dielectric constants such as ethylene carbonate (EC) (dielectric constant=89.6) and propylene carbonate (PC) (dielectric constant=64.4) in a polymer matrix such as polyacrylonitrile, poly(tetraethylene glycol diacrylate), or poly(vinyl pyrrolidinone).

Synthesis and structural studies on cerium substituted La0.4Ca0.6MnO3 as solid oxide fuel cell electrode material

NASA Astrophysics Data System (ADS)

Singh, Monika; Kumar, Dinesh; Singh, Akhilesh Kumar

2018-04-01

For solid oxide fuel cell electrode material, calcium doped lanthanum manganite La0.4Ca0.6MnO3 (LCMO) and cerium-incorporated on Ca-site with composition La0.40Ca0.55Ce0.05MnO3 (LCCMO) were synthesized using most feasible and efficient glycine-nitrate method. The formation of crystalline single phase was confirmed by x-ray diffraction (XRD). The Rietveld analysis reveals that both systems crystallize into orthorhombic crystal structure with Pnma space group. Additionally, 8 mole % Y2O3 stabilized ZrO2 (8YSZ) solid electrolyte was also synthesized using high energy ball mill to check the reaction with electrode materials. It was found that the substitution of Ce+4 cations in LCMO perovskite suppressed formation of undesired insulating CaZrO3 phase.

Novel thixotropic gel electrolytes based on dicationic bis-imidazolium salts for quasi-solid-state dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Kim, Jun Young; Kim, Tae Ho; Kim, Dong Young; Park, Nam-Gyu; Ahn, Kwang-Duk

Novel thixotropic gel electrolytes have been successfully prepared by utilizing oligomeric poly(ethylene oxide) (PEO)-based bis-imidazolium diiodide salts and hydrophilic silica nanoparticles for application in quasi-solid-state dye-sensitized solar cells (DSSCs). The thixotropic gel-state of the ionic liquid-based composite electrolytes is confirmed by observing the typical hysteresis loop and temporary hydrogen bonding. On using the PEO-based composite electrolyte, a quasi-solid-state DSSC exhibited highly improved properties such as easy penetration of the electrolyte into the cell without leakage, long-term stability, high open-circuit voltage without the use of 4- tert-butylpyridine, and a high energy-conversion efficiency of 5.25% under AM 1.5 illumination (100 mW cm -2).

Superior Conductive Solid-like Electrolytes: Nanoconfining Liquids within the Hollow Structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jinshui; Bai, Ying; Sun, Xiao-Guang

2015-01-01

The growth and proliferation of lithium (Li) dendrites during cell recharge is unavoidable, which seriously hinders the development and application of rechargeable Li metal batteries. Solid electrolytes with robust mechanical modulus are regarded as a promising approach to overcome the dendrite problems. However, their room-temperature ionic conductivities are usually too low to reach the level required for normal battery operation. Here, a class of novel solid electrolytes with liquid-like room-temperature ionic conductivities (> 1 mS cm-1) has been successfully synthesized by taking advantage of the unique nanoarchitectures of hollow silica (HS) spheres to confine liquid electrolytes in hollow space tomore » afford high conductivities. In a symmetric lithium/lithium cell, such kind of solid-like electrolytes demonstrates a robust performance against Li dendrite problems, well stabilizing the cell system from short circuiting in a long-time operation at current densities ranging from 0.16 to 0.32 mA cm-2. Moreover, the high flexibility and compatibility of HS nanoarchitectures, in principle, enables broad tunability to choose desired liquids for the fabrication of other kinds of solid-like electrolytes, such as those containing Na+, Mg2+ or Al3+ as conductive media, providing a useful alternative strategy for the development of next generation rechargeable batteries.« less

Cellulose nanocrystal-based composite electrolyte with superior dimensional stability for alkaline fuel cell membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Yuan; Artmentrout, Aaron A.; Li, Juchuan

2015-05-13

Cellulose nanocrystal (CNC)-based composite films were prepared as a solid electrolyte for alkaline fuel cells. Poly (vinyl alcohol) (PVA) and silica gel hybrid was used to bind the CNCs to form a robust composite film. The mass ratio (i.e., 1 : 1, 1 : 2) of PVA and silica gel was tuned to control the hydrophobicity of the resulting films. Composite films with a range of CNC content (i.e., 20 to 60%) were prepared to demonstrate the impact of CNC on the performance of these materials as a solid electrolyte for alkaline fuel cells. Different from previously reported cross-linked polymermore » films, CNC-based composite films with 40% hydrophobic binder (i.e., PVA : silica gel=1 : 2) exhibited simultaneous low water swelling (e.g., ~5%) and high water uptake (e.g., ~80%) due to the hydrophilicity and extraordinary dimensional stability of CNC. It also showed a conductivity of 0.044 and 0.065 S/cm at 20 and 60 oC, respectively. To the best of our knowledge, the film with 60% CNC and 40% binder is characterized by the lowest hydroxide conductivity-normalized swelling ratio. Decreased CNC content (i.e., 40 and 20%) resulted in comparable hydroxide conductivity but a greater swelling ratio. Finally, these results demonstrate the advantage of CNC as a key component for a solid electrolyte for alkaline fuel cells over conventional polymers, suggesting the great potential of CNCs in improving the dimensional stability while maintaining the conductivity of existing anion exchange membranes.« less

Study of solid electrolyte layers in I{sub 2}(P2VP)-Li power sources by the galvanostatic pulse technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nimon, E.S.; Shirokov, A.V.; Kovynev, N.P.

1995-04-01

Transport properties of solid-electrolyte layers (SEL) formed in lithium-iodine batteries were studied by the galvanostatic pulse technique. It was found that the rate of the anodic process at the lithium electrode is determined by the formation of an ionic space charge of lithium cations injected into solid-electrolyte layers. The mobility and concentration of mobile lithium cations in SELs at various depths of discharge of the power source were determined.

Solid Polymer Electrolyte (SPE) fuel cell technology program

NASA Technical Reports Server (NTRS)

1979-01-01

The overall objectives of the Phase IV Solid Polymer Electrolyte Fuel Cell Technology Program were to: (1) establish fuel cell life and performance at temperatures, pressures and current densities significantly higher than those previously demonstrated; (2) provide the ground work for a space energy storage system based on the solid polymer electrolyte technology (i.e., regenerative H2/O2 fuel cell); (3) design, fabricate and test evaluate a full-scale single cell unit. During this phase, significant progress was made toward the accomplishment of these objectives.

Development of planar solid oxide fuel cells for power generation applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minh, N.Q.

1996-04-01

Planar solid oxide fuel cells (SOFCs) are presently being developed for a variety of electric power generation application. The planar design offers simple cell geometry, high power density, and multiple fabrication and gas manifolding options. Planar SOFC technology has received much attention recently, and significant progress has been made in this area. Recent effort at AlliedSignal has focused on the development of high-performance, lightweight planar SOFCs, having thin-electrolyte films, that can be operated efficiently at reduced temperatures (< 1000{degrees}C). The advantages of reduced-temperature operation include wider material choice (including use of metallic interconnects), expected longer cell life, reduced thermal stress,more » improved reliability, and reduced fuel cell cost. The key aspect in the development of thin-film SIFCs is to incorporate the thin electrolyte layer into the desired structure of cells in a manner that yields the required characteristics. AlliedSignal has developed a simple and cost-effective method based on tape calendering for the fabrication of thin-electrolyte SOFCs. Thin-electrolyte cells made by tape calendering have shown extraordinary performance, e.g., producing more than 500mW/cm{sup 2} at 700{degrees}C and 800mW/cm{sup 2} at 800{degrees}C with hydrogen as fuel and air is oxidant. thin-electrolyte single cells have been incorporated into a compliant metallic stack structure and operated at reduced and operated at reduced-temperature conditions.« less

Optimization of Pore Structure of Cathodic Carbon Supports for Solvate Ionic Liquid Electrolytes Based Lithium-Sulfur Batteries.

PubMed

Zhang, Shiguo; Ikoma, Ai; Li, Zhe; Ueno, Kazuhide; Ma, Xiaofeng; Dokko, Kaoru; Watanabe, Masayoshi

2016-10-04

Lithium-sulfur (Li-S) batteries are a promising energy-storage technology owing to their high theoretical capacity and energy density. However, their practical application remains a challenge because of the serve shuttle effect caused by the dissolution of polysulfides in common organic electrolytes. Polysulfide-insoluble electrolytes, such as solvate ionic liquids (ILs), have recently emerged as alternative candidates and shown great potential in suppressing the shuttle effect and improving the cycle stability of Li-S batteries. Redox electrochemical reactions in polysulfide-insoluble electrolytes occur via a solid-state process at the interphase between the electrolyte and the composite cathode; therefore, creating an appropriate interface between sulfur and a carbon support is of great importance. Nevertheless, the porous carbon supports established for conventional organic electrolytes may not be suitable for polysulfide-insoluble electrolytes. In this work, we investigated the effect of the porous structure of carbon materials on the Li-S battery performance in polysulfide-insoluble electrolytes using solvate ILs as a model electrolyte. We determined that the pore volume (rather than the surface area) exerts a major influence on the discharge capacity of S composite cathodes. In particular, inverse opal carbons with three-dimensionally ordered interconnected macropores and a large pore volume deliver the highest discharge capacity. The battery performance in both polysulfide-soluble electrolytes and solvate ILs was used to study the effect of electrolytes. We propose a plausible mechanism to explain the different porous structure requirements in polysulfide-soluble and polysulfide-insoluble electrolytes.

Water-Free Proton-Conducting Membranes for Fuel Cells

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram; Yen, Shiao-Pin

2007-01-01

Poly-4-vinylpyridinebisulfate (P4VPBS) is a polymeric salt that has shown promise as a water-free proton-conducting material (solid electrolyte) suitable for use in membrane/electrode assemblies in fuel cells. Heretofore, proton-conducting membranes in fuel cells have been made from perfluorinated ionomers that cannot conduct protons in the absence of water and, consequently, cannot function at temperatures >100 C. In addition, the stability of perfluorinated ionomers at temperatures >100 C is questionable. However, the performances of fuel cells of the power systems of which they are parts could be improved if operating temperatures could be raised above 140 C. What is needed to make this possible is a solid-electrolyte material, such as P4VPBS, that can be cast into membranes and that both retains proton conductivity and remains stable in the desired higher operating temperature range. A family of solid-electrolyte materials different from P4VPBS was described in Anhydrous Proton-Conducting Membranes for Fuel Cells (NPO-30493), NASA Tech Briefs, Vol. 29, No. 8 (August 2005), page 48. Those materials notably include polymeric quaternized amine salts. If molecules of such a polymeric salt could be endowed with flexible chain structures, it would be possible to overcome the deficiencies of simple organic amine salts that must melt before being able to conduct protons. However, no polymeric quaternized amine salts have yet shown to be useful in this respect. The present solid electrolyte is made by quaternizing the linear polymer poly- 4-vinylpyridine (P4VP) to obtain P4VPBS. It is important to start with P4VP having a molecular weight of 160,000 daltons because P4VPBS made from lower-molecular-weight P4VP yields brittle membranes. In an experimental synthesis, P4VP was dissolved in methanol and then reacted with an excess of sulfuric acid to precipitate P4VPBS. The precipitate was recovered, washed several times with methanol to remove traces of acid, and dried to a white granular solid. In another synthesis, nanoparticles of silica rich with surface hydroxyl groups were added to P4VP in methanol solution, which was then reacted with excess sulfuric acid to precipitate granules of a composite that most probably had the composition (P4VPBS)-SiO2-SiO(HSO4)2. The granular P4VPBS produced in the first-mentioned synthesis was dissolved in water to make a glue-like, turbid solution; the granular P4VPBS/silica composite produced in the second-mentioned synthesis was mixed with water to make a turbid, glue-like suspension. The proportions of polymer salt to water in such preparations can be varied; it was found that approximately equal parts of water and polymer salt yield a solution or suspension amenable to further processing.

Fluorine-doped antiperovskite electrolyte for all-solid-state Lithium-ion batteries

DOE PAGES

Li, Yutao; Zhou, Weidong; Xin, Sen; ...

2016-06-30

A fluorine-doped antiperovskite Li-ion conducto Li 2(OH)X (X=Cl, Br) is shown to be a promising candidat for a solid electrolyte in an all-solid-state Li-ion rechargeabl battery. Substitution of F¯ for OH¯ transforms orthorhombi Li 2OHCl to a room-temperature cubic phase, which show electrochemical stability to 9 V versus Li +/Li and two orders o magnitude higher Li-ion conductivity than that of orthorhombi Li 2OHCl. As a result, an all-solid-state Li/LiFePO 4 with F-dope Li 2OHCl as the solid electrolyte showed good cyclability an a high coulombic efficiency over 40 charge/discharge cycles

Addressing the Interface Issues in All-Solid-State Bulk-Type Lithium Ion Battery via an All-Composite Approach.

PubMed

Chen, Ru-Jun; Zhang, Yi-Bo; Liu, Ting; Xu, Bing-Qing; Lin, Yuan-Hua; Nan, Ce-Wen; Shen, Yang

2017-03-22

All-solid-state bulk-type lithium ion batteries (LIBs) are considered ultimate solutions to the safety issues associated with conventional LIBs using flammable liquid electrolyte. The development of bulk-type all-solid-state LIBs has been hindered by the low loading of active cathode materials, hence low specific surface capacity, and by the high interface resistance, which results in low rate and cyclic performance. In this contribution, we propose and demonstrate a synergistic all-composite approach to fabricating flexible all-solid-state LIBs. PEO-based composite cathode layers (filled with LiFePO 4 particles) of ∼300 μm in thickness and composite electrolyte layers (filled with Al-LLZTO particles) are stacked layer-by-layer with lithium foils as negative layer and hot-pressed into a monolithic all-solid-state LIB. The flexible LIB delivers a high specific discharge capacity of 155 mAh/g, which corresponds to an ultrahigh surface capacity of 10.8 mAh/cm 2 , exhibits excellent capacity retention up to at least 10 cycles and could work properly under harsh operating conditions such as bending or being sectioned into pieces. The all-composite approach is favorable for improving both mesoscopic and microscopic interfaces inside the all-solid-state LIB and may provide a new toolbox for design and fabrication of all-solid-state LIBs.

An experimental study on PEO polymer electrolyte based all-solid-state supercapacitor

NASA Astrophysics Data System (ADS)

Yijing, Yin

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I 2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.