WO2012112229A2 - Compositions d'électrolyte solide antipérovskite - Google Patents

Compositions d'électrolyte solide antipérovskite Download PDF

Info

Publication number
WO2012112229A2
WO2012112229A2 PCT/US2012/000093 US2012000093W WO2012112229A2 WO 2012112229 A2 WO2012112229 A2 WO 2012112229A2 US 2012000093 W US2012000093 W US 2012000093W WO 2012112229 A2 WO2012112229 A2 WO 2012112229A2
Authority
WO
WIPO (PCT)
Prior art keywords
sample
solid electrolyte
powder
mixture
chloride
Prior art date
Application number
PCT/US2012/000093
Other languages
English (en)
Other versions
WO2012112229A3 (fr
Inventor
Yusheng Zhao
Luc Louis DAEMEN
Maria Helena BRAGA
Original Assignee
Los Alamos National Security, Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Los Alamos National Security, Llc filed Critical Los Alamos National Security, Llc
Publication of WO2012112229A2 publication Critical patent/WO2012112229A2/fr
Publication of WO2012112229A3 publication Critical patent/WO2012112229A3/fr
Priority to US13/833,124 priority Critical patent/US9246188B2/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates generally to solid electrolyte compositions and devices such as batteries and capacitors employing the compositions.
  • Gel-liquid chemical systems are the electrolytes present in lithium batteries and other electrochemical devices.
  • Gel-liquid chemical systems include solvents, and they utilize solvated lithium ions for ion conduction. To deliver energy at a high rate, these electrolytes must be able to sustain a high capacity for rapid transport of lithium ions to and from the electrodes of the batteries over a broad range of temperatures.
  • Solvents in lithium batteries promote rapid lithium transport but they can limit the applied voltage, they allow the formation of lithium dendrites that can short the electronics, they do not allow for operation at high temperatures, and they can leak out of the battery.
  • Improvements in lithium ion transport in solid electrolytes to reach a super-ionic state would allow the application of a lithium metal anode to improve battery performance in terms of high energy density, high temperature function, no electronics shorting, and no fluid leakage. Enhanced lithium transfer rates would boost ionic conduction and thus improve the battery performance in terms of high power capacity. The development of better lithium ion conductors is expected to lead to better rechargeable batteries for electric vehicles.
  • the present invention includes a solid electrolyte composition of the formula Li 3 OCl or of the formula Li ⁇ M ⁇ OA , wherein 0 ⁇ x ⁇ 0.8, wherein M is selected from the group consisting of magnesium, calcium, barium, strontium, and mixtures thereof, and wherein A is selected from the group consisting of fluoride, chloride, bromide, iodide, and mixtures thereof.
  • the invention also includes an electrochemical device that comprises a solid electrolyte composition of the formula Li 3 OCl or of the formula wherein 0 ⁇ x ⁇ 0.8, wherein M is selected from the group consisting of magnesium calcium, barium, strontium, and mixtures thereof, and wherein A is selected from the group consisting of fluoride, chloride, bromide, iodide, and mixtures thereof.
  • electrochemical devices include, but are not limited to, a battery and a capacitor.
  • the invention also includes a solid electrolyte composition of the formula Li(3 -x )Mx 3 OA ; wherein 0 ⁇ x ⁇ 0.90, wherein M is a cation Q +3 , and wherein A is selected from the group consisting of fluoride, chloride, bromide, iodide, and mixtures thereof
  • the invention is concerned with solid electrolytes that are anti-perovskites.
  • An embodiment solid electrolyte has the formula Li 3 OCl.
  • Some other embodiments of these solid electrolytes have the general formula wherein M is an alkaline earth cation selected from Mg 2+ , Ca 2+ , Ba 2+ , Sr 2+ , and combinations thereof, and A is a halide anion selected from fluoride, chloride, bromide, iodide, and combinations thereof.
  • the value of x in the formula is 0 ⁇ x ⁇ 0.80.
  • x Some non-limiting values of x include, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, and 0.80; x may have a value smaller than 0.10.
  • some values of x that are less than 0.10 include 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, and 0.09.
  • M is an alkaline earth cation, or a mixture of alkaline earth cations
  • A is a halide or mixture of halides.
  • A can be a mixture of chloride and bromide.
  • A can be a mixture of chloride and fluoride.
  • A can be a mixture of fluoride and chloride.
  • A can be a mixture of chloride and bromide and iodide. It should be understood that A can be a mixture of any two halides, any 3 halides, and also of all four halides.
  • An explanation of what is meant by an anti-perovskite may be better understood in relation to for following explanation of what a normal perovskite is.
  • a normal perovskite has a composition of the formula ABX 3 wherein A is a cation A + , B is a cation B 2+ and X is an anion X ⁇ .
  • a normal perovskite is also a composition of the formula ABX 3 wherein A is a cation A +3 , B is a cation B +3 , and X is an anion X "2 .
  • a normal perovskite has a perovskite crystal structure, which is a well known crystal structure.
  • An antiperovskite composition also has the formula ABX 3 , but in contrast to a normal perovskite, A and B in an antiperovskite are the anions and X is the cation.
  • the antiperovskite ABX 3 having the chemical formula C10Li 3 has a perovskite crystal structure but the A (i.e. CI " ) is an anion, the B (O 2 ) is an anion, and X (i.e. Lf 1" ) is a cation.
  • C10Li 3 can be rewritten as Li 3 OCl.
  • Li 3 OCl is an example of an embodiment antiperovskite.
  • This invention is concerned with the solid electrolyte antiperovskite Li 3 OCl, and also with solid electrolyte antiperovskite compositions that have the chemical formula Li(3-x ) M 3 ⁇ 43 ⁇ 4 OA.
  • the invention is also concerned with antiperovskite solid electrolytes of the formula Li (3 . X) M x/3 OA wherein M is a cation with a +3 charge (e.g. Al +3 ), A is halide (e.g. F, CP, Br ⁇ , ⁇ , and mixtures thereof), and 0 ⁇ x ⁇ 0.90.
  • Solid electrolytes of this invention may be used as the electrolytes in lithium batteries, capacitors, and other electrochemical devices. These solid electrolytes provide advantages over more conventional gel-liquid systems. These solid electrolytes provide excellent lithium ion conduction without dendrite formation. Also, these solid electrolytes do not leak from the device.
  • Solid electrolyte antiperovskites were prepared. In some cases, a wet chemistry method was used to prepare these compositions. The wet chemistry method involved preparing an aqueous solution of various precursors, evaporating the solvent (i.e. water), and heating the resulting solid under a vacuum to form the solid electrolyte.
  • precursor powders lithium hydroxide (LiOH), calcium hydroxide
  • Li 3 OCl An aqueous solution was prepared by dissolving an amount of 4.790 grams of LiOH and an amount of 4.239 grams LiCl in a small amount of deionized water. The amounts of these precursors provided the stoichiometric ratio corresponding to the formulas Li 3 OCl + H 2 0. Most of the water from the solution was evaporated within 1-2 hours using a rotary evaporator and a bath temperature of about 90°C. The resulting solid was placed into an alumina boat. The boat was placed inside a furnace and was heated under a vacuum at a temperature of about 280°C for about 48 hours to give the reaction product, which was the solid electrolyte Li 3 OCl.
  • Powder X-ray diffraction was used to confirm the identity of the reaction product.
  • X-ray diffractograms typically in a 2 ⁇ range from 10° to 70°, were collected using a RIGAKU ULTIMA III diffractometer with a CuK context source. The step was 0.02° and the exposure time was 10 seconds per bin.
  • An X-ray diffraction pattern of the reaction product was dominated by the anti-perovskite Li 3 OCl.
  • Some additional, weaker, diffraction lines also appeared that matched those for a monoclinic Li 4 (OH) 3 Cl, whose presence is likely a result of rehydration of Li 3 OCl at ambient conditions during the post heat-treatment handling of the reaction product.
  • the ionic conductivity of the reaction product Li 3 OCl was obtained from impedence match measurements.
  • the ionic conductivity ( ⁇ ) of the reaction product Li 3 OCl was in the range of approximately 10 "4 to 10 "3 S/cm at room temperature, indicating super-ionic behavior.
  • the ionic conductivity ( ⁇ ) increased to approximately 10 "2 to 10 "1 S/cm as the temperature increased above 525 K, also indicating superionic behavior for Li 3 OCl.
  • Li 2 9 0 Cao o 5 0Cl Li 2 9 0 Cao o 5 0Cl. Most of the water from the solution was evaporated within 1-2 hours using a rotary evaporator and a bath temperature of about 80-90°C. The resulting solid mass was placed into an alumina boat. The boat was placed inside a glass tube furnace and heated under a vacuum at a temperature of about 280°C for about 48 hours to give the reaction product Li 2 9 0 Cao o 5 OCl. [0018] Both Li 3 OCl and Li 2 9 0 Cao 05OCI are antiperovskites. The latter can be thought of relative to the former as having some of the sites that would have been occupied with Li + now being replaced with the higher valence cation Ca 2+ .
  • Li 2 8 Mgo IOCI Li 2 8 Mgo IOCI. Most of the water from the solution was evaporated within 1 -2 hours using a rotary evaporator and a bath temperature of about 90°C. The resulting solid mass was placed into an alumina boat. The boat was placed inside a glass tube furnace and heated under a vacuum at a temperature of about 280°C for about 48 hours to give the reaction product Li 2 8 Mg 0 .iOCl.
  • Both Li 3 OCl and Li 2.8 Mg 0. iOCl are antiperovskites. The latter can be thought of relative to the former as having some of the sites that would have been occupied with Li + now being replaced with the higher valence cation Mg 2+ . This replacement introduces vacancies in the anti-perovskite crystal lattice. It is believed that replacement of 2 Li + with a Mg 2+ introduced a vacancy in the antiperovskite crystal lattice. Impendence measurements show that Li 2 8 Mg 0 1 OCl has a substantially higher ionic conductivity than Li 3 OCl.
  • Embodiment anhydrous antiperovskite solid electrolytes of this invention were prepared by subjecting a homogeneous mixture of various solid precursors to elevated pressures and temperatures. This method is sometimes referred to as a sintering method.
  • anhydrous antiperovskite electrolytes of the formula Li ⁇ M ⁇ OA wherein M is an alkaline earth cation (Mg 2+ , for example), and wherein A is a halide or a mixture of halides, and wherein 0 ⁇ x ⁇ 0.8.
  • an embodiment antiperovskite solid electrolyte was prepared by mechanically mixing precursor powders of lithium oxide (Li 2 0), calcium oxide (CaO) and lithium halide (e.g. LiCl), ball-milling the powders under a dry argon atmosphere to form a homogeneous mixture, and subjecting the ball-milled mixture to elevated pressures and temperatures.
  • precursor powders of Li 2 0, MgO, and lithium halides (LiF, LiCl, and/or LiBr) were mechanically mixed and then subjected to ball-milling under a dry argon atmosphere to form a homogeneous powder mixture.
  • the homogeneous powders were sent to the National Synchrotron Light Source at
  • the sintering method was monitored by in-situ and real-time synchrotron x-ray diffraction using a cubic-anvil apparatus at Beamline X17B2 of the National Synchrotron Light Source at Brookhaven National Laboratory.
  • the pressure was determined using a reference standard of NaCl and the temperature was measured using a W/Re25%-W Re3% thermocouple. The uncertainty in pressure measurements is mainly attributed to statistical variation in the position of diffraction lines of NaCl and was typically less than 2% of the cited values.
  • the temperature variations over the entire length of sample container at 1500 K were of the order of 20 K, and the radial temperature gradients were less than 20 at this condition.
  • X-ray diffraction patterns were obtained for the reference NaCl and for the sample in close proximity to the thermocouple junction. The uncertainties in temperature measurements were thus estimated to be approximately ⁇ 10°C.
  • EXAMPLES D, E, F, G, H, I, and J describe nonlimiting embodiments of antiperovskite electrolytes prepared by subjecting a homogeneous mixture of powder precursors to elevated temperatures and pressures.
  • High purity powders the precursors Li 2 0 (98% pure) and LiCl (99% pure) or LiBr (99% pure) were obtained from ACROS, and CaO (> 99% pure) was obtained from FISHER.
  • Table 1 summarizes the formula of the antiperovskite, the formulas of the precursors, their weights in grams, and the molar ratio of the precursors.
  • EXAMPLE D an amount of 0.413 grams Li 2 0, and amount of 0.587 grams of LiCl, which corresponds to a molar ratio of Li 2 0:LiCl of 1 : 1 , were mixed in a glove box under a dry argon atmosphere. The mixture was then grinded by ball milling for 2 hours inside the glove box using a SPEX SAMPLE PREP, 5100 MIXER MILL in a stainless steel crucible and under the dry argon atmosphere. The ball milled powder was then enclosed inside a container with its cap sealed using high-performance SCOTCH
  • TAPE® TAPE®
  • the bottle and powder inside were shipped to National Synchrotron Light Source at Brookhaven National Laboratory where the container was taken into a glove box under a dry argon atmosphere.
  • the cap was unsealed and the powder was loaded into a high pressure cell that consisted of a cubic mixture of amorphous boron and epoxy resin ("BE"), an amorphous carbon cylinder as a heating element, a cylindrical alumina sleeve that separated the BE from the carbon cylinder, and a hexagonal boron nitride (“BN”) sample container of 1 millimeter inner diameter and 2 millimeter length.
  • BE amorphous boron and epoxy resin
  • BN hexagonal boron nitride
  • This BN disk prevented the powder mixture from interacting with the NaCl powder (i.e. the pressure standard).
  • the volume ratio for the two powders was approximately 1 : 1.
  • EXAMPLE E was prepared by combining an amount of 0.386 grams Li 2 0, an amount of 0.576 grams CaO, and amount of 0.576 grams of LiCl, which corresponds to a molar ratio of Li 2 0:CaO:LiCl of 0.95:0.05: 1, were mixed in a glove box under an argon atmosphere. The mixture was then grinded by ball milling for 2 hours inside the glove box using a SPEX SAMPLE PREP, 5100 MIXER MILL in a stainless steel crucible and under the dry argon atmosphere. The ball milled powder was then enclosed inside a container with its cap sealed using high-performance SCOTCH TAPE®.
  • the bottle and powder inside were shipped to National Synchrotron Light Source at Brookhaven National Laboratory where the container was taken into a glove box under a dry argon atmosphere.
  • the cap was unsealed and the powder was loaded into a high pressure cell that consisted of a cubic mixture of amorphous boron and epoxy resin ("BE"), an amorphous carbon cylinder as a heating element, a cylindrical alumina sleeve that separated the BE from the carbon cylinder, and a hexagonal boron nitride ("BN”) sample container of 1 millimeter inner diameter and 2 millimeter length.
  • BE amorphous boron and epoxy resin
  • BN hexagonal boron nitride
  • This BN disk prevented the powder mixture from interacting with the NaCl powder (i.e. the pressure standard).
  • the volume ratio for the two powders was approximately 1 : 1.
  • Synchrotron x-ray diffraction data were collected for both the sample and the NaCl along the heating path at temperatures of 27°C, 100°C, 150°C, 195°C, 215°C, 227°C, and 250°C. The experiment ended by cooling to room temperature and then decompression to ambient conditions. Afterward, diffraction data were collected on the recovered sample at three different sample conditions.
  • EXAMPLE F was prepared by combining an amount of 0.359 grams Li 2 0, an amount of 0.075 grams CaO, and amount of 0.566 grams of LiCl, which corresponds to a molar ratio of Li 2 0:CaO:LiCl of 0.90:0.1 : 1 , were mixed in a glove box under a dry argon atmosphere. The mixture was then grinded by ball milling for 2 hours inside the glove box using a SPEX SAMPLE PREP, 5100 MIXER MILL in a stainless steel crucible and under the dry argon atmosphere. The ball milled powder was then enclosed inside a container with its cap sealed using high-performance SCOTCH TAPE®. The bottle and powder inside were shipped to National Synchrotron Light Source at Brookhaven
  • the volume ratio for the two powders was approximately 1 : 1.
  • all air pathways on the pressure cell were covered by DUCO® cement to isolate the powders from moisture.
  • the resulting as-finished pressure cell was placed into a capped plastic tube with both ends sealed by high-performance electrical tape.
  • the pressure cell was removed from the plastic tube, placed into a cubic anvil module inside a hydraulic press, and rapidly pumped up to a pressure of about 0.1 GPa sample pressure. Typically, it took 10-15 minutes to set up the anvil pressure module into the hydraulic press and then pump the oil pressure up so as to reach a sample pressure condition of approximately 0.1 GPa by squeezing the cubic sample assembly with six synchronized anvils.
  • the bottle and powder inside were shipped to National Synchrotron Light Source at Brookhaven National Laboratory where the container was taken into a glove box under a dry argon atmosphere.
  • the cap was unsealed and the powder was loaded into a high pressure cell that consisted of a cubic mixture of amorphous boron and epoxy resin ("BE"), an amorphous carbon cylinder as a heating element, a cylindrical alumina sleeve that separated the BE from the carbon cylinder, and a hexagonal boron nitride ("BN”) sample container of 1 millimeter inner diameter and 2 millimeter length.
  • BE amorphous boron and epoxy resin
  • BN hexagonal boron nitride
  • This BN disk prevented the powder mixture from interacting with the NaCl powder (i.e. the pressure standard).
  • the volume ratio for the two powders was approximately 1 : 1.
  • the cap was unsealed and the powder was loaded into a high pressure cell that consisted of a cubic mixture of amorphous boron and epoxy resin ("BE"), an amorphous carbon cylinder as a heating element, a cylindrical alumina sleeve that separated the BE from the carbon cylinder, and a hexagonal boron nitride (“BN”) sample container of 1 millimeter inner diameter and 2 millimeter length.
  • BE amorphous boron and epoxy resin
  • BN hexagonal boron nitride
  • the powder mixture and the NaCl powder were packed into the BN container, with a thin disk of BN separating the starting powder sample mixture from the NaCl powder. This BN disk prevented the powder mixture from interacting with the NaCl powder (i.e. the pressure standard).
  • the volume ratio for the two powders was approximately 1 : 1.
  • the pressure cell was completely assembled, all air pathways on the pressure cell were covered by DUCO® cement to isolate the powders from moisture.
  • the resulting as-finished pressure cell was placed into a capped plastic tube with both ends sealed by high-performance electrical tape.
  • the pressure cell was removed from the plastic tube, placed into a cubic anvil module inside a hydraulic press, and rapidly pumped up to a pressure of about 0.1 GPa sample pressure. Typically, it took 10-15 minutes to set up the anvil pressure module into the hydraulic press and then pump the oil pressure up so as to reach a sample pressure condition of approximately 0.1 GPa by squeezing the cubic sample assembly with six synchronized anvils. It was believed that these steps isolated the sample contents of the pressure cell from room air.
  • EXAMPLE I was prepared by combining an amount of 0.512 grams Li 2 0, and amount of 1.483 grams of LiBr, which corresponds to a molar ratio of Li 2 0:LiBr of 1 : 1, were mixed in a glove box under an argon atmosphere The mixture was then grinded by ball milling for 2 hours inside the glove box using a SPEX SAMPLE PREP, 5100 MIXER MILL in a stainless steel crucible and under the dry argon atmosphere. The ball milled powder was then enclosed inside a container with its cap sealed using high- performance SCOTCH TAPE®. The bottle and powder inside were shipped to National Synchrotron Light Source at Brookhaven National Laboratory.
  • the container was taken into a glove box under a dry argon atmosphere.
  • the cap was unsealed and the powder was loaded into a high pressure cell.
  • the high pressure cell consisted of a cubic mixture of amorphous boron and epoxy resin ("BE"), an amorphous carbon cylinder as a heating element, a cylindrical alumina sleeve that separated the BE from the carbon cylinder, and a hexagonal boron nitride ("BN”) sample container of 1 millimeter inner diameter and 2 millimeter length.
  • BE amorphous boron and epoxy resin
  • BN hexagonal boron nitride
  • This BN disk prevented the powder mixture from interacting with the NaCl powder (i.e. the pressure standard).
  • the volume ratio for the two powders was approximately 1 : 1.
  • Synchrotron x-ray diffraction data were collected for both powder mixture and NaCl along the heating path at 27°C, 100°C, 150°C, 175°C, 200°C, 213°C, 230°C, 250°C, 275°C, 300°C,. The experiment was ended by cooling to room temperature and then decompression to ambient conditions.
  • the ionic conductivity of the reaction product Li 3 OCl 0 5 Br 0 5 was obtained from impedence match measurements.
  • the ionic conductivity ( ⁇ ) was in the range of approximately 10 "4 to 10 "3 S/cm at room temperature, which means that the ionic conductivity of the reaction product Li 3 0Clo .5 Br 0 .5 reached super-ionic conduction (i.e. exhibited super-ionic behavior).
  • Li 3 OCl 0.5 Br 0 5 like Li 3 OCl, exhibited super-ionic behavior. It is believed that the mixing of large (Br ) anions and small (CI ) anions created interstitial ionic pathways for super- ionic conduction.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Primary Cells (AREA)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention porte sur des compositions d'électrolyte solide antipérovskite pour des batteries, des condensateurs et autres dispositifs électrochimiques, répondant à la formule chimique Li3OCl ou Li(3-x)Mx/2OA dans laquelle 0 < x < 0,8, M est choisi parmi le magnésium, le calcium, le baryum, le strontium et les mélanges de ceux-ci et A est choisi parmi les ions fluorure, chlorure, bromure, iodure et les mélanges de ceux-ci. D'autres compositions d'électrolyte solide antipérovskite, pour des dispositifs électrochimiques, répondent à la formule chimique Li(3-x)Mx/3OA dans laquelle 0 < x < 0,90, M représente un cation Q3+ et A est choisi parmi les ions fluorure, chlorure, bromure, iodure et les mélanges de ceux-ci.
PCT/US2012/000093 2011-02-14 2012-02-14 Compositions d'électrolyte solide antipérovskite WO2012112229A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/833,124 US9246188B2 (en) 2011-02-14 2013-03-15 Anti-perovskite solid electrolyte compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161442667P 2011-02-14 2011-02-14
US61/442,667 2011-02-14

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/833,124 Continuation-In-Part US9246188B2 (en) 2011-02-14 2013-03-15 Anti-perovskite solid electrolyte compositions

Publications (2)

Publication Number Publication Date
WO2012112229A2 true WO2012112229A2 (fr) 2012-08-23
WO2012112229A3 WO2012112229A3 (fr) 2012-10-11

Family

ID=46673080

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/000093 WO2012112229A2 (fr) 2011-02-14 2012-02-14 Compositions d'électrolyte solide antipérovskite

Country Status (1)

Country Link
WO (1) WO2012112229A2 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014150763A1 (fr) * 2013-03-15 2014-09-25 Los Alamos National Security, Llc Compositions d'électrolyte solide antipérovskite
WO2015128834A1 (fr) * 2014-02-26 2015-09-03 Universidade Do Porto Verre d'électrolyte solide pour conduction d'ions de lithium ou de sodium
US20150364788A1 (en) * 2014-06-11 2015-12-17 Los Alamos National Security, Llc Methods for growth of lithium-rich antiperovskite electrolyte films and use thereof
WO2016205064A1 (fr) * 2015-06-18 2016-12-22 Board Of Regents, The University Of Texas System Conducteurs ioniques à solide verre/amorphe solvaté dans l'eau
WO2018062770A1 (fr) * 2016-09-30 2018-04-05 주식회사 엘지화학 Composé antipérovskite riche en lithium, électrolyte de batterie secondaire au lithium le comprenant, et batterie secondaire au lithium le comprenant
CN109155411A (zh) * 2016-09-23 2019-01-04 株式会社Lg化学 富锂反钙钛矿涂覆的lco类锂复合物、其制备方法以及包含其的正极活性材料和锂二次电池
US10177406B2 (en) 2015-07-21 2019-01-08 Samsung Electronics Co., Ltd. Solid electrolyte and/or electroactive material
CN109546209A (zh) * 2018-11-07 2019-03-29 南京工业大学 一种全固态聚合物电解质及可充电氯离子电池
CN109534367A (zh) * 2017-12-29 2019-03-29 蜂巢能源科技有限公司 反钙钛矿型固态电解质及合成方法、电池、车辆
WO2019093222A1 (fr) 2017-11-10 2019-05-16 日本碍子株式会社 Batterie au lithium entièrement solide et son procédé de fabrication
US10361454B2 (en) 2016-07-11 2019-07-23 Board Of Regents, The University Of Texas System Metal plating-based electrical energy storage cell
US10490360B2 (en) 2017-10-12 2019-11-26 Board Of Regents, The University Of Texas System Heat energy-powered electrochemical cells
US10680282B2 (en) 2016-09-30 2020-06-09 Lg Chem, Ltd. Lithium-rich antiperovskite compound, lithium secondary battery electrolyte comprising same, and lithium secondary battery comprising same
US10991976B2 (en) 2018-05-16 2021-04-27 South Dakota Board Of Regents Solid-state electrolytes based on lithium halides for all-solid-state lithium-ion battery operating at elevated temperatures
US11011796B2 (en) 2016-10-21 2021-05-18 Quantumscape Battery, Inc. Electrolyte separators including lithium borohydride and composite electrolyte separators of lithium-stuffed garnet and lithium borohydride
CN113054245A (zh) * 2021-03-12 2021-06-29 南方科技大学 反钙钛矿固态电解质材料及其制备方法、固态电解质片、全固态电池
CN113299979A (zh) * 2021-05-20 2021-08-24 南方科技大学 固态电解质材料、其制备方法、固态电解质片及全固态电池
US11276880B2 (en) 2018-05-16 2022-03-15 South Dakota Board Of Regents Solid-state electrolytes based on lithium halides for all-solid-state lithium-ion battery operating at elevated temperatures
US11404683B2 (en) 2017-12-12 2022-08-02 Ngk Insulators, Ltd. All-solid-state lithium battery and method for manufacturing same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4307163A (en) * 1980-10-24 1981-12-22 Ray-O-Vac Corporation Lithium oxide halide solid state electrolyte
US4833050A (en) * 1987-11-25 1989-05-23 Duracell Inc. Electrochemical cells
US20070003833A1 (en) * 2004-05-17 2007-01-04 Wen Li Battery with molten salt electrolyte and phosphorus-containing cathode
US20070148553A1 (en) * 2004-03-06 2007-06-28 Werner Weppner Chemically stable solid lithium ion conductor
US20100266899A1 (en) * 2003-04-03 2010-10-21 Valence Technology, Inc. Electrodes Comprising Mixed Active Particles
US20110008680A1 (en) * 2009-06-24 2011-01-13 Toyota Motor Engineering & Manufacturing North America, Inc. High voltage electrolyte

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4307163A (en) * 1980-10-24 1981-12-22 Ray-O-Vac Corporation Lithium oxide halide solid state electrolyte
US4833050A (en) * 1987-11-25 1989-05-23 Duracell Inc. Electrochemical cells
US20100266899A1 (en) * 2003-04-03 2010-10-21 Valence Technology, Inc. Electrodes Comprising Mixed Active Particles
US20070148553A1 (en) * 2004-03-06 2007-06-28 Werner Weppner Chemically stable solid lithium ion conductor
US20070003833A1 (en) * 2004-05-17 2007-01-04 Wen Li Battery with molten salt electrolyte and phosphorus-containing cathode
US20110008680A1 (en) * 2009-06-24 2011-01-13 Toyota Motor Engineering & Manufacturing North America, Inc. High voltage electrolyte

Cited By (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9246188B2 (en) 2011-02-14 2016-01-26 Los Alamos National Security, Llc Anti-perovskite solid electrolyte compositions
WO2014150763A1 (fr) * 2013-03-15 2014-09-25 Los Alamos National Security, Llc Compositions d'électrolyte solide antipérovskite
WO2015128834A1 (fr) * 2014-02-26 2015-09-03 Universidade Do Porto Verre d'électrolyte solide pour conduction d'ions de lithium ou de sodium
KR20160142293A (ko) * 2014-02-26 2016-12-12 유니베르시다데 도 포르토 리튬 또는 나트륨 이온 전도를 위한 고체 전해질 유리
CN110010963A (zh) * 2014-02-26 2019-07-12 波尔图大学 用于锂或钠离子导电的固体电解质玻璃
CN106663550A (zh) * 2014-02-26 2017-05-10 波尔图大学 用于锂或钠离子导电的固体电解质玻璃
US10411293B2 (en) 2014-02-26 2019-09-10 Universidade Do Porto Solid electrolyte glass for lithium or sodium ions conduction
CN106663550B (zh) * 2014-02-26 2019-03-01 波尔图大学 用于锂或钠离子导电的固体电解质玻璃
KR102454061B1 (ko) * 2014-02-26 2022-10-14 유니베르시다데 도 포르토 리튬 또는 나트륨 이온 전도를 위한 고체 전해질 유리
US20150364788A1 (en) * 2014-06-11 2015-12-17 Los Alamos National Security, Llc Methods for growth of lithium-rich antiperovskite electrolyte films and use thereof
US10044061B2 (en) * 2014-06-11 2018-08-07 Los Alamos National Security, Llc Methods for growth of lithium-rich antiperovskite electrolyte films and use thereof
CN107750406A (zh) * 2015-06-18 2018-03-02 德克萨斯大学***董事会 水溶剂化玻璃/非晶态固体离子导体
CN107750406B (zh) * 2015-06-18 2021-02-12 德克萨斯大学***董事会 水溶剂化玻璃/非晶态固体离子导体
US9890048B2 (en) 2015-06-18 2018-02-13 Board Of Regents, The University Of Texas System Water solvated glass/amorphous solid ionic conductors
WO2016205064A1 (fr) * 2015-06-18 2016-12-22 Board Of Regents, The University Of Texas System Conducteurs ioniques à solide verre/amorphe solvaté dans l'eau
US10177406B2 (en) 2015-07-21 2019-01-08 Samsung Electronics Co., Ltd. Solid electrolyte and/or electroactive material
US10381683B2 (en) 2016-07-11 2019-08-13 Board Of Regents, The University Of Texas System Metal plating-based electrical energy storage cell
US10511055B2 (en) 2016-07-11 2019-12-17 Board Of Regents, The University Of Texas System Metal plating-based electrical energy storage cell
US10361454B2 (en) 2016-07-11 2019-07-23 Board Of Regents, The University Of Texas System Metal plating-based electrical energy storage cell
CN109155411A (zh) * 2016-09-23 2019-01-04 株式会社Lg化学 富锂反钙钛矿涂覆的lco类锂复合物、其制备方法以及包含其的正极活性材料和锂二次电池
US10964972B2 (en) 2016-09-23 2021-03-30 Lg Chem, Ltd. Lithium-rich antiperovskite-coated LCO-based lithium composite, method for preparing same, and positive electrode active material and lithium secondary battery comprising same
CN109155411B (zh) * 2016-09-23 2022-02-08 株式会社Lg化学 富锂反钙钛矿涂覆的lco类锂复合物、其制备方法以及包含其的正极活性材料和锂二次电池
WO2018062770A1 (fr) * 2016-09-30 2018-04-05 주식회사 엘지화학 Composé antipérovskite riche en lithium, électrolyte de batterie secondaire au lithium le comprenant, et batterie secondaire au lithium le comprenant
US10680282B2 (en) 2016-09-30 2020-06-09 Lg Chem, Ltd. Lithium-rich antiperovskite compound, lithium secondary battery electrolyte comprising same, and lithium secondary battery comprising same
US11855251B2 (en) 2016-10-21 2023-12-26 Quantumscape Battery, Inc. Electrolyte separators including lithium borohydride and composite electrolyte separators of lithium-stuffed garnet and lithium borohydride
US11581612B2 (en) 2016-10-21 2023-02-14 Quantumscape Battery, Inc. Electrolyte separators including lithium borohydride and composite electrolyte separators of lithium-stuffed garnet and lithium borohydride
US11011796B2 (en) 2016-10-21 2021-05-18 Quantumscape Battery, Inc. Electrolyte separators including lithium borohydride and composite electrolyte separators of lithium-stuffed garnet and lithium borohydride
US11049667B2 (en) 2017-10-12 2021-06-29 Hydro-Quebec Heat energy-powered electrochemical cells
US10804040B2 (en) 2017-10-12 2020-10-13 Hydro-Quebec Heat energy-powered electrochemical cells
US10490360B2 (en) 2017-10-12 2019-11-26 Board Of Regents, The University Of Texas System Heat energy-powered electrochemical cells
CN111279538A (zh) * 2017-11-10 2020-06-12 日本碍子株式会社 全固体锂电池及其制造方法
KR20200052962A (ko) 2017-11-10 2020-05-15 엔지케이 인슐레이터 엘티디 전고체 리튬 전지 및 그 제조 방법
WO2019093222A1 (fr) 2017-11-10 2019-05-16 日本碍子株式会社 Batterie au lithium entièrement solide et son procédé de fabrication
JPWO2019093222A1 (ja) * 2017-11-10 2020-11-19 日本碍子株式会社 全固体リチウム電池及びその製造方法
US11837699B2 (en) 2017-11-10 2023-12-05 Ngk Insulators, Ltd. All-solid lithium battery and method of manufacturing same
KR102325924B1 (ko) * 2017-11-10 2021-11-12 엔지케이 인슐레이터 엘티디 전고체 리튬 전지 및 그 제조 방법
CN111279538B (zh) * 2017-11-10 2023-07-25 日本碍子株式会社 全固体锂电池及其制造方法
US11404683B2 (en) 2017-12-12 2022-08-02 Ngk Insulators, Ltd. All-solid-state lithium battery and method for manufacturing same
CN109534367A (zh) * 2017-12-29 2019-03-29 蜂巢能源科技有限公司 反钙钛矿型固态电解质及合成方法、电池、车辆
US11276880B2 (en) 2018-05-16 2022-03-15 South Dakota Board Of Regents Solid-state electrolytes based on lithium halides for all-solid-state lithium-ion battery operating at elevated temperatures
US10991976B2 (en) 2018-05-16 2021-04-27 South Dakota Board Of Regents Solid-state electrolytes based on lithium halides for all-solid-state lithium-ion battery operating at elevated temperatures
CN109546209A (zh) * 2018-11-07 2019-03-29 南京工业大学 一种全固态聚合物电解质及可充电氯离子电池
CN113054245B (zh) * 2021-03-12 2022-08-19 南方科技大学 反钙钛矿固态电解质材料及其制备方法、固态电解质片、全固态电池
CN113054245A (zh) * 2021-03-12 2021-06-29 南方科技大学 反钙钛矿固态电解质材料及其制备方法、固态电解质片、全固态电池
CN113299979B (zh) * 2021-05-20 2023-03-21 南方科技大学 固态电解质材料、其制备方法、固态电解质片及全固态电池
CN113299979A (zh) * 2021-05-20 2021-08-24 南方科技大学 固态电解质材料、其制备方法、固态电解质片及全固态电池

Also Published As

Publication number Publication date
WO2012112229A3 (fr) 2012-10-11

Similar Documents

Publication Publication Date Title
WO2012112229A2 (fr) Compositions d&#39;électrolyte solide antipérovskite
US9246188B2 (en) Anti-perovskite solid electrolyte compositions
JP5957144B2 (ja) リチウムイオン電池用硫化物系固体電解質
EP3171444B1 (fr) Électrolyte solide à base de sulfure pour batteries au lithium-ion et procede de fabrication de l&#39;electrolyte
US20200176813A1 (en) Solid electrolyte glass for lithium or sodium ions conduction
CN104124467B (zh) 一种利用锂镧锆氧前驱体包覆粉体制备固体电解质的方法
EP3502051A1 (fr) Électrolyte solide pour batterie totalement solide ayant une structure cristalline de type argyrodite dérivée d&#39;élément unique et son procédé de préparation
US20210323824A1 (en) Solid lithium ion conducting material and process for preparation thereof
CN109417194A (zh) 锂二次电池用硫化物系固体电解质
JP5584902B2 (ja) 電気化学電池セル用電解質
CN112042018A (zh) 氟化物离子二次电池用负极活性物质、使用了该活性物质的负极、及氟化物离子二次电池、以及该活性物质的制造方法
KR102628721B1 (ko) 나노입자 재료 및 불화물 이온 배터리의 제조 방법
KR20220020960A (ko) 리튬-이온 전도성 할로보로-옥시설파이드
JP2021150289A (ja) 硫化物固体電解質材料の製造方法
Bejaoui et al. Synthesis, electrical and dielectrical properties of (LixNa1–x) 6Mg (SO4) 4 vanthoffite ceramics as new attractive electrode materials for Li-and Na-ion batteries
US9231275B2 (en) Method for manufacturing sulfide-based solid electrolyte
US20180226676A1 (en) Solid-state silver-lithium / iodine dual-function battery formed via self-assembly
US11817550B2 (en) Method of synthesizing a solid-state electrolyte for use in a lithium-ion battery
KR20240062102A (ko) 리튬 가넷 물질 및 이를 포함하는 고체 리튬 배터리

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12747701

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12747701

Country of ref document: EP

Kind code of ref document: A2