USRE40302E1 - Polyelectrolyte, non-aqueous electrolyte, and electrical device containing the same - Google Patents

Polyelectrolyte, non-aqueous electrolyte, and electrical device containing the same Download PDF

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USRE40302E1
USRE40302E1 US11/327,829 US32782900A USRE40302E US RE40302 E1 USRE40302 E1 US RE40302E1 US 32782900 A US32782900 A US 32782900A US RE40302 E USRE40302 E US RE40302E
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group
polymeric
formula
electrolyte according
polymeric electrolyte
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Masahito Nishiura
Michiyuki Kono
Masayoshi Watanabe
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DKS Co Ltd
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Dai Ichi Kogyo Seiyaku Co Ltd
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Priority claimed from JP24889199A external-priority patent/JP2001076755A/ja
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    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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

Definitions

  • the present invention relates to a polymeric electrolyte and a nonaqueous electrolyte which can improve a transport rate of charge carrier ions upon using a compound having boron atoms in the structure as an additive, and an electric device using the same.
  • polymeric electrolytes and nonaqueous electrolytes According to the development of cells having a high voltage and a high capacity, a large number of various polymeric electrolytes and nonaqueous electrolytes have been proposed.
  • polymeric electrolytes and nonaqueous electrolytes have an ionic conductivity which is lower than that of aqueous electrolytes by more than one figure.
  • a polymeric electrolyte using polyethylene glycol has defects that it is low in transfer and transport rates of charge carrier ions. Thus, attempts of improvement have been made by using various methods.
  • Japanese Patent Laid-Open No. 3,728/1999 discloses a nonaqueous electrolytic solution secondary cell comprising a positive electrode and a negative electrode containing a material capable of occluding and releasing lithium reversibly, a nonaqueous electrolytic solution containing a lithium salt and a separator, at least one organic boron compound being contained in the cell in a predetermined amount.
  • the invention has been made, and aims to provide a polymeric electrolyte and a nonaqueous electrolyte which increases a dissociation degree of an electrolytic salt, which can improve a transport rate of charge carrier ions and in which an effective concentration region of an additive is wide and an effect provided by its addition per weight is great, and an electric device using the same.
  • the present inventors have assiduously conducted investigations to solve the problems. They have consequently conceived that counter ions of charge carrier ions are trapped and less moved to control a transport rate of charge carrier ions, and have found that the use of a compound containing plural trivalent boron atoms in the structure, a Lewis acid, as an additive, is effective for solving the problems. This finding has led to the completion of the invention.
  • the polymeric electrolyte of the invention is a polymeric electrolyte made of an electrolyte salt and a polymeric compound forming a complex with the electrolytic salt, the polymeric electrolyte containing one or more compounds having boron atoms in the structure.
  • nonaqueous electrolyte of the invention is a nonaqueous electrolyte made of an electrolytic salt and a nonaqueous solvent that dissolves the electrolytic salt, the nonaqueous electrolyte containing one or more compounds having boron atoms in the structure.
  • the compound having boron atoms in the structure is preferably selected from the group consisting of compounds represented by the following general formulas (1) to (4).
  • R 11 , R 12 , R 13 , R 14 , R 15 and R 16 formula (1), R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 in formula (2), R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 and R 310 in formula (3), and R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 410 , R 411 and R 412 in formula (4), which may be the same or different, each represent a hydrogen atom, a halogen atom or a monovalent group, or are bound to each other to form a ring.
  • Ra in formula (1) represents a group having a site capable of being bound to at least 3 boron atoms which are the same or different
  • Rb in formula (2) represents a group having a site capable of being bound to at least 4 boron atoms which are the same or different
  • Rc in formula (3) represents a group having a site capable of being bound to at least 5 boron atoms which are the same or different
  • Rd in formula (4) represents a group having a site capable of being bound to at least 6 boron atoms which are the same or different.
  • the polymeric compound used in the polymeric electrolyte of the invention includes, for example, a polyalkylene, a polyether, a polyester, a polyamine, a polyimide, a polyurethane, a polysulfide, a polyphosphazene, a polysiloxane, derivatives thereof, copolymers thereof and crosslinked products thereof.
  • a lithium salt is preferably used.
  • an aprotic solvent is preferably used.
  • the electric device of the invention is manufactured using any of the polymeric electrolytes and the nonaqueous electrolytes.
  • the electric device when it is a cell, it is obtained by linking a positive electrode and a negative electrode through any of the polymeric electrolytes or through any of the nonaqueous electrolytes and a separator.
  • the compounds represented by general formulas (1) to (4) are preferably used as described earlier.
  • Examples of the monovalent group include an alkyl group, an alkoxy group, an aryl group, an alkenyl group, an alkinyl group, an aralkyl group, a cycloalkyl group, a cyano group, a hydroxyl group, a formyl group, an aryloxy group, an alkylthio group, an arylthio group, an acyloxy group, a sulfonyloxy group, an amino group, an alkylamino group, an arylamino group, a carboxyamino group, an oxysulfonylamino group, a sulfonamido group, an oxycarbonylamino group, a ureido group, an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfinyl group, an oxysulfonyl group, a sul
  • R 1 , R 2 and R 3 herein each represent a hydrogen atom, a halogen atom or a monovalent group.
  • Examples of the monovalent group include an alkyl group, an alkoxy group, an aryl group, an alkenyl group, an alkinyl group, an aralkyl group, a cycloalkyl group, a cyano group, a hydroxyl group, a formyl group, an aryloxy group, an alkylthio group, an arylthio group, an acyloxy group, a sulfonyloxy group, an amino group, an alkylamino group, an arylamino group, a carboxyamino group, an oxysulfonylamino group, a sulfonamide group, an oxycarbonylamino group, a ureido group, an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfinyl group, an oxysulfonyl group, a sulfam
  • R 11 , R 12 , R 13 , R 14 , R 15 and R 16 in formula (1), R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 in formula (2), R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 and R 310 in formula (3), and R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 410 , R 411 and R 412 in formula (4) may be bound to each other to form a ring, and this ring may have a substituent. Moreover, each group may be substituted with a group which can be substituted.
  • Examples of the group having a site capable of being bound to at least 3 boron atoms which are the same or different, as represented by Ra, in formula (1) include residues such as glycerin, trimethylolethane, trihydroxybenzene, dihydroxybenzoic acid, diaminobenzoic acid, tribromobenzene and the like.
  • Examples of the group having a site capable of being bound to at least 4 boron atoms which are the same or different, as represented by Rb, in formula (2) include residues such as diglycerin, pentaerythritol, tetrabromobenzene and the like.
  • Examples of the group having a site capable of being bound to at least 5 boron atoms which are the same or different, as represented by Rc, in formula (3) include residues such as glucose, morin and the like.
  • Examples of the group having a site capable of being bound to at least 6 boron atoms which are the same or different, as represented by Rd, in formula (4) include residues such as galactaric acid, myricetin and the like.
  • polymeric compound used as the polymeric electrolyte of the invention examples include a polyalkylene, a polyether, a polyester, a polyamine, a polyimide, a polyurethane, a polysulfide, a polyphosphazene, a polysiloxane, a polyalkylene oxide, a polyvinylidene fluoride, polyhexafluoropropylene, polyacrylonitrile, polymethyl methacrylate, derivatives thereof, copolymers thereof and crosslinked products thereof. They are used either singly or in combination.
  • a polymeric compound made of a polyalkylene oxide, and/or derivatives thereof, and/or crosslinked products thereof is preferable.
  • a polymer or a copolymer of compound (A) represented by the following formula (5) and/or compound (B) represented by the following formula (6) can be used.
  • R 1 represents a methyl group, an ethyl group, a propyl group, a butyl group or a group represented by the following formula (7).
  • r represents 0 or an integer of 1 or more
  • Ra represents a methyl group, an ethyl group, a propyl group or a butyl group.
  • the electrolytic salt is preferably a metallic salt, more preferably a lithium salt.
  • a metallic salt more preferably a lithium salt.
  • examples thereof include LiBF 4 , LiPF 6 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , LiCl, LiF, LiBr, LiI, derivatives thereof and like. These lithium salts may be used either singly or in combination.
  • the concentration of these electrolytic salts is usually 0.01 mol/kg to 10 mols/kg, preferably 0.2 mol/kg to 6 mols/kg.
  • the nonaqueous solvent is preferably an aprotic solvent.
  • aprotic solvent examples thereof include carbonates, lactones, ethers, sulfolanes and dioxolanes. These aprotic solvents may be used either singly or in combination.
  • the polymeric compound to aprotic solvent mixing ratio is 1/99 to 99/1, preferably 5/95 to 95/5, more preferably 10/90 to 90/10 in terms of a weight ratio.
  • a molar ratio of the compound having boron atoms in the structure to the electrolytic salt is preferably 0.1:100 to 300:100, more preferably 1:100 to 200:100, further preferably 50:100 to 100:100.
  • Examples of the electrolytic salt and the nonaqueous solvent used in the nonaqueous electrolyte of the invention are the same as those listed on the foregoing polymeric electrolyte. Further, the concentration of the electrolytic salt and the molar ratio of the boron atom-containing compound to the electrolytic salt may be in the same ranges as mentioned on the foregoing polymeric electrolyte.
  • the polymeric electrolyte of the invention can be applied to various electric devices, and examples thereof include cells, capacitors and the like. Typical of these are cells which are obtained by linking a positive electrode and a negative electrode through any of the foregoing polymeric electrolytes or through any of the foregoing nonaqueous electrolytes and a separator.
  • a double metal oxide capable of occluding and releasing lithium ions is used.
  • examples thereof include cobalt lithium oxide, nickel lithium oxide, manganese lithium oxide, vanadium pentoxide and the like.
  • a lithium metal, a lithium alloy or a substance capable of reversibly occluding and releasing lithium ions is used.
  • a substance capable of reversibly occluding and releasing lithium ions is used. Examples of such a substance include carbon and the like
  • a porous film, a nonwoven fabric, a woven fabric or the like which can permeate lithium ions is used as the separator.
  • the material thereof include olefinic polymers such as polyethylene, polypropylene and the like, fluoropolymers, cellulose-based polymers, glass fibers and the like.
  • Potassium hydroxide (0.01 mol) was added to 1 mol of ethylene glycol monobutyl ether as a starting material, and a vessel was purged with nitrogen while stirring the mixture. Subsequently, the pressure inside the vessel was reduced using a vacuum pump. The temperature was then raised to 120° C., and the reaction was conducted using 1 mol of ethylene oxide as a monomer. After the completion of the reaction, the reaction mixture was cooled until the temperature inside the vessel reached room temperature. A methanol solution of 1.1 mols of sodium methylate was added, and the temperature was slowly raised to 50° C. while reducing the pressure. After methanol was completely removed, 1.2 mols of epichlorohydrin was added, and the mixturewas reacted for 4 hours. Afterthecompletion of the reaction, adsorption treatment was conducted. After dehydration under reduced pressure, the residue was filtered to obtain a desired product.
  • a desired product was obtained in the same manner as monomer A except that ethylene glycol monomethyl ether was used as a starting material and 9 mols of ethylene oxide was used as a monomer.
  • a desired product was obtained in the same manner as monomer A except that ethylene glycol monopropyl ether was used as a starting material and 2 mols of ethylene oxide was used as a monomer.
  • a desired product was obtained in the same manner as monomer A except that ethylene glycol monoethly ether was used as a starting material and 49 mols of ethylene oxide was used as a monomer.
  • a desired product was obtained in the same manner as monomer A except that ethylene glycol monomethyl ether was used as a starting material and 1 mol of ethylene oxide was used as a monomer.
  • Potassium hydroxide (0.01 mol) was added to 0.5 mol of ethylene glycol as a starting material, and a vessel was purges withnitrogenwhilestirringthemixture. Thepressureinside the vessel was reduced using a vacuum pump. The temperature was then raised to 120° C., and the reaction was conducted using 38,000 mols of ethylene oxide as a monomer. After the completion of the reaction, the reaction mixture was cooled until the temperature inside the vessel reached room temperature. A methanol solution of 1.1 mols of sodium methylate was added, and the temperature was slowly raised to 50° C. while reducing the pressure. After methanol was completely removed, the residue was allowed to cool. One kilogram of toluene was added, and 1 mol of acrylic acid chloride was added. The mixture was reacted for 4 hours. After acid and alkali adsorption treatment was conducted, the residue was filtered, and toluene was removed under reduced pressure to obtain a desired product.
  • a desired product was obtained in the same manner as polymeric compound precursor B-1 except that 0.33 mol of glycerin was used as a starting material, 28,000 mols of propylene oxide was used as a monomer and methacrylic acid chloride was used instead of acrylic acid chloride.
  • a desired product was obtained in the same manner as polymeric compound precursor B-1 except that 0.25 mol of diglycerin was used as a starting material, 150 mols of ethylene oxide and 600 mols of 1,2-epoxyhexane were used as monomers, allyl chloride was used instead of acrylic acid chloride.
  • a desired product was obtained in the same manner as polymeric compound precursor B-1 except that 0.5 mol of ethylene glycol was used as a starting material, 2 mols of ethylene oxide and 1 mol of butylene oxide were used as monomers and vinyl chloride was used instead of acrylic acid chloride.
  • a desired product was obtained in the same manner as polymeric compound precursor B-1 except that 0.33 mol of glycerin was used as a starting material and 150 mols of ethylene oxide and 29 mols of 1,2-epoxypentane were used as monomers.
  • a desired product was obtained in the same manner as polymeric compound precursor B-1 except that 600 mols of monomer A was used as a monomer.
  • a desired product was obtained in the same manner as polymeric compound precursor B-2 except that 50 mols of ethylene oxide and 15 mols of monomer B were used as monomers.
  • a desired product was obtained in the same manner as polymeric compound precursor B-3 except that 1 mol of ethylene oxide and 1 mol of monomer C were used as monomers.
  • a desired product was obtained in the same manner as polymeric compound precursor B-4 except that 1,600 mols of ethylene oxide and 400 mols of monomer D were used as monomers.
  • a desired product was obtained in the same manner as polymeric compound precursor B-5 except that 126 mols of ethylene oxide and 24 mols of monomer E were used as monomers.
  • Z is an active hydrogen residue.
  • Z is an active hydrogen residue.
  • the additive (1 mol/kg) represented by the formula 3Z-3, 1 mol/kg of LiBF 4 , 1.2 g of ⁇ -butyrolactone and a photopolymerization initiator were added to 1 g of polymeric compound precursor B-1. These were dissolved at 40° C., and poured between glass plates. The mixture was then irradiated with ultraviolet rays in an argon atmosphere to obtain a polymeric electrolyte having a thickness of 500 ⁇ m.
  • Polymeric electrolytes were obtained in the same manner as in Example 1 except that types and amounts of polymeric compound precursors, additives, salts and aprotic solvents shown in Table 1were used.
  • Polymeric electrolytes were obtained in the same manner as in Example 1 except that types and amounts of polymeric compound precursors, additives, salts and aprotic solvents shown in Table 1 were used.
  • Each of the polymeric electrolytes obtained in the foregoing Examples and Comparative Examples was cut in a circle having a diameter of 13 mm, and this was held between lithium metal electrodes having the same diameter. A lithium ion transport rate was measured by a DC polarization method.
  • the additive (1 mol/kg) represented by the formula 3Z-3 and 1 mol/kg of LiBF 4 were added to 1.2 g of ⁇ -butyrolactone, and there were dissolved in a glove box at 40° C. to obtain a nonaqueous electrolyte.
  • Nonaqueous electrolytes were obtained in the same manner as in Example 1 except that types and amounts of additives, salts and aprotic solvents shown in Table 2 were used.
  • Nonaqueous electrolytes were obtained in the same manner as in Example 1 except that types and amount of additives, salts and aprotic solvents shown in Table 2 were used.
  • a polypropylene porous separator having a diameter of 13 mm was dipped with each of the nonaqueous electrolytes obtained in the foregoing Examples and Comparative Examples. After the dipping was conducted satisfactorily, the resulting separator was held between lithium metal electrodes having the same diameter. A lithium ion transport rate was measured by a DC polarization method. The results are also shown in Table 2.
  • the polymeric electrolyte and the nonaqueous electrolyte of the invention can accelerate dissociation of an electrolytic salt upon using a compound having plural trivalent boron atoms in the structure, a Lewis acid, as an additive and consequently improve a transport rate of charge carrier ions. Besides, since an effect of addition per unit weight is great, the transport rate can be improved much, and an effective concentration region of the additive is also wide.
  • cells having a higher voltage and a higher capacity than usual ones can provide cells having a higher voltage and a higher capacity than usual ones.
  • the usage of cells is not limited, they are preferably used in portable electric appliances such as a video, a camera, a personal computer, a cellular phone and the like.

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  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
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US11/327,829 1999-09-02 2000-08-28 Polyelectrolyte, non-aqueous electrolyte, and electrical device containing the same Expired - Fee Related USRE40302E1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP24889099A JP3557962B2 (ja) 1999-09-02 1999-09-02 高分子電解質及びこれを用いてなる電気化学デバイス
JP24889199A JP2001076755A (ja) 1999-09-02 1999-09-02 非水電解質及びこれを用いてなる電気化学デバイス
PCT/JP2000/005812 WO2001018898A1 (fr) 1999-09-02 2000-08-28 Polyelectrolyte, electrolyte non aqueuse et dispositif electrique les renfermant

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JP5021867B2 (ja) 2001-04-09 2012-09-12 第一工業製薬株式会社 ポリエーテル系高分子化合物、これを用いてなるイオン伝導性高分子組成物及び電気化学デバイス
US20040253520A1 (en) * 2003-05-13 2004-12-16 Wensley C. Glen Polyimide matrix electrolyte and improved batteries therefrom
US20040229127A1 (en) 2003-05-13 2004-11-18 Wensley C. Glen Polyimide matrix electrolyte
US6936377B2 (en) * 2003-05-13 2005-08-30 C. Glen Wensley Card with embedded IC and electrochemical cell
US7390336B2 (en) * 2003-07-29 2008-06-24 Solicore, Inc. Polyimide-based lithium metal battery
TWI377729B (en) * 2004-07-22 2012-11-21 Solicore Inc Battery and electronic device comprising the same
CN112038690B (zh) * 2019-06-04 2022-12-06 北京卫蓝新能源科技有限公司 一种含硼聚合物固态电解质及其应用
EP3764434A1 (de) * 2019-07-10 2021-01-13 LITRONIK Batterietechnologie GmbH Eliminierung des voltage-delays und stabilisierung der impedanz durch elektrolytzusätze in alkali-metallelektrochemischen zellen

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EP1130671A1 (en) 2001-09-05
WO2001018898A1 (fr) 2001-03-15
CA2344243A1 (en) 2001-03-15
US6673495B1 (en) 2004-01-06
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