EP1417726A2 - Polymerelektrolyte und deren verwendung in galvanischen zellen - Google Patents

Polymerelektrolyte und deren verwendung in galvanischen zellen

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Publication number
EP1417726A2
EP1417726A2 EP02760270A EP02760270A EP1417726A2 EP 1417726 A2 EP1417726 A2 EP 1417726A2 EP 02760270 A EP02760270 A EP 02760270A EP 02760270 A EP02760270 A EP 02760270A EP 1417726 A2 EP1417726 A2 EP 1417726A2
Authority
EP
European Patent Office
Prior art keywords
carbonate
lithium
component
methyl
mixture according
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP02760270A
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German (de)
English (en)
French (fr)
Inventor
Michael Schmidt
Frank Ott
Winfried Geissler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1417726A2 publication Critical patent/EP1417726A2/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • 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
    • H01M10/0565—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
    • H01M10/056—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
    • 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • 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
    • 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
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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 to mixtures of borate or phosphate salts and polymers and their use in electrolytes, batteries, capacitors, supercapacitors and galvanic cells.
  • Battery cells based on liquid electrolytes generally have relatively good ionic conductivities, but tend to leak, which then leads to the release of liquids that are potentially dangerous to humans and the environment. The production of such battery cells is also limited with regard to the possible sizes and shapes of these cells.
  • Polymer electrolytes are usually based on an optionally crosslinked polymer and a conductive salt.
  • conventional polymer electrolytes often show only low ionic conductivities, which do not meet the high demands placed on modern batteries.
  • Gel or hybrid electrolytes are understood to mean electrolyte systems which, in addition to an optionally crosslinked polymer and a conducting salt, contain a solvent.
  • the crosslinking of these polymers is often carried out at relatively high temperatures in the presence of the conductive salts.
  • the corresponding conductive salts must therefore have a relatively high thermal solution
  • REPLACEMENT BLA ⁇ (RULE 26) Have stability, since otherwise there is a risk of their decomposition and thus a reduction in the ionic conductivity of the resulting gel electrolyte.
  • LiPF 6 Due to the low thermal stability, LiPF 6 , which has the greatest commercial distribution as a salt in liquid electrolytes, is not suitable for use in polymer or gel electrolytes. In addition, LiPF ⁇ is extremely sensitive to hydrolysis. Hydrofluoric acid HF can quickly develop in contact with moist air or with residual water from the solvents. In addition to its toxic properties, HF has a very negative effect on the cycle behavior and thus on the life and performance of the electrochemical cells.
  • the aluminum usually used as a cathodic current arrester is not sufficiently passivated by imides (LA Dominey, Current State of Art on Lithium Battery Electrolyte in G. Pistoia (ed.) Lithium Batteries; New Materials, Development and Perspectives, Amsterdam, Elsevier, 1994 and literature cited therein).
  • imides LA Dominey, Current State of Art on Lithium Battery Electrolyte in G. Pistoia (ed.) Lithium Batteries; New Materials, Development and Perspectives, Amsterdam, Elsevier, 1994 and literature cited therein.
  • methanides can only be produced and purified with great effort.
  • the electrochemical properties such as oxidation stability and passivation of aluminum depend very much on the purity of the methanide.
  • EP 698 301 and WO 98/07729 disclose lithium spiroborates with aromatic ligands and their use as conductive salts in galvanic cells. The use of these salts as conductive salts in polymer electrolytes is not described.
  • lithium bis (oxalato) borate and lithium tris (oxalato) phosphate describe two salts and their use as conductive salts.
  • Polymer electrolytes based on these salts are also not disclosed here.
  • the object of the invention was to provide electrolytes which do not have the disadvantages of the prior art. The task was therefore to provide electrolytes which, in addition to good ionic conductivity, also have high thermal stability.
  • Another object of the present invention was to extend or improve the life and performance of batteries, capacitors, supercapacitors and galvanic cells.
  • R 4 , R 5 , R 6 are the same, different or in pairs different, optionally directly connected to one another by a single or double bond and each have the individually or together
  • aromatic or a heteroaromatic ring preferably phenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, pyrazyl or pyrimidyl,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 partially or completely with further groups, preferably with F, Cl, Br,
  • C n F (2n + 1-x) H x can be substituted with 1 ⁇ n ⁇ 6 and 1 ⁇ x ⁇ 2n + 1.
  • a mixture in the sense of the present invention comprises pure mixtures of components a) and b), mixtures in which the salt of component a) is included in the polymer of component b) and mixtures in which between the salt of component a) and the polymer of component b) chemical and / or physical bonds exist.
  • the mixture according to the invention can contain component a) in an amount of 3 to 99% by weight and component b) in an amount of 97 to 1% by weight.
  • the mixture can particularly preferably contain component a) in an amount of 10 to 99% by weight and component b) in an amount of 90 to 1% by weight.
  • the weight ratios given above each relate to the sum of components a) and b).
  • the mixtures according to the invention preferably each contain a salt of the general formula (I) or (II) as component a) and a polymer of component b). In this way, particularly good reproducibility of the electrochemical properties can be achieved.
  • the mixtures according to the invention can also each contain two or more salts of the general formulas (I) and (II) as component a) and / or two or more polymers of component b).
  • salts of the general formulas (I) or (II) in a mixture with further lithium salts known to the person skilled in the art in the mixtures according to the invention. They can be used in proportions between 1 and 99% in combination with other conductive salts which are used in electrochemical cells.
  • conductive salts selected from the group LiPF 6 , LiBF 4 , LiCIO 4 , LiAsF 6 , LiSO 3 CF 3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , LiN (SO 2 C 2 F 5 ) 2 , LiB (OC 2 ) 2 or Li [F ⁇ P (CnF 2n + ⁇ ) 6-x] with 1 ⁇ x ⁇ 5 and 1 ⁇ n ⁇ 8 and their mixtures.
  • the mixtures according to the invention contain spiroborate or spirophosphate salts as salts of the general formulas (I) or (II).
  • mixtures particularly preferably contain salts of the general formulas (I) or (II), the anions of which are selected from the following group:
  • the mixture according to the invention preferably contains a homopolymer or copolymer of unsaturated nitriles, preferably acrylonitrile, vinylidenes, preferably vinylidene difluoride, methacrylates, preferably methyl methacrylate, cyclic ethers, preferably tetrahydrofuran, alkylene oxides, preferably ethylene oxide, siloxane, phosphazene, alkoxysilanes or organically modified keramics , distributed under the Brand names ORMOCERE®, or a mixture of at least two of the above-mentioned homopolymers and / or copolymers.
  • unsaturated nitriles preferably acrylonitrile, vinylidenes, preferably vinylidene difluoride, methacrylates, preferably methyl methacrylate, cyclic ethers, preferably tetrahydrofuran, alkylene oxides, preferably ethylene oxide, siloxane, phosphazen
  • Component b) is particularly preferably a homopolymer or copolymer of vinylidene difluoride, acrylonitrile, methyl (meth) acrylate, tetrahydrofuran, very particularly preferably a homopolymer or copolymer of vinylidene difluoride.
  • These homopolymers and copolymers of vinylidene difluoride are e.g. marketed under the names Kynar® and Kynarflex® by Atofina Chemicals, Inc. and under the name Solef® by Solvay.
  • polymers used according to the invention can be at least partially crosslinked.
  • Crosslinking can be carried out using known crosslinking agents by customary methods known to those skilled in the art.
  • the mixture according to the invention can additionally contain a solvent or a solvent mixture of two or more solvents.
  • Preferred solvents are organic carbonates, organic esters, organic ethers, organic amides, sulfur-containing solvents, aprotic solvents or at least partially fluorinated derivatives of the abovementioned solvents or mixtures of at least two of these solvents and / or fluorinated derivatives of these solvents.
  • Ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, vinylene carbonate or methyl propyl carbonate are preferably used as organic carbonates, and methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate or ⁇ -organic ether sulfate is preferably used as the organic ester Diethyl ether, dimethoxyethane or diethoxyethane, as organic amides preferably dimethylformamide or dimethylacetamide, as sulfur-containing solvent preferably dimethyl sulfoxide, dimethyl sulfite, diethyl sulfite or propane sultone and as aprotic solvent preferably acetonitrile, acrylonitrile or acetone.
  • the invention further relates to a process for the preparation of lithium salts of the general formula (I) in electrochemically pure quality (> 99%), in which lithium hydroxide or lithium carbonate with boric acid or boron trioxide and the corresponding ligand of the salt of the general formula (I) is implemented by a process known to the person skilled in the art, wherein according to the invention only solvents are used which have a high electrochemical voltage window, such as organic carbonates.
  • E rec ⁇ ⁇ 1.5 V against Li / Li + and E ox > 4.5 V against Li / Li + applies to a high electrochemical voltage window .
  • Only open-chain carbonates are preferably used as the solvent, in particular dimethyl carbonate, diethyl carbonate and / or ethyl methyl carbonate.
  • the invention further relates to lithium salts of the general formula (I) in electrochemically pure quality (> 99%). These can be obtained by reacting lithium hydroxide or lithium carbonate with boric acid or boron trioxide and the corresponding ligand of the salt of the general formula (I), using only solvents which have a high electrochemical voltage window.
  • the invention also relates to the lithium salts defined in claims 17 and 18.
  • Another object of the invention is the use of at least one mixture according to the invention in electrolytes, primary and secondary batteries, capacitors, supercapacitors and galvanic cells.
  • the invention further relates to electrolytes, primary batteries, secondary batteries, capacitors, supercapacitors and galvanic cells which contain at least one mixture according to the invention and, if appropriate, further lithium salts and / or additives.
  • These other lithium salts and additives are known to the person skilled in the art, for example from Doron Aurbach, Nonaqueous Electrochemistry, Marc Dekker Inc., New York 1999; D. Linden, Handbook of Batteries, Second Edition, McGraw-Hill Inc., New York 1995 and G. Mamantov and Al Popov, Chemistry of Nonaqueous Solutions, Current Progress, VCH Verlagstician, Weinheim 1994. They are hereby introduced as a reference and are therefore considered part of the disclosure.
  • Organic isocyanates (DE 199 44 603) can be included to reduce the water content.
  • N (CF 3 ) 2 may be included, with Kt N, P, As, Sb, S, Se AN, P, P (O), O, S, S (O), SO 2 , As, As (O), Sb, Sb (O)
  • R 1 , R 2 , R 3 are the same or different
  • Kt may be included in cyclic or heterocyclic ring, and the groups attached to Kt may be the same or different.
  • mixtures according to the invention can also be contained in electrolytes which
  • Lithium complex salts of the formula (DE 199 32 317)
  • R 1 , R 2 are the same or different, optionally connected directly to one another by a single or double formation, in each case individually or together, the meaning of an aromatic ring from the group phenyl, naphthyl, anthracenyl or phenanthrenyl, which is unsubstituted or one to six times alkyl
  • alkoxy groups (Ci to C 6 ) or halogen (F, Cl, Br) may be substituted, or in each case individually or together the meaning of an aromatic heterocyclic ring from the group pyridyl, pyrazyl or pyrimidyl, the can be unsubstituted or mono- to tetrasubstituted by alkyl (Ci to C 6 ), alkoxy groups (d to C 6 ) or halogen (F, Cl, Br), or in each case individually or jointly the meaning of an aromatic ring from the group hydroxylbenzoecarboxyl, hydroxylnaphthalenecarboxyl, hydroxylbenzenesulfonyl and hydroxylnaphthalenesulfonyl, which is unsubstituted or one to four times by alkyl (Ci to C 6 ), alkoxy groups (Ci to C 6 ) or halogen (F, Cl .
  • Br may have, R 3 to R 6 each individually or in pairs, optionally directly linked to one another by a single or double bond, have the following meanings: 1. Alkyl (Ci to C ⁇ ), alkyloxy (Ci to C 6 ) or halogen (F, Cl, Br)
  • Phenyl, naphthyl, anthracenyl or phenanthrenyl which may be unsubstituted or monosubstituted or substituted six times by alkyl (Ci to CQ), alkoxy groups (Ci to C 6 ) or halogen (F, Cl, Br), pyridyl, pyrazyl or pyrimidyl, the unsubstituted or mono- to tetrasubstituted by alkyl (Ci to C 6 ), alkoxy groups (Ci to C 6 ) or halogen (F, Cl, Br).
  • E is a Lewis acid selected from the group BR 1 R 2 R 3 , AIR 1 R 2 R 3 , PR 1 R 2 R 3 R 4 R 5 , AsR 1 R 2 R 3 R 4 R 5 , VR 1 R 2 R 3 R 4 R 5 with
  • R 1 to R 5 are the same or different, optionally connected directly to one another by a single or double formation, in each case individually or together, the meaning of a halogen (F, Cl, Br), an alkyl or alkoxy radical (Ci to C 8 ), the can be partially or completely substituted by F, Cl, Br, an optionally linked via oxygen aromatic ring from the group phenyl, naphthyl, anthracenyl or phenanthrenyl, which is unsubstituted or one to six times by alkyl (Ci to C 8 ) or F, Cl , Br can be substituted, an optionally linked via oxygen aromatic heterocyclic ring from the group pyridyl, pyrazyl or Pyrimidyl, which may be unsubstituted or mono- to tetrasubstituted by alkyl (Ci to Cs) or F, Cl, Br and may have Z OR 6 , NR 6 R 7 , CR 6 R 7 R 8 , OSO
  • R 6 to R 8 are the same or different, optionally connected directly to one another by a single or double bond, each individually or together has the meaning of a hydrogen or the meaning of R 1 to R 5 .
  • borate salts (DE 199 59 722) of the general formula
  • M is a metal ion or tetraalkylammonium ion x, y 1, 2, 3, 4, 5 or 6 R 1 to R 4, the same or different, optionally linked by a single or double bond alkoxy or carboxy radicals (C ⁇ -C 8 ).
  • Additives such as silane compounds of the general formula (DE 100 276 26) SiR 1 R 2 R 3 R 4 can also be present, where R 1 to R 4 H
  • R 1 to R 4 are the same or different with the meaning of an aromatic ring from the group phenyl, naphthyl which is unsubstituted or one or more times by F, C y F 2 y + ⁇ - z H z or OC y F 2y + ⁇ - z H z , OC (O) C y F 2y + ⁇ - z H z , OS ⁇ 2 CyF 2y + ⁇ - z H z , N (CnF 2 n + ⁇ - z H z ) 2 , or with the meaning of a heterocyclic aromatic ring from the group phenyl, naphthyl which is unsubstituted or one or more times by F, C y F 2 y + ⁇ - z H z or OC y F 2y + ⁇ - z H z , OC (O) C y F 2y + ⁇ - z H z , OS ⁇ 2 CyF 2y + ⁇ -
  • mixtures according to the invention can also be used in electrolytes which contain lithium fluoroalkyl phosphates of the following formula (DE 100 089 55)
  • Ligands (CHbF c (CF 3 ) d) may be the same or different.
  • Salt is cleaned and isolated according to the usual methods.
  • mixtures according to the invention can also be used in electrolytes, the salts of the formula (DE 100 16801)
  • the compounds are represented by the conversion of phosphorus (V) -
  • K + A ' can be contained in the electrolyte, in which K + is a cation selected from the group
  • R 1 to R 5 are identical or different, optionally connected directly to one another by a single or double bond and each, individually or together, has the following meaning: - H,
  • C n F (2n + ⁇ -x) H x can be substituted with 1 ⁇ n ⁇ 6 and 0 ⁇ x ⁇ 13 and
  • a ⁇ an anion selected from the group [B (OR 1 ) n (OR 2 ) m (OR 3 ) 0 (OR 4 ) P r with 0 ⁇ n, m, o, p ⁇ 4 and m + n + o + p 4
  • R 1 to R 4 are different or in pairs the same, optionally connected directly to one another by a single or double formation, in each case individually or together, the meaning of an aromatic ring from the group phenyl, naphthyl, anthracenyl or phenanthrenyl, which is unsubstituted or one or more times can be substituted by C n F ( 2n + ⁇ -x) H x with 1 ⁇ n ⁇ 6 and 0 ⁇ x ⁇ 13 or halogen (F, Cl, Br), the meaning of an aromatic heterocyclic ring from the group pyridyl, pyrazyl or pyrimidyl which is unsubstituted or one or more times by C n F ( 2 ⁇ + ⁇ -x) H x with 1 ⁇ n ⁇ 6 and 0 ⁇ x ⁇ 13 or halogen or halogen (F, Cl, Br) can be substituted, or have the meaning of an alkyl radical (Ci to C 8 ) which is partially or
  • N (C n F (2n + 1-x) H x ) 2, O (C n F (2n + 1-x) H x ), S ⁇ 2 (C n F (2n + 1-x) H x ), C n F (2n + 1-x) H x can be substituted by 1 ⁇ n ⁇ 6 and 0 ⁇ x ⁇ 13, or OR 1 to OR 4 individually or together have the meaning of an aromatic or aliphatic carboxyl, dicarboxyl, Oxysulfonyl or oxycarboxyl radicals' which are partially or completely replaced by further groups, preferably F, Cl, N (C n F (2n + ⁇ -x) H x ) 2 , 0 (C n F (2 n + ⁇ -x) H x ), S0 2 (C n F ( 2 n + ⁇ -x) H x ), C n F ( 2 n + ⁇ -x) H x can be substituted with 1 ⁇ n ⁇ 6 and 0 ⁇ x
  • Ionic liquids K + A " (DE 100 279 95) with K + as above and A " also define an anion selected from the group
  • the mixtures according to the invention can be used in electrolytes for electrochemical cells which contain anode material consisting of coated metal cores selected from the group Sb, Bi, Cd, In, Pb, Ga and tin or their alloys (DE 100 16 024).
  • the process for producing this anode material is characterized in that a) a suspension or a sol of the metal or alloy core is produced in urotropin, b) the suspension is emulsified with hydrocarbons with C 5 -C 12, c) the emulsion on the metal or alloy cores and d) the metal hydroxides or metal oxides are converted into the corresponding oxide by tempering the system.
  • the mixtures according to the invention can also be used in electrolytes for electrochemical cells, with cathodes made of common lithium intercalation and insertion compounds, but also with cathode materials consisting of lithium mixed oxide particles which are coated with one or more metal oxides (DE 199 22 522) by suspending the particles in an organic solvent, adding a solution of a hydrolyzable metal compound and a hydrolysis solution to the suspension and then filtering off the coated particles, drying them and optionally calcining them.
  • cathodes made of common lithium intercalation and insertion compounds
  • cathode materials consisting of lithium mixed oxide particles which are coated with one or more metal oxides (DE 199 22 522) by suspending the particles in an organic solvent, adding a solution of a hydrolyzable metal compound and a hydrolysis solution to the suspension and then filtering off the coated particles, drying them and optionally calcining them.
  • They can also consist of lithium mixed oxide particles which are coated with one or more polymers (DE 19946 066) obtained by
  • the mixtures according to the invention can likewise be used in systems with cathodes which consist of lithium mixed oxide particles which are coated one or more times with alkali metal compounds and metal oxides (DE 100 14 884).
  • the process for producing these materials is characterized in that the particles are suspended in an organic solvent, an alkali metal salt compound suspended in an organic solvent is added, metal oxides dissolved in an organic solvent are added, the suspension is mixed with a hydrolysis solution and then the coated Particles are filtered off, dried and calcined.
  • the mixtures according to the invention can likewise be used in systems which contain anode materials with doped tin oxide (DE 100 257 61).
  • This anode material is produced by a) adding urea to a tin chloride solution, b) adding urotropin and a suitable doping compound to the solution, c) emulsifying the sol thus obtained in petroleum ether, d) washing the gel obtained and suctioning off the solvent such as e) the gel is dried and tempered.
  • the mixtures according to the invention can also be used in systems which contain anode materials with reduced tin oxide (DE 100 257 62).
  • This anode material is produced by a) adding urea to a tin chloride solution, b) adding urotropin to the solution, c) emulsifying the sol thus obtained in petroleum ether, d) washing the gel obtained and suctioning off the solvent, e ) the gel is dried and tempered and f) the SnO 2 obtained is exposed to a reducing gas stream in a fumigable furnace.
  • the mixtures according to the invention have the advantage that they show no or almost no signs of thermal decomposition over a very wide temperature range.
  • mixtures according to the invention have high thermal, chemical and electrochemical stability. This applies in particular to mixtures which contain salts of bisoxalatoborate, bismalonatoborate or bis [bis (trifluoromethyl) hydroxyacetato] borate.
  • Lithium tris (oxalato) phosphate is synthesized according to DE 199 33 898.
  • the lithium tris (oxalato) phosphate polymer / gel electrolyte is produced analogously to the second stage from example 1.
  • Step 1
  • the lithium bis [bis (trifluoromethyl) hydroxyacetato] borate polymer / gel electrolyte is prepared analogously to the second stage from Example 1.
  • Step 1
  • Lithium tris [bis (trifluoromethyl) hydroxyacetato] phosphate is synthesized analogously to lithium tris (oxalato) phosphate according to DE 199 33 898, with the difference that bis (trifluoromethyl) hydroxyacetic acid is used as the ligand instead of oxalic acid.
  • the lithium tris [bis (trifluoromethyl) hydroxyacetato] phosphate polymer / gel electrolyte is produced analogously to the second stage from example 1.

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EP02760270A 2001-08-17 2002-07-25 Polymerelektrolyte und deren verwendung in galvanischen zellen Withdrawn EP1417726A2 (de)

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DE10139409A DE10139409A1 (de) 2001-08-17 2001-08-17 Polymerelektrolyte und deren Verwendung in galvanischen Zellen
DE10139409 2001-08-17
PCT/EP2002/008287 WO2003017409A2 (de) 2001-08-17 2002-07-25 Polymerelektrolyte und deren verwendung in galvanischen zellen

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JP2005005117A (ja) * 2003-06-11 2005-01-06 Sony Corp 電池
JP4701595B2 (ja) * 2003-09-03 2011-06-15 ソニー株式会社 リチウムイオン二次電池
JP2006196250A (ja) * 2005-01-12 2006-07-27 Sanyo Electric Co Ltd リチウム二次電池
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JP4346565B2 (ja) 2004-03-30 2009-10-21 株式会社東芝 非水電解質二次電池
KR101373093B1 (ko) * 2005-07-29 2014-03-12 삼성에스디아이 주식회사 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지
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JP6121897B2 (ja) * 2010-04-01 2017-04-26 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 塩で変性された静電気散逸性ポリマー
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CA2457633A1 (en) 2003-02-27
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