# US 7,744,772 B2 · Cross-linkable composition for a battery electrolyte

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- Number: US 7,744,772 B2
- Document ID: US7744772B2
- Status: Granted
- Kind: B2
- Application number: 10/551,712
- Filed: 2004-03-23
- Published: 2007-06-07
- Granted: 2010-06-29
- Earliest claimed: 2003-04-03
- Assignees: Rhodia Chimie
- Inventors: Lucile Gambut-Garel; Carroll Vergelati; Jean-Yves Sanchez; Fannie Alloin
- Web page: https://patentgrep.com/patent/US7744772B2

## CPC

- H01M 10/052: Li-accumulators
- C08L 83/06: containing silicon bound to oxygen-containing groups (C08L83/12 takes precedence)
- H01M 6/181: {with polymeric electrolytes}
- H01M 6/188: {Processes of manufacture}
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 10/0567: characterised by the additives
- H01M 6/166: {by the solute}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- Y02E 60/10: Energy storage using batteries
- Y02T 10/70: Energy storage systems for electromobility, e.g. batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

The field of the present invention relates to the field of batteries and of polymer electrolytes for batteries and more particularly to the field of lithium batteries. The invention relates to a composition which can be polymerized and/or crosslinked photochemically or under an electron beam for a battery electrolyte comprising: (a) at least one polyorganosiloxane (POS) (A) comprising, per molecule at least 2 siloxyl units carrying radicals comprising an epoxy (Epx) functional group with optionally an ether (Eth) functional group, and at least one of the siloxyl units carries a polyoxyalkylene (Poa) ether radical; (b) at least one electrolyte salt ; and (c) an effective amount of at least one cationic photoinitiator.

## Claims

### Claim 1

A composition for use in the manufacture of a battery electrolyte, comprising:
(a) at least one polyorganosiloxane (POS) (A) comprising siloxyl units of formula (I)
R1xR2yR3zSiO(4−x−y−z)/2 (I)
in which formula the various symbols have the following meanings:
x, y and z are integers with 1≦x+y+z≦3;
the R1, R2 and R3 radicals are identical to or different from one another and represent an optionally substituted, linear or branched, C1-C12 alkyl radical, an optionally substituted C5-C10 cycloalkyl radical, an optionally substituted C6-C18 aryl radical, an optionally substituted aralkyl radical or an —OR4 radical where R4 represents a hydrogen or a linear or branched alkyl radical having from 1 to 15 carbon atoms, and
wherein the POS (A) comprises, per molecule:
at least 2 siloxyl units of formula (I), one of the radicals of which comprises a functional group of epoxy type (Epx) and optionally a functional group of ether type (Eth); and
at least one of the siloxyl units of formula (I) comprises at least one radical carrying a polyoxyalkylene (Poa) ether functional group;
(b) at least one electrolyte salt; and
(c) an effective amount of at least one cationic and/or radical photoinitiator, wherein said composition is polymerizable and/or crosslinkable by the cationic and/or radical route under irradiation and/or by (an) electron beam(s),

### Claim 2 (depends on 1)

The composition as claimed in claim 1, wherein the composition further comprises at least one POS (B) of formula (II)
R1xR2yR3zSiO(4−x−y−z)/2 (II)
in which formula the various symbols have the following meanings:
x, y and z are integers with 1≦x+y+z≦3;
the R1, R2 and R3 radicals are identical to or different from one another and represent an optionally substituted, linear or branched, C1-C12 alkyl radical, an optionally substituted C5-C10 cycloalkyl radical, an optionally substituted C6-C18 aryl radical, an optionally substituted aralkyl radical or an —OR4 radical where R4 represents a hydrogen or a linear or branched alkyl radical having from 1 to 15 carbon atoms;
with the condition that the POS (B) comprises, per molecule, at least 2 siloxyl units comprising a functional group of epoxy type (Epx) and optionally a functional group of ether type (Eth).

### Claim 3 (depends on 1)

The composition as claimed in claim 1, wherein the radical carrying a functional group of epoxy type (Epx) which can optionally carry a functional group of ether type (Eth) is selected from the following radicals:

### Claim 4 (depends on 1)

The composition as claimed in claim 1, wherein the polyoxyalkylene (Poa) ether group is of polyoxyethylene ether and/or polyoxypropylene ether type.

### Claim 5 (depends on 1)

The composition as claimed in claim 1, wherein the POS (A) is an essentially linear random or block copolymer having the mean general formula (VIII)
which can optionally comprise units of formula RSiO3/2 (T);
in which formula:
the R symbols, which are identical to or different from one another, each represent an optionally substituted, linear or branched, C1-C12 alkyl radical, an optionally substituted C6-C18 aryl radical, an optionally substituted C5-C10 cycloalkyl radical or an optionally substituted aralkyl radical;
the Z symbols, which are identical to or different from one another, each represent a hydroxyl radical or a linear or branched alkoxyl radical having from 1 to 15 carbon atoms;
the R′ symbols, which are identical to or different from one another, each represent a radical comprising from 2 to 50 carbon atoms;
the Poa symbols, which are identical to or different from one another, each represent groups of polyoxyalkylene ether type;
the R″ symbols, which are identical to or different from one another, each represent a radical comprising from 2 to 50 carbon atoms, which radical can optionally comprise functional groups of —O— ether type;
the (Epx) symbols represent an epoxy functional group, this functional group being either present as ending of the R″ hydrocarbon chain, of the following type:
or in an intermediate position of the R″ hydrocarbon chain, of the following type:
it being possible for this intermediate position of this epoxy functional group to be present on a cyclic part of the chain, in particular a ring having from 5 to 7 members;
the A symbols, which are identical to or different from one another, each represent a monovalent radical selected from —R, H, —R″-Epx and —OR4, where R4 represents a hydrogen or a linear or branched alkyl radical having from 1 to 15 carbon atoms;
m is an integer or fractional number greater than or equal to 0;
n is an integer or fractional number varying from 0 to 5;
o is an integer or fractional number greater than or equal to 1;
p is an integer or fractional number greater than or equal to 2; and
q is an integer or fractional number greater than or equal to 0.

### Claim 6 (depends on 5)

The composition as claimed in claim 5, wherein the numbers m, o p and q satisfy the following condition:
the ratio (m+n+p+q)/o ≦10.

### Claim 7 (depends on 5)

The as claimed in claim 5, wherein the groups of —R″-Epx type are selected from the group consisting of:

### Claim 8 (depends on 5)

The composition as claimed in claim 5, wherein the —R′-Poa groups are selected from:
—(CH2)3—O—(CH2CH2—O)m—CH3; —(CH2)2—O—(CH2CH2—O)m—CH3; and —(CH2)3—O—(CH(CH3)—CH2—O)m—CH3 and —(CH2)2—O—(CH(CH3)—CH2—O)m—CH3 , with m≦14.

### Claim 9 (depends on 1)

The composition as claimed in claim 1, wherein the electrolyte salt (b) is composed:
of a cation selected from the group consisting of metal cations, ammonium ions, amidinium ions and guanidinium ions; and
of an anion selected from the group consisting of chloride ions, bromide ions, iodide ions, perchlorate ions, thiocyanate ions, tetrafluoroborate ions, nitrate ions, AsF6−, PF6−, stearylsulfonate ions, trifluoromethanesulfonate ions, octylsulfonate ions, dodecylbenzenesulfonate ions, R4SO3−, (R4SO2)(R5SO2)N− and (R4SO2)(R5SO2)(R6SO2)C−; in each formula, the R4, R5 and R6 radicals are identical or different and represent electron-withdrawing groups.

### Claim 10 (depends on 9)

The composition as claimed in claim 9, wherein the R4, R5 and R6 radicals are perfluoroaryl or perfluoroalkyl type radicals, wherein the perfluoroalkyl groups comprising from 1 to 6 carbon atoms.

### Claim 11 (depends on 9)

The composition as claimed in claim 9, wherein the electrolyte salt (b) comprises a metal cation selected from alkali metals and alkaline earth metals of Groups 1 and 2 of the Periodic Table.

### Claim 12 (depends on 11)

The composition as claimed in claim 11, wherein the metal cation is lithium.

### Claim 13 (depends on 1)

The composition as claimed in claim 1, wherein the electrolyte salt (b) is selected from the group consisting of LiClO4, LiBF4, LiPF6, LiAsF6, LiCF3SO3, LiN(CF3SO2)2, and LiN(C2F5SO2)2 and a mixture of these compounds.

### Claim 14 (depends on 11)

The composition as claimed in claim 11, wherein the metal cation is a transition metal.

### Claim 15 (depends on 14)

The as claimed in claim 14, wherein the metal cation is selected from the group consisting of manganese, iron, cobalt, nickel, copper, zinc, calcium and silver.

### Claim 16 (depends on 1)

The composition as claimed in claim 1, it comprises further comprising an organic electrolyte (d).

### Claim 17 (depends on 16)

The composition as claimed in claim 16, wherein the organic electrolyte (d) is selected from the group consisting of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, 1,3-dioxolane, dimethoxyethane, tetrahydrofuran, dimethyl sulfoxide and polyethylene glycol dimethyl ether.

### Claim 18 (depends on 1)

The composition as claimed in claim 1, wherein the polymerization and/or crosslinking cationic photoinitiator (c) is an onium borate.

### Claim 19 (depends on 18)

The composition as claimed in claim 18, wherein the onium borate comprises a cation from:
a) onium cations of formula (IX)
[(R1)n−A−(R2)m]+ (IX)
in which formula:
A represents an element from groups 15 to 17, such as, for example: I, S, Se, P or N;
R1 represents a C6-C20 carbocyclic or heterocyclic aryl radical, it being possible for said heterocyclic radical to comprise nitrogen or sulfur as heteroelements;
R2 represents R1 or a linear or branched C1-C30 alkyl or those radical;
said R1 and R2 radicals optionally being substituted by a C1-C25 alkoxy, C1-C25 alky, nitro, chloro, bromo, cyano, carboxyl, ester or mercapto group;
n is an integer ranging from 1 to v+1, v being the valency of the element A; and
m is an integer ranging from 0 to v−1, with n+m=v+1,
b) organometallic cations of formula (X)
(L1L2L3M)q+
in which formula:
M represents a metal from Groups 4 to 10, in particular iron, manganese, chromium or cobalt;
L1 represents a ligand bonded to the metal M via π electrons, which ligand is chosen from η3-alkyl, η5-cyclopentadienyl and η7-cycloheptatrienyl ligands and η6-aromatic compounds chosen from η6-benzene ligands which are optionally substituted and compounds having from 2 to 4 condensed rings, each ring being capable of contributing via 3 to 8 π electrons to the valence layer of the metal M;
L2 represents a ligand bonded to the metal M via π electrons, which ligand is chosen from η7-cycloheptatrienyl ligands and η6-aromatic compounds chosen from η6-benzene ligands which are optionally substituted and compounds having from 2 to 4 condensed rings, each ring being capable of contributing via 6 or 7 π electrons to the valence layer of the metal M; and
L3 represents from 0 to 3 identical or different ligands bonded to the metal M via σ electrons, which ligand(s) is (are) chosen from CO and NO2+; the total electronic charge of the complex to which L1, L2 and L3 and the ionic charge of the metal M contribute being positive and equal to 1 or 2;
c) oxoisothiochromanium cations having the formula (XI)
(XI)
where the R3 radical represents a linear or branched C1-C20 alkyl radical, and
d) the organometallic cations of formula (XIII)
(L1L2L3M)q+ (XIII)
in which formula:
M represents a metal from Groups 4 to 10;
L1 and L2 each represent a ligand bonded to the metal M via π electrons,
L3 represents from 0 to 3 identical or different ligands bonded to the metal M via σ electrons, which ligand(s) is (are) chosen from CO and NO2+; and
the total electronic charge q being positive and equal to 1 or 2.

### Claim 20 (depends on 18)

The composition as claimed in claim 18, wherein the polymerization and/or crosslinking cationic photoinitiator (c) of borate type comprises an anion having the formula (XII)
[BXaRb]− (XII)
in which formula:
a and b are integers ranging from 0 to 4 with a+b=4;
the X symbols represent a chlorine atom or a fluorine atom when a=0 to 3 and an OH functional group (when a=0 to 2),
the R symbols are identical or different and represent:
a phenyl radical substituted by at least one electron-withdrawing group selected from CF3, NO2 and CN or by at least 2 fluorine atoms, this being the case when the cationic entity is an onium of an element from Groups 15 to 17,
a phenyl radical substituted by at least one electron-withdrawing element or at least one electron-withdrawing group selected from a fluorine atom, CF3, NO2 and CN, this being the case when the cationic entity is an organometallic complex of an element from the Groups 4 to 10, and/or
an aryl radical comprising at least two aromatic rings which is optionally substituted by at least one electron-withdrawing element or at least one electron-withdrawing group selected from a fluorine atom, CF3, NO2 or CN, whatever the cationic entity.

### Claim 21 (depends on 20)

The composition as claimed in claim 20, wherein the anionic entity of the borate is selected from the group consisting of:
[B(C6F5)4]−, [B(C6H4CF3)4]−, [B(C6H4CF3)4]−, [(C6F5)2BF2]−, [C6F5BF3]−, [B(C6H3F2)4]−,and [B(C6F4OCF3)4]−.

### Claim 22 (depends on 19)

The composition which can be polymerized and/or crosslinked under irradiation, preferably actinic irradiation and/or by (an) electron beam(s), by the cationic and/or radical route, for a battery electrolyte as claimed in claim 19, wherein the cationic entity is selected from the group consisting of:
[(Φ)2I]+, [C8H17—O-Φ-I-Φ]+, [(Φ-CH3)2I]+, [C12H25-Φ-I-Φ]+, [(C8H17—O-Φ)2I]+, [C8H17—O-Φ-I-Φ]+, [(Φ)3S]+, [(Φ)2-S-Φ-O—C8H17]+, [CH3-Φ-I-Φ-CH(CH3)2]+, [Φ-S-Φ-S-(Φ)2]+, [(C12H25-Φ)2I]+, [CH3-Φ-I-Φ-OC2H5]+, (η5-cyclopentadienyl)(η6-toluene)Fe+, (η5-cyclopentadienyl)(η6-1-methylnaphthalene)Fe+, and (η5-cyclopentadienyl)(η6-cumene)Fe+.

### Claim 23 (depends on 18)

The composition as claimed in claim 18, wherein the polymerization and/or crosslinking cationic photoinitiator (c) of borate type is selected from the group consisting of:
[(Φ)2I]+[B(C6F5)4]−; [(C8H17)-O-Φ-I-Φ]+[B(C6F5) 4]−, [C12H25-Φ-I-Φ]+[B(C6F5)4]−; [(C8H17—O-Φ)2I]+[B(C6F5)4]−, [(C8H17)—O-Φ-I-Φ]+[B(C6F5)4]−; [(Φ)3S]+[B(C6F5)4]−, [(Φ)2S-Φ-O—C8H17]+[B(C6H4CF3)4]−; [(C12H25-Φ)2I]+[B(C6F5)4]−, [(Φ)3S]+[B(C6F4OCF3)4]−; [(Φ-CH3)2I]+[B(C6F5)4]−, [(Φ-CH3)2I]+[B(C6F4OCF3)4]−; [CH3-Φ-I-Φ-CH(CH3)2]+[B(C6F5)4]−, (η5-cyclopentadienyl)(η6-toluene)Fe+[B(C6F5)4]−, (η5-cyclopentadienyl)(η6-1-methylnaphthalene)Fe+[B(C6F5)4]−, and (η5-cyclopentadienyl) (η6-cumene)Fe+[B(C6F5)4]−, and their mixture.

### Claim 24 (depends on 1)

The composition as claimed in claim 1, wherein it comprises at least one aromatic hydrocarbon photosensitizer (e) comprising one or more substituted or unsubstituted aromatic rings having a residual light absorption of between 200 and 500 nm.

### Claim 25 (depends on 24)

The composition claimed in claim 24, wherein the photosensitizer (e) is selected from the group consisting of:
4,4′-dimethoxybenzoin, 2,4-diethylthioxanthone, 2-ethylanthraquinone, 2-methylanthraquinone, 1,8-dihydroxyanthraquinone, dibenzoyl peroxide, 2,2-dimethoxy-2-phenylacetophenone, benzoin, 2-hydroxy-2-methylpropiophenone, benzaldehyde, 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-methylpropyl) ketone, benzoylacetone,
2-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and 4-isopropylthioxanthone and mixtures thereof.

### Claim 26 (depends on 1)

A polymer electrolyte for a battery obtained by polymerization and/or crosslinking by the cationic and/or radical route of a composition as claimed in claim 1.

### Claim 27 (depends on 26)

A polymer battery comprising a polymer electrolyte as claimed in claim 26 positioned between an anode and a cathode.

### Claim 28 (depends on 27)

The polymer battery as claimed in claim 27, wherein at least one of the constituents of the cathode is selected from the group consisting of the following compounds:
lithium metal, lithium alloys, inorganic materials comprising lithium insertions and carbonate materials comprising lithium insertions.