Electrolyte composition containing oligomeric silyl phosphonate ester

Abstract

To provide an electrolyte composition, an electrochemical cell comprising the electrolyte composition, and a method of making the electrochemical cell.SOLUTION: An electrolyte composition contains: at least one aprotic organic solvent; at least one conducting salt including at least one lithium salt; and at least one silyl ester phosphonate comprising the structure of the formula (I) in the figure. The electrolyte composition contains the at least one silyl ester phosphonate in an amount of 0.01 to 10 mass% based on the total mass of the electrolyte composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention is defined below by R 3 An electrolyte composition containing a silyl phosphonate ester containing the structure of formula (I) having T, [ka] The present invention relates to the use of a silyl phosphonate ester containing the structure of formula (I) in an electrolyte composition for an electrochemical battery, and to an electrochemical battery comprising the said electrolyte composition. [Background technology]

[0002] The storage of electrical energy remains a growing area of ​​interest. Efficiently storing electrical energy allows for its generation when advantageous and its use when needed. Electrochemical rechargeable batteries are well-suited for this purpose because they reversibly convert chemical energy into electrical energy (making them rechargeable). Lithium-ion batteries are of particular interest for energy storage because, compared to other battery systems, they offer high energy density and specific energy due to the small atomic weight of lithium ions and the resulting high battery voltage (typically 3-5V). Therefore, these systems are widely used as power sources for many portable electronic devices such as mobile phones, laptop computers, and mini-cameras.

[0003] In lithium-ion batteries and other lithium-ion rechargeable batteries, organic carbonates, ethers, esters, and ionic liquids are used as sufficiently polar solvents to dissolve the conductive salts. Generally, most modern lithium-ion batteries contain a solvent mixture of different organic aprotic solvents rather than a single solvent.

[0004] In addition to solvents and conductive salts, electrolyte compositions typically further contain additives to improve specific properties of the electrolyte composition and the electrochemical battery containing the electrolyte composition. Common additives include, for example, flame retardants, overcharge protection additives, and film-forming additives that react during the first charge / discharge cycle on the electrode surface, thereby forming a film on the electrode. Various Si and / or P-containing additives are known for use in electrolyte compositions.

[0005] US 8,734,668 B2 describes electrolyte compositions comprising silicon-containing compounds which may further contain heteroatoms such as B, Al, P, S, F, Cl, Br, and I.

[0006] EP 2 573 854 A1 discloses an electrolyte composition for use in lithium-ion batteries that includes a silyl ester group-containing phosphonic acid derivative in order to suppress the increase in battery resistance and the degradation of battery performance under high-temperature conditions.

[0007] US 2013 / 0164604 A1 refers to the use of phosphite esters, phosphonic acid esters, and bisphosphonic acid esters as additives in electrolyte compositions for use in lithium-ion batteries.

[0008] Novel cathode active materials are being used to improve the performance of lithium batteries. These cathode active materials have higher specific energy and / or higher operating voltage. Examples of such cathode active materials include high-energy NCM (lithium-ionized mixed oxide of Ni, Co, and Mn, so-called HE-NCM), high-voltage manganese spinel with a layered structure containing additional transition metals, and lithium nickel-cobalt aluminum oxide (also known as NCA). Some of these cathode active materials require the use of high cutoff voltages during charging to obtain the desired high specific energy. These cathode active materials impose new requirements on the electrolyte composition used, for example, in terms of stability at high voltages, O2 release, metal dissolution due to the dissolution of transition metal cations, and gas generation during storage.

[0009] There is still a need to improve the performance of electrochemical batteries, particularly those containing the aforementioned cathode active materials, in terms of, for example, high capacity retention, good long-term performance, high safety, reduced gas generation, and reduced impedance accumulation. [Overview of the project] [Problems that the invention aims to solve]

[0010] An object of the present invention is to provide additives for use in electrochemical batteries that improve the performance of the electrochemical battery, for example, with respect to high capacity retention, good long-term performance, high safety, reduced gas generation, and reduced impedance accumulation. In particular, additives for improving the performance of electrochemical batteries should be provided that include a cathode active material having high specific energy and / or high operating voltage. Another object of the present invention is to provide an electrolyte composition for electrochemical batteries that results in an electrochemical battery having high capacity retention, good long-term performance, and high safety. In particular, an electrolyte composition for use with a cathode active material having high specific energy and / or high operating voltage should be provided. An object of the present invention is also to provide an electrochemical battery that exhibits high capacity retention, good long-term performance, high safety, reduced gas generation, and reduced impedance accumulation. [Means for solving the problem]

[0011] Therefore, an electrolyte composition containing the following is provided. (i) at least one aprotic organic solvent; (ii) at least one conductive salt; (iii) At least one silyl phosphonate containing the structure of formula (I) [ka] Here, T is [ka] and [Chemical formula] selected from p is an integer from 0 to 6, and one or more CH2 groups of (CH2) p may be substituted with O, and one or more H of (CH2) p may be substituted with C1-C4 alkyl, R 1 each independently is H, F, Cl, R 4 , OR 4 , OSi(R 5 )3, OSi(OR 4 )3, and OP(O)(OR 4 )R 5 independently selected from R 4 each independently is C1-C 10 alkyl, C3-C7 (hetero) cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C5-C7 (hetero) aryl, and C6-C 13 (hetero) aralkyl, independently selected from, and may be substituted with one or more substituents selected from CN and F, and one or more CH2 groups of alkyl, alkenyl, and alkynyl not directly bonded to the Si atom or O atom may be substituted with O, R 3 and R 5 each independently is H, F, C1-C 10 alkyl, C3-C7 (hetero) cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C5-C7 (hetero) aryl and C6-C 13 (hetero) aralkyl, may be substituted with one or more substituents selected from CN and F, and one or more CH2 groups of alkyl, alkenyl and alkynyl not directly bonded to the P atom may be substituted with O, and (iv) optionally one or more additives.

[0012] Furthermore, the use of silyl phosphonate esters containing the unit of formula (I) in electrochemical batteries is provided, for example, as additives in electrochemical batteries and electrolyte compositions for electrochemical batteries. The electrochemical battery according to the present invention exhibits good capacity retention, good long-term performance, reduced battery resistance, and reduced gas generation during storage at high temperatures. Silyl phosphonate esters containing the unit of formula (I) are non-volatile under conditions during the preparation, storage, and use of the electrochemical battery, thereby facilitating the handling and storage of the electrolyte composition.

[0013] The present invention will be described in detail below. [Modes for carrying out the invention]

[0014] Chemically speaking, an electrolyte composition is any composition containing free ions and consequently possessing electrical conductivity. The electrolyte composition functions as a medium for moving ions involved in electrochemical reactions that occur within an electrochemical battery. In the case of lithium batteries, the ions involved in the electrochemical reactions are typically lithium ions. The most common electrolyte compositions are aqueous ionic solutions, but molten and solid electrolyte compositions are equally possible. Therefore, the electrolyte composition of the present invention is an electrically conductive medium due to the presence of at least one substance, primarily in a dissolved and / or molten state, i.e., electrical conductivity supported by the movement of ionic species. In liquid or gel electrolyte compositions, the conductive salt is typically dissolved in one or more aprotic organic solvents.

[0015] The electrolyte composition contains at least one aprotic organic solvent (i). The at least one aprotic organic solvent may optionally be selected from fluorinated aprotic organic solvents, i.e., fluorinated aprotic organic solvents and non-fluorinated aprotic organic solvents. The electrolyte composition may also contain a mixture of fluorinated aprotic organic solvents and non-fluorinated aprotic organic solvents.

[0016] The aprotic organic solvent is preferably selected from optionally fluorinated cyclic and acyclic organic carbonates, optionally fluorinated acyclic ethers and polyethers, optionally fluorinated cyclic ethers, optionally fluorinated cyclic and acyclic acetals and ketals, optionally fluorinated orthocarboxylic acid esters, optionally fluorinated esters and diesters of cyclic and acyclic carboxylic acids, optionally fluorinated cyclic and acyclic sulfones, optionally fluorinated cyclic and acyclic nitriles and dinitriles, optionally fluorinated cyclic and acyclic phosphates, and mixtures thereof.

[0017] Examples of optionally fluorinated cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC), where one or more H atoms may be substituted with F and / or C1-C4 alkyl groups, for example, 4-methylethylene carbonate, monofluoroethylene carbonate (FEC), and cis- and trans-difluoroethylene carbonates. Preferred optionally fluorinated cyclic carbonates are ethylene carbonate, monofluoroethylene carbonate, propylene carbonate, and especially ethylene carbonate.

[0018] Examples of arbitrarily fluorinated acyclic carbonates include di-C1~C 10 - Alkyl carbonates, where each alkyl group is independently selected and one or more H atoms may be substituted with F atoms. Preferably, optionally fluorinated di-C1-C4 alkyl carbonates. Examples include, for example, diethyl carbonate (DEC), ethyl methyl carbonate (EMC), 2,2,2-trifluoroethyl methyl carbonate (TFEMC), dimethyl carbonate (DMC), trifluoromethyl carbonate (TFMMC), and methyl propyl carbonate. Preferred acyclic carbonates are diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC).

[0019] In one embodiment of the present invention, the electrolyte composition contains a mixture of optionally fluorinated acyclic organic carbonates and cyclic organic carbonates in a mass ratio of 1:10 to 10:1, preferably 3:1 to 1:1.

[0020] Examples of arbitrarily fluorinated acyclic ethers and polyethers include arbitrarily fluorinated di-C1~C 10 -Alkyl ethers, optionally fluorinated di-C1~C4-alkyl-C2~C6 alkylene ethers, optionally fluorinated polyethers, and formula R'-(O-CF r H 2-r ) q -R'' is a fluorinated ether, where R' is C1~C 10 Alkyl or C3-C 10 It is a cycloalkyl group, where one or more H atoms of the alkyl and / or cycloalkyl group are substituted with F atoms, and R'' is H, F, C1-C 10 Alkyl or C3-C 10 It is a cycloalkyl group, where one or more H atoms of the alkyl group and / or cycloalkyl group are substituted with F atoms, r is 1 or 2, and q is 1, 2, or 3.

[0021] According to the present invention, optionally fluorinated di-C1~C 10 -Each alkyl group in the alkyl ether is selected independently of the others, and one or more H atoms of the alkyl group may be substituted with F. Optionally fluorinated di-C1~C 10 Examples of alkyl ethers include dimethyl ether, ethyl methyl ether, diethyl ether, methyl propyl ether, diisopropyl ether, di-n-butyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (CF2HCF2CH2OCF2CF2H), and 1H,1H,5H-perfluoropentyl-1,1,2,2-tetrafluoroethyl ether (CF2H(CF2)3CH2OCF2CF2H).

[0022] Examples of optionally fluorinated di-C1~C4-alkyl-C2~C6-alkylene ethers are 1,2-dimethoxyethane, 1,2-diethoxyethane, diglym (diethylene glycol dimethyl ether), triglyceride (triethylene glycol dimethyl ether), tetraglyceride (tetraethylene glycol dimethyl ether), and diethylene glycol diethyl ether.

[0023] Examples of suitable optionally fluorinated polyethers are polyalkylene glycols, preferably poly-C1-C4-alkylene glycols, particularly polyethylene glycols, in which one or more H atoms of the alkyl or alkylene group may be substituted with F atoms. The polyethylene glycol may contain up to 20 mol% of one or more C1-C4-alkylene glycols in copolymer form. The polyalkylene glycol is preferably a dimethyl- or diethyl-endcapped polyalkylene glycol. The molecular weight Mw of a suitable polyalkylene glycol, particularly a suitable polyethylene glycol, may be at least 400 g / mol. The molecular weight Mw of a suitable polyalkylene glycol, particularly a suitable polyethylene glycol, may be up to 5,000,000 g / mol, preferably up to 2,000,000 g / mol.

[0024] Formula R'-(O-CF p H 2-p ) q Examples of fluorinated ethers with -R'' include 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (CF2HCF2CH2OCF2CF2H) and 1H,1H,5H-perfluoropentyl-1,1,2,2-tetrafluoroethyl ether (CF2H(CF2)3CH2OCF2CF2H).

[0025] Examples of optionally fluorinated cyclic ethers are 1,4-dioxane, tetrahydrofuran, and their derivatives such as 2-methyltetrahydrofuran, in which, for example, one or more H atoms of the alkyl group may be substituted with F atoms.

[0026] Examples of optionally fluorinated acyclic acetals are 1,1-dimethoxymethane and 1,1-diethoxymethane. Examples of cyclic acetals are 1,3-dioxane, 1,3-dioxolane, and their derivatives such as methyldioxolane, in which, for example, one or more H atoms may be substituted with F atoms.

[0027] Examples of optionally fluorinated acyclic orthocarboxylic acid esters are tri-C1-C4 alkoxymethanes, particularly trimethoxymethane and triethoxymethane. Preferred examples of cyclic orthocarboxylic acid esters are 1,4-dimethyl-3,5,8-trioxabicyclo[2.2.2]octane and 4-ethyl-1-methyl-3,5,8-trioxabicyclo[2.2.2]octane, in which one or more hydrogen atoms may be substituted with fluorine.

[0028] Examples of optionally fluorinated acyclic esters of carboxylic acids include ethyl formic acid and methyl formate, ethyl acetate and methyl acetate, ethyl propionate and methyl propionate, and ethyl butanoate and methyl butanoate, as well as esters of dicarboxylic acids such as 1,3-dimethylpropanedioate, in which one or more H atoms may be substituted with F atoms. An example of a cyclic ester (lactone) of a carboxylic acid is γ-butyrolactone.

[0029] Examples of optionally fluorinated cyclic and acyclic sulfones include ethylmethylsulfone, dimethylsulfone, and tetrahydrothiophene-S,S-dioxide (sulfolane).

[0030] Examples of optionally fluorinated cyclic and acyclic nitriles and dinitriles are adiposinitrile, acetonitrile, propionitrile, and butyronitrile, in which one or more H atoms may be substituted with F atoms.

[0031] Examples of optionally fluorinated cyclic and acyclic phosphates include trialkyl phosphates, such as trimethyl phosphate, triethyl phosphate, and tris(2,2,2-trifluoroethyl) phosphate, in which one or more H atoms of the alkyl group may be substituted with F atoms.

[0032] More preferably, the aprotic organic solvent is selected from optionally fluorinated ethers and polyethers, optionally fluorinated cyclic and acyclic organic carbonates, optionally fluorinated cyclic and acyclic esters and diesters of carboxylic acids, and mixtures thereof. Even more preferably, the aprotic solvent is selected from optionally fluorinated ethers and polyethers, optionally fluorinated cyclic and acyclic organic carbonates, and mixtures thereof.

[0033] According to one embodiment, the electrolyte composition is a fluorinated ether and a polyether, for example, CF2HCF2CH2OCF2CF2H or CF2H(CF2)3CH2OCF2CF2H, which is defined by the formula R'-(O-CF p H 2-p ) q It contains at least one solvent selected from compounds of the formula fluorinated ether -R''.

[0034] According to another embodiment, the electrolyte composition contains at least one solvent selected from fluorinated cyclic carbonates, such as 1-fluoroethyl carbonate.

[0035] According to further embodiments, the electrolyte composition includes at least one solvent selected from fluorinated cyclic carbonates, such as 1-fluoroethyl carbonate, as well as fluorinated ethers and polyethers, such as CF2HCF2CH2OCF2CF2H or CF2H(CF2)3CH2OCF2CF2H, which are defined above as R'-(O-CF r H 2-r ) s It contains at least one solvent selected from compounds of fluorinated ethers of the formula -R''.

[0036] According to another embodiment, the electrolyte composition contains at least one fluorinated cyclic carbonate, for example, 1-fluoroethyl carbonate, and at least one non-fluorinated acyclic organic carbonate, for example, dimethyl carbonate, diethyl carbonate, or ethylmethyl carbonate.

[0037] The electrolyte composition contains at least one conductive salt (ii). The electrolyte composition functions as a medium for moving ions involved in the electrochemical reactions occurring in the electrochemical cell. The conductive salt (ii) present in the electrolyte composition is usually solvated in an aprotic organic solvent (i). Preferably, at least one conductive salt (ii) is selected from lithium salts. Examples of lithium ion-containing conductive salts are: · Li[F6-xP(CyF 2y+1 ) x In the equation, x is an integer in the range of 0 to 6, and y is an integer in the range of 1 to 20. Li[B(R I )4], Li[B(R I )2(OR II O)] and Li[B(OR II O)2], where each R I These are independently selected from F, Cl, Br, I, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, OC1-C4 alkyl, OC2-C4 alkenyl, and OC2-C4 alkynyl, and alkyl, alkenyl, and alkynyl are one or more OR III It may be replaced with OR III (OR II O) is a divalent group derived from a 1,2- or 1,3-diol, a 1,2- or 1,3-dicarboxylic acid, or a 1,2- or 1,3-hydroxycarboxylic acid, where the divalent group forms a 5-membered or 6-membered ring via the central B atom and both oxygen atoms; • LiClO4; LiAsF6; LiCF3SO3; Li2SiF6; LiSbF6; LiAlCl4; Li(N(SO2F)2), lithium tetrafluoro(oxalato) phosphate; lithium oxalate; and · General formula Li[Z(C n F 2n+1 SO2) m The salt of ], where m and n are defined as follows: If Z is selected from oxygen and sulfur, then m=1, When Z is selected from nitrogen and phosphorus, m=2, When Z is selected from carbon and silicon, m=3, n is an integer in the range of 1 to 20.

[0038] divalent group (OR II Suitable 1,2- and 1,3-diols derived from O) may be aliphatic or aromatic and may be selected from, for example, 1,2-dihydroxybenzene, propane-1,2-diol, butane-1,2-diol, propane-1,3-diol, butane-1,3-diol, cyclohexyl-trans-1,2-diol and naphthalene-2,3-diol, optionally substituted with one or more F and / or at least one linear or branched non-fluorinated, partially fluorinated or fully fluorinated C1-C4 alkyl group. An example of such a 1,2- or 1,3-diol is 1,1,2,2-tetra(trifluoromethyl)-1,2-ethanediol. "Fully fluorinated C1-C4 alkyl group" means that all H atoms of the alkyl group are substituted with F.

[0039] divalent group (OR IIA suitable 1,2- or 1,3-dicarboxylic acid derived from O) may be aliphatic or aromatic, and may be, for example, oxalic acid, malonic acid (propane-1,3-dicarboxylic acid), phthalic acid or isophthalic acid, preferably oxalic acid. The 1,2- or 1,3-dicarboxylic acid is optionally substituted with one or more F and / or at least one linear or branched non-fluorinated partially fluorinated or fully fluorinated C1-C4 alkyl group.

[0040] divalent group (OR II Suitable 1,2- or 1,3-hydroxycarboxylic acids derived from O) may be aliphatic or aromatic and are, for example, salicylic acid, tetrahydrosalicylic acid, malic acid, and 2-hydroxyacetic acid, optionally substituted with one or more F and / or at least one linear or branched non-fluorinated, partially fluorinated or fully fluorinated C1-C4 alkyl group. An example of such a 1,2- or 1,3-hydroxycarboxylic acid is 2,2-bis(trifluoromethyl)-2-hydroxyacetic acid.

[0041] Li[B(R I )4], Li[B(R I )2(OR II O)] and Li[B(OR II Examples of [O)2] include LiBF4, lithium difluorooxalatoborate, and lithium dioxalatoborate.

[0042] Preferably, at least one lithium ion-containing conductive salt is selected from LiPF6, LiAsF6, LiSbF6, LiCF3SO3, LiBF4, lithium bis(oxalato)borate, LiClO4, LiN(SO2C2F5)2, LiN(SO2CF3)2, LiN(SO2F)2, and LiPF3(CF2CF3)3. More preferably, the conductive salt is selected from LiPF6, LiN(SO2F)2, and LiBF4, with LiPF6 being the most preferred conductive salt.

[0043] The conductive salt is usually present in the total electrolyte composition at a minimum concentration of at least 0.1 mol / l, and preferably the concentration of the ion-containing conductive salt is 0.5 to 2 mol / l.

[0044] The electrolyte composition contains at least one silyl phosphonate ester having the structure of formula (I), [ka] During the ceremony, T is [ka] and [ka] Selected from; p is an integer from 0 to 6, (CH2) p One or more CH2 groups may be substituted with O, (CH2) p One or more of the hydrogen atoms may be substituted with C1-C4 alkyl groups; R 1 These are H, F, Cl, and R, respectively. 4 , OR 4 OSi(R 5 )3, OSi(OR 4 )3, and OP(O)(OR 4 )R 5 Selected independently from; R 4 C1-C may each be substituted with one or more substituents selected from CN and F. 10 Alkyl, C3-C7 (hetero)cycloalkyl, C2-C 10 Alkenyl, C2~C 10 Alkynyl, C5-C7 (hetero)aryl, and C6-C 13 Independently selected from (hetero)aralkyl groups, where one or more CH2 groups of alkyl, alkenyl, and alkynyl groups not directly bonded to a Si or O atom may be substituted with O; R 3 and R 5H, F, C1-C may each be substituted with one or more substituents selected from CN and F. 10 Alkyl, C3-C7 (hetero)cycloalkyl, C2-C 10 Alkenyl, C2~C 10 Alkinyl, C5-C7 (hetero)aryl and C6-C 13 Independently selected from (hetero)aralkyl groups, where one or more CH2 groups of alkyl, alkenyl, and alkynyl groups not directly bonded to the P atom may be substituted with O.

[0045] Silyl phosphonate esters containing the structure of formula (I) are also called component (iii) of the electrolyte composition.

[0046] As used herein, the term "C1~C 10 "Alkyl" refers to a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms with one free valence. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, 2-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, and n-decyl. Preferably, C1-C6 alkyl groups are preferred, more preferably C1-C4 alkyl groups are preferred, even more preferably methyl, ethyl, and n- and isopropyl groups are preferred, and most preferably methyl and ethyl groups are preferred.

[0047] As used herein, the term "C3-C7 (hetero)cycloalkyl" means a saturated 3- to 7-membered hydrocarbon ring having one free valence, wherein one or more C atoms of the saturated ring may be independently substituted by heteroatoms selected from N, S, O, and P. Examples of C3-C7 cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, with cyclohexyl being preferred. Examples of C3-C7 heterocycloalkyls include oxyranil, tetrahydrofuryl, pyrrolidyl, piperidyl, and morpholinil.

[0048] As used herein, the term "C2~C" 10 An "alkenyl" refers to an unsaturated linear or branched hydrocarbon group having 2 to 10 carbon atoms with one free valence. Unsaturated means that the alkenyl group contains at least one C2-C double bond. 10 Alkenyls include, for example, ethenyl, propenyl, 1-n-butenyl, 2-n-butenyl, isobutenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, and 1-decenyl. Preferably, C2-C6 alkenyl groups are preferred, more preferably C2-C4 alkenyl groups are preferred, even more preferably ethenyl and propenyl are preferred, and most preferably is 1-propen-3-yl, also known as allyl.

[0049] As used herein, the term "C2~C" 10 "Alkynyl" refers to an unsaturated linear or branched hydrocarbon group having 2 to 10 carbon atoms with one free valence, and the hydrocarbon group contains at least one C2-C6 triple bond. Examples of C2-C6 alkynyls include ethynyl, propynyl, 1-n-butynyl, 2-n-butynyl, isobutynyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octinyl, 1-nonyl, and 1-decinyl. Preferably, C2-C6 alkynyls are preferred, more preferably C2-C4 alkynyls, and still more preferably ethynyl and 1-propyne-3-yl (propargyl).

[0050] As used herein, the term “C5-C7(hetero)aryl” refers to an aromatic 5- to 7-membered hydrocarbon ring or fused ring having one free valence, wherein one or more of the C atoms of the aromatic ring may be independently substituted by heteroatoms selected from N, S, O, and P. Examples of C5-C7(hetero)aryls are pyrrolyl, furanyl, thiophenyl, pyridinyl, pyranyl, thiopyranyl, and phenyl. Phenyl is preferred.

[0051] As used herein, the term "C6-C 13 (hetero)aralkyl" refers to an aromatic 5- to 7-member hydrocarbon ring substituted by one or more C1-C6 alkyls, and one or more of the C atoms of the aromatic ring may be independently substituted by heteroatoms selected from N, S, O, and P. C6-C 13 (hetero)aralkyl groups contain a total of 6-13 C atoms and heteroatoms and have one free valence. The free valence may be located on the aromatic ring or on a C1-C6 alkyl group, i.e., C6-C 13 (hetero)aralkyl groups may be bonded via a (hetero)aromatic moiety or via the alkyl moiety of the group. C6-C 13 Examples of (hetero)aralkyl include methylphenyl, 2-methylpyridyl, 1,2-dimethylphenyl, 1,3-dimethylphenyl, 1,4-dimethylphenyl, ethylphenyl, 2-propylphenyl, benzyl, 2-CH2-pyridyl, and the like.

[0052] R 1 are each independently selected from H, F, Cl, R 4 , OR 4 , OSi(R 5 )3, OSi(OR 4 )3, and OP(O)(OR 4 )R 5 .

[0053] R 4 are each independently C1-C 10 alkyl, C3-C7(hetero)cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C5-C7(hetero)aryl, and C6-C 13 (hetero)aralkyl, each optionally substituted by one or more substituents selected from CN and F, and one or more CH2 groups of the alkyl, alkenyl, and alkynyl that are not directly bonded to the Si atom or O atom may be substituted by O. Preferably, R 4 are each independently C1-C10 One or more CH2 groups of alkyl, alkenyl, and alkynyl groups, independently selected from alkyl groups and not directly bonded to a Si or O atom, may be substituted with O, more preferably R 4 Each of these is independently selected from C1-C4 alkyl groups, which may be substituted with one or more substituents selected from CN and F. For example, R 4 This may be selected from methyl, ethyl, n-propyl, i-propyl, phenyl, cyclohexyl, CF3, CF2CF3, or CH2CN.

[0054] R 5 H, F, C1-C may each be substituted with one or more substituents selected from CN and F. 10 Alkyl, C3-C7 (hetero)cycloalkyl, C2-C 10 Alkenyl, C2~C 10 Alkynyl, C5-C7 (hetero)aryl, and C6-C 13 (Hetero)aralkyl groups may be independently selected, and one or more CH2 groups of alkyl, alkenyl, and alkynyl groups that are not directly bonded to the P atom may be substituted with O, preferably R 5 H, F, and C1-C may each be substituted with one or more F and / or CN. 10 One or more CH2 groups of an alkyl group independently selected from alkyls and not directly bonded to the P atom may be substituted with O, and a more preferred R 5 Each of these may be replaced by one or more F and / or CN C1~C 10 R is independently selected from alkyl groups and is even more preferable. 5 In generation, H and C1-C4 alkyl groups are independently selected, which may be substituted with one or more F and / or CN groups. For example, R 5 This may be selected from H, F, methyl, ethyl, n-propyl, i-propyl, phenyl, cyclohexyl, CF3, CF2CF3, or CH2CN.

[0055] Preferably, R 1 These are H, F, Cl, and C1-C, respectively.10 Alkyl, and OC1-C 10 A alkyl group is independently selected, and the alkyl group may be substituted with one or more substituents selected from CN and F, and one or more CH2 groups of the alkyl group that are not directly bonded to a Si or O atom may be substituted with O, and more preferably R 1 C1-C may be substituted with one or more substituents selected from CN and F. 10 R is independently selected from alkyl groups and is particularly preferred. 1 R is independently selected from C1-C4 alkyl groups, which may be substituted with one or more substituents selected from CN and F. 1 Each of these is independently selected from, for example, H, F, Cl, methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, i-propoxy, i-propyl, phenyl, phenoxy, CF3, OCF3, CF2CF3, OCF2CF3, and CH2CN, and is preferably selected from methyl, ethyl, i-propyl, and n-propyl.

[0056] R 3 H, F, C1-C may each be substituted with one or more substituents selected from CN and F. 10 Alkyl, C3-C7 (hetero)cycloalkyl, C2-C 10 Alkenyl, C2~C 10 Alkynyl, C5-C7 (hetero)aryl, and C6-C 13 One or more CH2 groups of alkyl, alkenyl, and alkynyl groups, independently selected from (hetero)aralkyl groups and not directly bonded to the P atom, may be rearranged by O, preferably R 3 H, F, C1-C may each be substituted with one or more substituents selected from CN and F. 10 One or more CH2 groups of alkyl, alkenyl, and alkynyl alkyls, which are independently selected from alkyl, C3-C7 (hetero)cycloalkyl, and C5-C7 (hetero)aryl alkyls and are not directly bonded to the P atom may be substituted with O, and more preferably, R 3H, F, and C1-C may each be substituted with one or more F and / or CN. 10 One or more CH2 groups of an alkyl group independently selected from alkyls and not directly bonded to the P atom may be substituted with O, and more preferably R 3 H and C1-C may each be replaced by one or more F and / or CN. 10 One or more CH2 groups of an alkyl group independently selected from the alkyl group and not directly bonded to the P atom may be substituted with O. Most preferred R 3 Each of these is independently selected from H and C1-C4 alkyl groups, which may be substituted with one or more F and / or CN. 3 For example, this may be selected from H, F, methyl, ethyl, n-propyl, i-propyl, cyclohexyl, phenyl, CF3, CF2CF3, CH2CH2OCH3, CH2CH2OCH3, and CH2CN. 3 It is particularly preferable that it is H.

[0057] T is [ka] and [ka] Selected from the following, p is an integer from 0 to 6, and may be 1, 2, 3, 4, 5, or 6. (CH2) p One or more CH2 groups may be substituted with oxygen, resulting in, for example, CH2-O-CH2 or CH2-O-CH2-O-CH2. If one or more CH2 groups are substituted with oxygen, the oxygen-substituted CH2 groups are not adjacent. (CH2) p One or more of the H atoms may be substituted with C1-C4 alkyl groups. Examples of (CH2)p groups in which one or more H atoms are substituted with C1-C4 alkyl groups are C(CH3)H, C(CH3)2, C(CH3)HCH2, C(CH3)HC(CH3)H, and C(CH3)HC(C2H4)H.

[0058] Examples of the structure of formula (I) are the following structures (I.1) through (I.5).

[0059] [ka]

[0060] Preferably, a silyl phosphonate ester containing the structure of formula (I) is -P(O)R 3 -A phosphonic acid group selected from -OC1~C6 alkyl groups, more preferably -P(O)R 3 -A phosphonic acid group selected from -OC1~C4 alkyl, particularly preferably -P(O)R 3 -OCH3 and -P(O)R 3 It is terminated by a phosphonic acid group selected from -OCH2CH3.

[0061] According to one embodiment, the silyl phosphonate contains the structure of formula (II), [ka]

[0062] In the formula, Q 1 Q is a monomer or oligomer group containing a chemical bond or one or more monomer units of formula (II.1), and 2 This is a monomer or oligomer group containing a chemical bond or one or more monomer units of formula (II.2).

[0063] [ka]

[0064] In the formula, T * These are, independently, Si or Si-(CH2) p -Si, where p is an integer from 0 to 6, i.e., p is selected from 0, 1, 2, 3, 4, 5, and 6, (CH2) p One or more CH2 groups may be substituted with O, (CH2) pOne or more of the H atoms may be substituted with C1-C4 alkyl groups, and T * If q is Si, 1 q is an integer from 0 to 2. 2 q is an integer from 0 to 2. 1 +q 2 = 2, that is, q 1 and q 2 is selected from 0, 1, and 2, and q 1 +q 2 = 2; T * is Si-(CH2) p -4, q 1 q is an integer from 0 to 4. 2 q is an integer from 0 to 4. 1 +q 2 =4, that is, q 1 and q 2 is selected from 0, 1, 2, 3, and 4, and q 1 +q 2 = 4; - * This is a continuation of the silyl phosphonate skeleton due to branching; and, R 1 and R 3 It is defined as described above and as preferred.

[0065] Q 1 Examples include: [ka] That is the case.

[0066] Q 2 Examples include: [ka] That is the case.

[0067] Q 1 and Q 2 The monomer units can be arranged in any way, for example, randomly, in blocks, or in an alternating order.

[0068] Preferably, Q 1and / or Q 2は Each comprises at least one monomer unit of formula (II.1) or formula (II.2) that is not a branched or crosslinked unit, i.e., where T * These are Si or Si-(CH2), respectively. p -Si, and p is an integer from 0 to 6, (CH2) p One or more CH2 groups may be substituted with O, (CH2) p One or more of the H atoms may be substituted with C1-C4 alkyl groups, and T * If q is Si, 1 is zero, and q 2 is 2, T * is Si-(CH2) p -If Si, q 1 is zero, and q 2 It is 4.

[0069] According to another embodiment, the silyl phosphonate ester has formula (III), [ka] During the ceremony, Q 1 Q 2 ,T and R 3 It is defined as described above; R 6 and R 7 R 8 and Si(OR 8 )3 and Si(R 9 ) Selected independently from 3; R 8 C1-C may each be substituted with one or more substituents selected from CN and F. 10 Alkyl, C3-C7 (hetero)cycloalkyl, C2-C 10 Alkenyl, C2~C 10 Alkynyl, C5-C7 (hetero)aryl, and C6-C 13 Independently selected from (hetero)aralkyls, one or more CH2 groups of alkyl, alkenyl, and alkynyl groups that are not directly bonded to an O atom or Si atom may be substituted with O; and R9 H, F, Cl, C1-C may each be substituted with one or more substituents selected from CN and F. 10 Alkyl, C3-C7 (hetero)cycloalkyl, C2-C 10 Alkenyl, C2~C 10 Alkynyl, C5-C7 (hetero)aryl, and C6-C 13 One or more CH2 groups of alkyl, alkenyl, and alkynyl groups, independently selected from (hetero)aralkyl groups and not directly bonded to an O atom, may be substituted with O.

[0070] R 6 and R 7 However, independently, C1~C 10 Alkyl, Si(OC1~C 10 Alkyl)3 and Si(R 9 ) Preferably selected from 3, R 9 These are H, F, Cl, and C1-C, respectively. 10 R is independently selected from alkyl groups and is more preferred. 9 R is selected from H, F, Cl, and C1-C4 alkyl groups. 6 and R 7 For example, it may be selected from methyl, ethyl, n-propyl, i-propyl, Si(CH3)3, Si(OCH3)3, Si(CH3)2Cl, and Si(CH3)Cl2. 6 and R 7 It is even more preferable that the C1-C4 alkyl group is independently selected, that is, that the silyl phosphonate is terminated with an alkoxy group such as methoxy, ethoxy, n-propoxy, and n-butoxy, and particularly preferred are silyl phosphonates terminated with methoxy and ethoxy.

[0071] In particular, silyl phosphonates may have formula (IV), [ka] During the ceremony, R 1 , R 3 , R 6 , R7 , T, T * , q 1 and q 2 These are defined as above, and as preferred; and r 1 and r 2 These are independent integers ranging from 0 to 300.

[0072] According to one embodiment of the present invention, a silyl phosphonate ester containing the structure of formula (I) is used as a mixture of different silyl phosphonate esters having different molecular weights, in particular as a mixture of a silyl phosphonate ester monomer containing the structure of formula (I) without repeating monomer units and at least one oligomer or polymer silyl phosphonate ester containing the structure of formula (I) and one or more repeating monomer units, for example, r 1 and r 2 Both are 0, and the compound of formula (IV) and r 1 +r 2 It is used as a mixture with at least one oligomeric or polymeric silyl phosphonate of formula (IV) having a value of >1.

[0073] The preparation of similar silyl phosphonate esters containing the structure of formula (I) is known to those skilled in the art; see, for example, K. Kellner and L. Rodewald, Monatshefte fuer Chemie, Vol. 121 (1990), pp. 1031-1038. The oligomeric silyl phosphonate esters used in the present invention can be prepared similarly. Depending on the starting materials, linear compounds or compounds with branching or crosslinking functions can be obtained. For example, reacting (CH3)2SiCl2 with dimethyl phosphite yields a linear silyl phosphonate ester. If a portion of (CH3)2SiCl2 is substituted with (CH3)SiCl3 or SiCl4, the monomer units are introduced into the silyl phosphonate ester that function as branching or crosslinking points. Furthermore, (CH3)2SiCl2 can be substituted with alkylidene-intersequenced dichlorodisilanes, such as Cl(CH3)2Si(CH2)2Si(CH3)2Cl. Depending on the starting compound, molar ratio, and reaction conditions, different silyl phosphonates, and often mixtures of monomeric silyl phosphonates and one or more oligomers and polymers of silyl phosphonates with different molecular weights, can be obtained.

[0074] Another aspect of the present invention is the use of silyl phosphonates containing the structure of formula (I) in electrolyte compositions for electrochemical batteries, such as lithium-ion capacitors, double-layer capacitors, and lithium batteries, particularly lithium secondary batteries as described below. Silyl phosphonates containing the structure of formula (I) are particularly suitable as cathode active substances that can interact with the cathode at the cathode-electrolyte interface, thereby reducing undesirable reactions between the cathode active substance and the electrolyte composition, and can suppress direct contact between components of the electrolyte composition and the cathode active substance, for example, by forming a film on the cathode or by preventing the formation of electrolyte decomposition products (e.g., HF) that are detrimental to the operation of the battery. Direct contact between the electrolyte composition and the cathode often leads to decomposition reactions.

[0075] Silyl phosphonates containing the structure of formula (I) can also be used as additives to reduce gas generation in electrolyte compositions for electrochemical batteries, such as lithium-ion capacitors, double-layer capacitors, and lithium batteries, particularly lithium secondary batteries as described below. Undesirable gas generation in electrochemical batteries is a safety issue because it can lead to increased internal pressure, which can result in battery leakage and loss of the electrolyte composition, and increases the possibility of ignition and the release of harmful compounds.

[0076] Silyl phosphonates containing the structure of formula (I) are typically used in electrolyte compositions by adding a desired amount of the compound of formula (I) to the electrolyte composition at the concentrations given below. Depending on the molecular weight and the presence of branched / crosslinked units, the silyl phosphonate may dissolve in a non-aqueous solvent (ii) or swell.

[0077] The electrolyte composition may contain one silyl phosphonate ester containing the structure of formula (I), or it may contain two or more silyl phosphonate esters containing the structure of formula (I), for example, two or three or more.

[0078] Typically, an electrolyte composition contains at least 0.01% by mass, preferably at least 0.02% by mass, and more preferably at least 0.1% by mass, of at least one silyl phosphonate ester containing the structure of formula (I), based on the total mass of the electrolyte composition. The upper limit of the total concentration of silyl phosphonate esters containing the structure of formula (I) in the electrolyte composition is typically 10% by mass, preferably 5% by mass, and more preferably 3% by mass, based on the total mass of the electrolyte composition. Typically, an electrolyte composition contains a total concentration of at least one silyl phosphonate ester containing the structure of formula (I) of 0.01 to 10% by mass, preferably 0.02 to 10% by mass, more preferably 0.1 to 5% by mass, and most preferably 0.1 to 3% by mass, based on the total mass of the electrolyte composition.

[0079] Furthermore, the electrolyte composition may contain at least one additional additive different from the silyl phosphonate containing the structure of formula (I). The at least one additional additive different from the silyl phosphonate containing the structure of formula (I) may be selected from polymers, film-forming additives, flame retardants, overcharge additives, wetting agents, HF and / or H2O scavengers, stabilizers for LiPF6 salts, ionic solvation accelerators, corrosion inhibitors, and gelling agents.

[0080] The minimum concentration of at least one further additive is typically 0.005% by mass, preferably 0.01% by mass, and more preferably 0.1% by mass, based on the total mass of the electrolyte composition. The maximum concentration of at least one further additive is typically 25% by mass.

[0081] One further class of additives is polymers. Polymers can be selected from polyvinylidene fluoride, polyvinylidene-hexafluoropropylene copolymer, polyvinylidene-hexafluoropropylene-chlorotrifluoroethylene copolymer, Nafion, polyethylene oxide, polymethyl methacrylate, polyacrylonitrile, polypropylene, polystyrene, polybutadiene, polyethylene glycol, polyvinylpyrrolidone, polyaniline, polypyrrole, and / or polythiophene. Polymers can be added to the formulations according to the present invention during aging to convert the liquid agent into a semi-solid or solid electrolyte and thus improve solvent residue. In this case, the polymer functions as a gelling agent.

[0082] Examples of flame retardants include organophosphorus compounds, such as cyclophosphazenes, phosphoramides, alkyl and / or aryl trisubstituted phosphates, alkyl and / or aryl disubstituted or trisubstituted phosphates, alkyl and / or aryl disubstituted phosphonates, alkyl and / or aryl trisubstituted phosphines, and their fluorinated derivatives. Examples of HF and / or H2O scavengers are optionally halogenated cyclic and acyclic silylamines.

[0083] Examples of overcharge protection additives include cyclohexylbenzene, o-terphenyl, p-terphenyl, and biphenyl, with cyclohexylbenzene and biphenyl being preferred.

[0084] Another class of additives, also called SEI-forming additives, are film-forming additives. The SEI-forming additives according to the present invention are compounds that decompose on the electrode to form a non-passivation layer on the electrode that prevents the decomposition of the electrolyte and / or the electrode. In this way, the battery life is significantly extended. Preferably, the SEI-forming additive forms a passivation layer on the anode. In the context of the present invention, the anode is understood as the negative electrode of the battery. Preferably, the anode has a reduction potential of 1 volt or less to lithium, such as a lithium intercalated graphite anode. To determine whether a compound is suitable as an anode film-forming additive, an electrochemical battery can be prepared comprising a graphite electrode and a metal counter electrode, as well as an electrolyte containing a small amount, typically 0.1 to 10% by mass of the electrolyte composition, preferably 0.2 to 5% by mass of the electrolyte composition, of the compound. When a voltage is applied between the anode and the lithium metal, the differential capacity of the electrochemical battery is recorded between 0.5V and 2V. If a large differential capacitance, e.g., -150 mAh / V at 1V, is observed during the first cycle, but is not observed or is essentially not observed during any subsequent cycles within the same voltage range, the compound can be considered an SEI-forming additive.

[0085] According to the present invention, the electrolyte composition preferably contains at least one SEI-forming additive. SEI-forming additives are known to those skilled in the art. More preferably, the electrolyte composition contains vinylene carbonates and their derivatives, such as vinylene carbonate and methylvinylene carbonate; fluorinated ethylene carbonates and their derivatives, such as monofluoroethylene carbonate, cis- and trans-difluorocarbonates; organic sultones, such as propylene sultone, propane sultone and their derivatives; ethylene sulfite and its derivatives; oxalate salts, including compounds such as lithium oxalate, dimethyl oxalate, lithium bis(oxalate)borate, lithium difluoro(oxalato)borate and ammonium bis(oxalato)borate, and oxalatophosphates, including lithium tetrafluoro(oxalato)phosphate; and at least one SEI-forming additive selected from sulfur-containing additives described in detail in WO 2013 / 026854 A1, particularly those described on page 12, line 22 to page 15, line 10.

[0086] The added compounds may have two or more effects in the electrolyte composition and in the electrochemical battery containing the electrolyte composition. For example, lithium oxalatoborate may be added as an additive that promotes SEI formation, but it may also function as a conductive salt.

[0087] In one embodiment of the present invention, the water content of the electrolyte composition is preferably less than 100 ppm, more preferably less than 50 ppm, and most preferably less than 30 ppm, based on the mass of each compound of the present invention. The water content can be determined by titration according to Karl Fischer, for example, as described in detail in DIN 51777 or ISO 760:1978. The minimum water content of the electrolyte composition may be selected from 3 ppm, and preferably from 5 ppm.

[0088] In one embodiment of the present invention, the HF content of the electrolyte composition is preferably less than 100 ppm, more preferably less than 50 ppm, and most preferably less than 30 ppm, based on the mass of each compound of the present invention. The HF content may be determined by titration.

[0089] The electrolyte composition is preferably liquid under the operating conditions, more preferably liquid at 1 bar and 25°C, even more preferably liquid at 1 bar and -15°C, particularly liquid at 1 bar and -30°C, and even more preferably liquid at 1 bar and -50°C. Such liquid electrolyte compositions are particularly suitable for outdoor applications, such as automotive batteries.

[0090] The electrolyte composition (A) can generally be prepared by dissolving a lithium conductive salt (i) in a corresponding solvent or solvent mixture (ii), as described above, by a method known to those skilled in the art in the field of electrolyte production, and by adding at least one silyl phosphonate ester containing the structure of formula (I), and optionally further additives (iv).

[0091] The electrochemical battery containing the electrolyte composition (A) may be a lithium battery, a double-layer capacitor, or a lithium-ion capacitor. The general structure of such electrochemical devices is well known, and the batteries are known to those skilled in the art.

[0092] Preferably, the electrochemical battery of the present invention is a lithium battery. As used herein, the term “lithium battery” means an electrochemical battery in which the anode contains lithium metal or lithium ions at some point during the charging / discharging of the battery. The anode may contain lithium metal or a lithium metal alloy, a substance that intercepts and releases lithium ions, or other lithium-containing compounds. The lithium battery is preferably a lithium secondary battery, i.e., a rechargeable lithium battery.

[0093] In a particularly preferred embodiment, the electrochemical battery is a lithium-ion battery, i.e., a secondary lithium-ion electrochemical battery comprising a cathode (A) containing a cathode active material capable of reversibly intercepting and releasing lithium ions, and an anode (B) containing an anode active material capable of reversibly intercepting and releasing lithium ions.

[0094] The anode (A) comprises an anodic active material capable of reversibly intercepting and releasing lithium ions, or forming an alloy with lithium. In particular, carbonaceous materials capable of reversibly intercepting and releasing lithium ions can be used as the anodic active material.

[0095] Suitable carbonaceous materials include graphite materials, more specifically crystalline carbon such as natural graphite, graphitized coke, graphitized MCMB and graphitized MPCF; amorphous carbon such as coke, mesocarbon microbeads (MCMB) calcined at temperatures below 1500°C, and mesophase pitch carbon fibers (MPCF); hard carbon; carbon composites, combustion organic polymers, carbon fibers, and other carbon anodic active materials (pyrolytic carbon, coke, graphite). The preferred carbonaceous material is graphite.

[0096] Further examples of anodic active materials include lithium metal and lithium metal alloys, i.e., materials containing elements that can form alloys with lithium. Non-limiting examples of materials containing elements that can form alloys with lithium include metals, metalloids, or alloys thereof. As used herein, the term “alloy” should be understood to refer to both alloys of two or more metals and alloys of one or more metals with one or more metalloids. If the alloy as a whole has metallic properties, the alloy may contain nonmetallic elements. The texture of an alloy may include solid solutions, eutectic (eutectic mixtures), intermetallic compounds, or two or more of these. Examples of such metallic or metalloid elements include, but are not limited to, titanium (Ti), tin (Sn), lead (Pb), aluminum, indium (In), zinc (Zn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), hafnium (Hf), zirconium (Zr), yttrium (Y), and silicon (Si). Metallic and metalloid elements of Group 4 or Group 14 of the long-period table of elements are preferred, with titanium, silicon, and tin being particularly preferred, and silicon being especially preferred. Examples of tin alloys include those having one or more elements selected from the group consisting of silicon, magnesium (Mg), nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium (Ti), germanium, bismuth, antimony, and chromium (Cr) as a second constituent element other than tin. Examples of silicon alloys include those containing one or more elements selected from the group consisting of tin, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, and chromium as a second constituent element other than silicon.

[0097] Further possible anodic active materials are silicon-containing materials. Silicon-containing materials include silicon itself, for example amorphous and crystalline silicon, silicon-containing compounds, for example, 0 <x<1.5のSiO xExamples include silicon alloys and compositions containing silicon and / or silicon-containing compounds, such as silicon / graphite composites and carbon-coated silicon-containing materials. Silicon itself can be used in different forms, such as nanowires, nanotubes, nanoparticles, films, nanoporous silicon, or silicon nanotubes. Silicon can be deposited on a current collector. The current collector may be selected from coated metal wires, coated metal grids, coated metal webs, coated metal sheets, coated metal foils, or coated metal plates. Preferably, the current collector is a coated metal foil, such as a coated copper foil. The silicon thin film may be deposited on the metal foil by any technique known to those skilled in the art, for example, by sputtering. One method for producing a silicon thin film electrode is described by R. Elazari et al. in Electrochem.Comm. 2012, 14, pp. 21-24.

[0098] Another possible anodic active material is lithium-ion intercalated oxide of Ti.

[0099] Preferably, the anode active material includes a carbonaceous material capable of reversibly intercepting and releasing lithium ions, and particularly preferably, a carbonaceous material capable of reversibly intercepting and releasing lithium ions. The carbonaceous materials that can be used are selected from crystalline carbon, hard carbon, and amorphous carbon. Graphite is particularly preferred. It is also preferred that the anode active material contains a silicon-containing material. It is even more preferred that the anode active material contains a lithium-ion intercalate oxide of Ti.

[0100] The electrochemical battery of the present invention comprises a cathode (B) containing at least one cathode active material. The at least one cathode active material contains a substance capable of intercalating and releasing lithium ions and is selected from: mixed lithium transition metal oxides containing Mn and at least one second transition metal; lithium intercalate mixed oxides containing Ni, Al and at least one second transition metal; LiNiPO4; LiNiPO4; and LiCoPO4.

[0101] An example of a mixed lithium transition metal oxide containing Mn and at least one second transition metal is formula (II) Li 1+e (NiaCo b Mn c M d ) 1-e O2 (II) During the ceremony, a is in the range of 0.05 to 0.9, preferably in the range of 0.1 to 0.8. b is in the range of 0 to 0.35. c is in the range of 0.1 to 0.9, preferably in the range of 0.2 to 0.8. d is in the range of 0 to 0.2. e is in the range of 0 to 0.3, preferably greater than 0 and up to 0.3, and more preferably in the range of 0.05 to 0.3. a+b+c+d=1, M is one or more metals selected from Na, K, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, Nb, Zr, and Zn.

[0102] The cobalt-containing compound of formula (II) is also called NCM.

[0103] Mixed lithium transition metal oxides having a layered structure of equation (II) where e is greater than 0 are also called overlithified.

[0104] Preferred lithium transition metal oxides having the layered structure of formula (II) are compounds that form a solid solution in which a LiM'O2 phase, in which M' is Ni and optionally one or more transition metals selected from Co and Mn, and a Li2MnO3 phase are mixed, and one or more metals M as defined above may be present. One or more metals M are usually present in trace amounts, for example, at a maximum of 10 mol% M, or at a maximum of 5 mol% M, or at a maximum of 1 mol%, based on the total amount of metals other than lithium present in the transition metal oxide, and are therefore also called "dopants" or "doping metals". When one or more metals M are present, they are usually present in amounts of at least 0.01 mol% or at least 0.1 mol%, based on the total amount of metals other than lithium present in the transition metal oxide. Furthermore, these compounds are of formula (IIa) zLiM'O2·(1-z)Li2MnO3 (IIa) In the formula, M' is Ni and at least one metal selected from Mn and Co; z ranges from 0.1 to 0.8. One or more metals selected from Na, K, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, Nb, Zr, and Zn may be present.

[0105] Electrochemically, the Ni and, if present, the Co atoms in the LiM'O2 phase are involved in reversible oxidation and reduction reactions, and Li + While voltages of less than 4.5V for / Li result in deintercalation and intercalation of Li ions, respectively, the Li2MnO3 phase, when the oxidation state of Mn in the Li2MnO3 phase is +4, + At voltages of 4.5V or higher relative to Li, oxidation and reduction reactions are only involved. Therefore, electrons are removed from the 2p orbitals of oxygen ions, not from the Mn atoms in this phase, resulting in the removal of oxygen from the lattice structure in the form of O2 gas, at least during the first charging cycle.

[0106] These compounds are also called HE-NCMs because they have a higher energy density than ordinary NCMs. Both HE-NCMs and NCMs are Li / Li + While they have an operating voltage of approximately 3.0-3.8V, to actually reach full charge and reap the benefits of their higher energy density, a high cutoff voltage is required for both the activation and cycling of the HE-NCM. Typically, Li / Li + The upper limit cutoff voltage of the cathode during charging is at least 4.5V, preferably at least 4.6V, more preferably at least 4.7V, and even more preferably at least 4.8V, for the activation of the HE-NCM. + The term "upper limit cutoff voltage during charging" refers to the upper limit of the voltage at which an electrochemical battery is charged (Li / Li). + This refers to the cathode voltage of an electrochemical cell relative to a reference anode. An example of HE-NCM is 0.33Li2MnO3·0.67Li(Ni 0.4 Co 0.2 Mn 0.4 )O2, 0.42Li2MnO3·0.58Li(Ni 0.4 Co 0.2 Mn 0.4 )O2, 0.50Li2MnO3·0.50Li(Ni 0.4 Co 0.2 Mn 0.4 )O2, 0.40Li2MnO3·0.60Li(Ni 0.8 Co 0.1 Mn 0.1 )O2 and 0.42Li2MnO3·0.58Li(Ni 0.6 Mn 0.4 It is O2.

[0107] An example of a manganese-containing transition metal oxide having a layered structure of equation (II) where d is 0 is LiNi 0.33 Mn 0.67 O2, LiLiLi 0.25 Mn 0.75 O2, LiLiLi 0.35 Co 0.15 Mn 0.5 O2, LiLiLi 0.21 Co0.08 Mn 0.71 O2, LiLiLi 0.22 Co 0.12 Mn 0.66 O2, LiLiLi 0.8 Co 0.1 Mn 0.1 O2, LiLiLi 0.6 Co 0.2 Mn 0.2 O2 and LiNi 0.5 Co 0.2 Mn 0.3 It is O2. It is preferable that the transition metal oxide of general formula (II) with d = 0 does not contain any further cations or anions in significant amounts.

[0108] An example of a manganese-containing transition metal oxide having a layered structure of formula (II) where d is greater than 0 is 0.33Li2MnO3·0.67Li(Ni 0.4 Co 0.2 Mn 0.4 )O2, 0.42Li2MnO3·0.58Li(Ni 0.4 Co 0.2 Mn 0.4 )O2, 0.50Li2MnO3·0.50Li(Ni 0.4 Co 0.2 Mn 0.4 )O2, 0.40Li2MnO3·0.60Li(Ni 0.8 Co 0.1 Mn 0.1 )O2 and 0.42Li2MnO3·0.58Li(Ni 0.6 Mn 0.4 The oxide is O2, and may contain one or more metals M selected from Na, K, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, Nb, Zr, and Zn. Preferably, one or more doping metals are present up to 1 mol%, based on the total amount of metals other than lithium present in the transition metal oxide.

[0109] Other preferred compounds of formula (II) are Ni-rich compounds, where the Ni content is at least 50 mol% based on the total amount of transition metals present. This includes compounds of formula (IIb), Li 1+e (Nia Co b Mn c M d ) 1-e O2 (IIb) During the ceremony, a is in the range of 0.5 to 0.9, preferably in the range of 0.5 to 0.8. b is in the range of 0 to 0.35. c is within the range of 0 to 0, and within the range of 0.2 to 0.5. d is in the range of 0 to 0.2. e is in the range of 0 to 0.3. a+b+c+d=1 M is one or more metals selected from Na, K, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, Nb, Zr, and Zn.

[0110] Examples of Ni-rich compounds of formula (I) include Li[Ni 0.8 Co 0.1 Mn 0.1 ]O2(NCM811), Li[Ni 0.6 Co 0.2 Mn 0.2 ]O2(NCM622), and Li[Ni 0.5 Co 0.2 Mn 0.3 ]O2(NCM523) is one example.

[0111] Further examples of mixed lithium transition metal oxides containing Mn and at least one second transition metal include manganese-containing spinel of formula (III), Li 1+t M 2-t O 4-s (III) During the ceremony, s ranges from 0 to 0.4. t is between 0 and 0.4, M is at least one further metal selected from Mn, Co, and Ni, preferably M is Mn and Ni, and optionally Co, i.e., part of M is Mn, another part of M, and any further part of M is selected from Co.

[0112] The cathode active material may also be selected from lithium intercalate mixed oxides containing Ni, Al and at least one second transition metal, such as lithium intercalate mixed oxides of Ni, Co and Al. An example of a Ni, Co and Al mixed oxide is the compound of formula (IV). Li[Ni h Co i Al j ]O2 (IV) During the ceremony, h is between 0.7 and 0.9, preferably between 0.8 and 0.87, more preferably between 0.8 and 0.85; i is between 0.15 and 0.20; and j is between 0.02 and 10, preferably between 0.02 and 1, more preferably between 0.2 and 0.1, and most preferably between 0.02 and 0.03.

[0113] The cathode active material may also be selected from LiMnPO4, LiNiPO4, and LiCoPO4. These phosphates typically exhibit an olivine structure and should typically be used to charge with an upper cutoff voltage of at least 4.5V.

[0114] Cathode (B) may further contain additional components such as binders and conductive materials such as conductive carbon. For example, cathode (B) may contain conductive polymorphs of carbon selected from, for example, graphite, carbon black, carbon nanotubes, graphene, or a mixture of at least two of the aforementioned substances. Examples of binders used in cathode (B) may include organic polymers such as polyethylene, polyacrylonitrile, polybutadiene, polypropylene, polystyrene, polyacrylate, polyvinyl alcohol, and polyisoprene, and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth)acrylonitrile, and 1,3-butadiene, particularly styrene-butadiene copolymers, and halogenated (co)polymers such as polyvinylidene chloride, polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride (PVdF), and polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, and copolymers of tetrafluoroethylene, vinylidene fluoride, and polyacrylonitrile.

[0115] The anode (A) and cathode (B) can be prepared by preparing an electrode slurry composition by dispersing an electrode active substance, a binder, optionally a conductive material, and optionally a thickener in a solvent, and then coating the slurry composition onto a current collector. The current collector may be a metal wire, a metal grid, a metal web, a metal sheet, a metal foil, or a metal plate. Preferably, the current collector is a metal foil, such as copper foil or aluminum foil.

[0116] The electrochemical cell of the present invention may conventionally contain further components, such as separators, housings, cable connectors, etc. The housing may be of any shape, for example, a cube or a cylinder, and the shape of the prism or housing used may be a metal-plastic composite film processed as a pouch. Suitable separators are, for example, glass fiber separators and polymer-based separators such as polyolefin separators or Nafion separators.

[0117] Some of the electrochemical batteries of the present invention may be coupled to one another, for example, in series or in parallel. Series connection is preferred. The present invention further provides the use of the electrochemical batteries of the present invention as described above in devices, in particular mobile devices. Examples of mobile devices include vehicles, such as automobiles, bicycles, aircraft, or water vehicles such as boats and ships. Other examples of mobile devices are portable devices, such as computers, in particular laptop computers, telephones, or power tools, such as those in the construction field, in particular drills, battery-powered screwdrivers, or battery-powered staplers. However, the electrochemical batteries of the present invention can also be used in stationary energy storage.

[0118] The present invention will be further illustrated by the following embodiments, but will not be limited thereto. [Examples]

[0119] I. Additives: I.1 Overview of the electrolyte additives used: [ka]

[0120] The units in square brackets indicate repeating monomer units. Oligomers are typically terminated with -OP(O)H-OCH3 or -OP(O)H-OCH2CH3, except for oligomers containing a Si(CH3)3 terminal group.

[0121] I.2 Preparation of Additives A commercially available comparative additive R1 was used. Comparative additive R2 was prepared according to R. Rabinowitz, J. Org. Chem. Vol. 28 (1963), pp. 2975-2978. Additive mixtures M1 to M12 containing molecular entities A1 to A19 were synthesized according to K. Kellner, L. Rodewald, Monatshefte fuer Chemie, Vol. 121 (1990), pp. 1031-1038.

[0122] All compounds were directly analyzed after preparation 1 using 1H NMR spectroscopy and 31 31P NMR spectroscopy. Samples were prepared and measured under an inert atmosphere with reference to CDCl3 (7.26 ppm); when analyzing electrolytes, a screw-cap NMR tube equipped with an inner tube filled with reference to C6D6 (7.16 ppm) was used. Spectra were recorded on a Bruker Avance III equipped with a CryoProbe Prodigy probehead or 1 a Varian NMR System 400 operating at a frequency of 1H: 500.36 MHz and 31 31P: 202.56 MHz. 31 31P NMR data were collected separately from protons: {1H} for clarity. 31 The relaxation time D1 for 31P NMR measurements was increased to 60 seconds, and the amount of each P species was determined accordingly. MNova software was used for spectral analysis.

[0123] An Anton Paar Physica MCR 51 was used for viscosity measurements. Measurements were carried out at 20 °C with a shear stress profile from 1 to 1000 s -1 and the average value was calculated to obtain a given value. An overview of all prepared additive mixtures is shown in Table 1.

[0124] Experiment 1 - Mixture M1: According to the method described above, Me2SiCl2 (1.0 eq, 800 mmol, 104.8 g) was added to dimethyl phosphite (1.0 eq, 800 mmol, 88.0 g) at room temperature (RT) and stirred at 90 °C for 1 hour until the formation of volatile methyl chloride ceased. A distillation bridge was attached to the flask with the formed colorless residue and heated (1 hour, 100 °C, 0.2 mbar) to obtain silyl-H-phosphonate M1 as a colorless oil (105 g, yield 95%; chloride content 55 ppm).

[0125] M1 was obtained as a mixture of the repeating unit of [PHO(OSiMe2O)], A1 having a CH3OP(O)H end group, dimer A2, and oligomer A3. The ratio of A1:A2:A3 was 31 evaluated by integrating all signals in the range of -14 to -17.5 ppm (for A3), -2.5 ppm (for A2), and 10.4 ppm (for A1) in the 31P NMR spectrum. Under the above conditions, the ratio of A1:A2:A3 was 1:27:72.

[0126] Viscosity: 170 mPas Mn(M1) = 957 g / mol was 31 determined by 31P NMR as follows: The oligomer A3 may theoretically be divided into different units: two P-containing end groups [2×CH3OP(O)H-, total 158.03 g / mol], n Si- and P-containing repeating units [n×(CH3)2SiO2P(O)H units, 138.14 g / mol per unit], and one additional (CH3)2SiO2 unit (90.15 g / mol) according to the structure

Chemical formula

[0127] the signal of the end group in the 31P-NMR spectrum (quantitatively measured with a relaxation time D1 = 60 s) was set to 2. As a result, the number n of repeating units was obtained from the signal of the repeating unit. The number-average molecular weight was calculated by adding the molecular weight of the end group, n×the molecular weight of the repeating unit, and the molecular weight of the additional (CH3)2SiO2 unit. 31

[0128] The reaction yield was calculated based on the difference between the amounts of starting materials, the amount of alkyl chloride released, and the mass of the obtained oligomer mixture.

[0129] Experiment 2 - Mixture M2: According to the conditions described in Experiment 1, Me2SiCl2 (0.9 eq, 765 mmol, 98.7 g), MeSiCl3 (0.1 eq, 85 mmol, 12.7 g), and dimethyl phosphite (1.0 eq, 850 mmol, 93.5 g) were converted to obtain M2 (95.0 g, 87% yield). The ratio of A1:A2:A4 was: 31 In the 1P NMR spectrum, all signals in the ranges of -14 to -17.5 ppm (for A4), -2.5 ppm (for A2), and 10.4 ppm (for A1) were evaluated by integrating them. Under the above conditions, the ratio of A1:A2:A4 was 2:35:63.

[0130] Viscosity: 180mPas

[0131] Experiment 3 - Mixture M3: M3 was obtained by converting Me2SiCl2 (0.9 eq, 72 mmol, 9.47 g), SiCl4 (0.1 eq, 8 mmol, 1.4 g), and dimethyl phosphite (1.0 eq, 80 mmol, 8.8 g) according to the conditions described in Experiment 1. The ratio of A1:A2:A5 was: 31 In the 1P NMR spectrum, all signals in the ranges of -14 to -17.5 ppm (for A5), -2.5 ppm (for A2), and 10.4 ppm (for A1) were evaluated by integrating them. Under the above conditions, the ratio of A1:A2:A5 was 1:20:79.

[0132] Experiment 4 - Mixture M4: According to the conditions described in Experiment 1, Me2SiCl2 (0.9 eq, 99 mmol, 12.9 g), Me3SiCl (0.1 eq, 11 mmol, 1.21 g), and dimethyl phosphite (0.73 eq, 80 mmol, 8.80 g) were converted to obtain M4 (8.80 g, 80% yield). The ratio of A1:A2:A6 was: 31In the 1P NMR spectrum, all signals in the ranges of -14 to -17.5 ppm (for A6), -2.5 ppm (for A2), and 10.4 ppm (for A1) were evaluated by integrating them. Under the above conditions, the ratio of A1:A2:A6 was 1:34:65.

[0133] Experiment 5 - Mixture M5: Following the conditions described in Experiment 1, Me2SiCl2 (1.0 eq, 850 mmol, 109.7 g) and dimethyl phosphite (1.0 eq, 850 mmol, 93.5 g) were reacted for a long period (4 hours) using a vertical high-power condenser with a cooling medium at -10°C. After distillation of the volatile substances, M5 was obtained (116.0 g, 98% yield). The ratio of A1:A2:A3 was: 31 In the 1P NMR spectrum, all signals in the ranges of -14 to -17.5 ppm (for A3), -2.5 ppm (for A2), and 10.4 ppm (for A1) were evaluated by integrating them. Under the above conditions, the ratio of A1:A2:A3 was 1:11:88.

[0134] Mn = 2021 g / mol is the same as in Experiment 1. 31 The determination was made by 1P NMR.

[0135] Viscosity: 750mPas

[0136] Experiment 6 - Mixture M6: According to the conditions described in Experiment 5, Me2SiCl2 (1.0 eq, 83 mmol, 107.5 g) and dimethyl phosphite (0.90 eq, 75 mmol, 82.5 g) were converted to obtain M6 (103.0 g, 99% yield). The ratio of A1:A2:A3 was: 31 In the 1P NMR spectrum, all signals in the ranges of -14 to -17.5 ppm (for A3), -2.5 ppm (for A2), and 10.4 ppm (for A1) were evaluated by integrating them. Under the above conditions, the ratio of A1:A2:A3 was 0:3:97.

[0137] Experiment 7 - Mixture M7: According to the conditions described in Experiment 1, Me2SiCl2 (1.0 eq, 70 mmol, 9.12 g) and dimethylmethylmethylphosphonate (1.0 eq, 70 mmol, 8.95 g) were converted to obtain M7 (9.80 g, 92% yield). The ratio of A7:A8:A9 was: 31 In the 3P NMR spectrum, all signals in the ranges of 8–12 ppm (for A9), 21–23 ppm (for A8), and 33 ppm (for A7) were evaluated by integration. Under the above conditions, a ratio of A7:A8:A9 = 1:30:69 was obtained.

[0138] Experiment 8 - Mixture M8: According to the conditions described in Experiment 1, Me2SiCl2 (1.0 eq, 50 mmol, 6.45 g) and diethyl phosphite (1.0 eq, 50 mmol, 7.12 g) were converted to obtain M8 (3.80 g, 53% yield). The ratio of A10:A11:A12 was: 31 The signals were evaluated by integrating all signals in the ranges of -14 to -17.5 ppm (for A12), -4.2 ppm (for A11), and 7.2 ppm (for A10) of the 1P NMR spectrum. Under the above conditions, the ratio of A10:A11:A12 was 1:81:18.

[0139] Experiment 10 - Mixture M10: According to the conditions described in Experiment 1, Me2SiCl2 (1.0 eq, 70 mmol, 9.17 g) and dimethylphenyl phosphonate (1.0 eq, 70 mmol, 13.30 g) were converted to obtain M10 neu (13.6 g, 88% yield). The ratio of A13 neu:A14 neu:A15 neu was: 31 In the 1P NMR spectrum, all signals in the ranges of -0.2 to -2.5 ppm (for A15 new), 10.4 ppm (for A14 new), and 21.5 ppm (for A13 new) were evaluated by integrating them. Under the above conditions, the ratio of A13 neu:A14 neu:A15 neu was 1:55:44.

[0140] Viscosity: 1519 mPas Mn = 753 g / mol, as described for Experiment 1 31 Determined by 31P NMR; excluding the end groups [2×CH3OP(O)H-, total 310.24 g / mol], n Si and P-containing repeating units [n×(CH3)2SiO2P(O)H units, 214.25 g / mol per unit], and one additional (CH3)2SiO2 unit (90.15 g / mol) due to the structure

[0141] Experiment 11 - Mixture M11: According to the conditions described in Experiment 1, Et2SiCl2 (1.0 eq, 70 mmol, 7.86 g) and dimethyl phosphite (1.0 eq, 70 mmol, 11.34 g) were converted to obtain M11 (15.3 g, 98% yield). The ratio of A17:A16:A12 was 31 Evaluated by integrating all signals in the range of -14 to -17.5 ppm (for A17), -4.2 ppm (for A16), and 10.4 ppm (for A1) in the 31P NMR spectrum. Under the above conditions, the ratio of A1:A16:A17 was 2:90:8

[0142] Experiment 12 - Mixture M12: According to the conditions described in Experiment 1, ClMe2SiOSiMe2Cl (1.0 eq, 80 mmol, 6.45 g) and dimethyl phosphite (1.0 eq, 80 mmol, 9.00 g) were converted to obtain M12 (15.40 g, 87% yield). The ratio of A1:A18:A19 was 31 Evaluated by integrating all signals in the range of -15 to -17.5 ppm (for A12), -2.7 ppm (for A11), and 10.4 ppm (for A1) in the 31P NMR spectrum. Under the above conditions, the ratio of A1:A18:A19 was 1:9:80

[0143] Experiments 9 to 12 - Mixtures M9 to M12: Mixtures M9 to M12 were prepared and evaluated as described in Experiment 1, using the free bodies, their ratios, and reaction conditions listed in Table 1. The composition of the resulting mixtures is also shown in Table 1.

[0144] [Table 1]

[0145] II. Electrolyte composition The electrolyte compositions were prepared by dissolving 1.0 M LiPF6 in various mixtures of ethyl carbonate (EC, BASF), diethyl carbonate (DEC, BASF), monofluoroethylene carbonate (FEC, BASF), and 1H,1H,5H-perfluoropentyl-1,1,1,2,2-tetrafluoroethyl ether (CF2H(CF2)3CH2OCF2CF2H, FPEE, Foosung co.Ltd.). Comparative additives R1 and R2, as well as the additive mixtures M1, M2, and M7 of the present invention, were added to these compositions as shown in Table 2. R2, M1, M2, and M7 were used without further purification. "Volume %" indicates the volume of solvent in the electrolyte composition, and "Mass %" indicates the total mass of the electrolyte composition. All solvents were dry (water content <3 ppm).

[0146] All electrolyte compositions were prepared and stored in an Ar-filled glove box with oxygen and water levels of 1.0 ppm or less. The electrolyte compositions used are summarized in Table 2.

[0147] [Table 2]

[0148] III. Electrochemical Cells III.1) HE-NCM / Graphite 2032 Full Coin Battery The positive electrode for the electrochemical cycle experiment was prepared by coating aluminum foil with a slurry containing 92.5% by mass of a cathode active substance suspended in N-ethyl-2-pyrrolidinone (NEP), 2% by mass of graphite, 2% by mass of super C65 carbon black, and 3.5% by mass of polyvinylidene fluoride (PVdF) binder. The cathode active substance was HE-NCM 0.42Li2MnO 3· 0.56Li(Ni 0.4 Mn 0.4 Co 0.2 (O2, HE-NCM, BASF) was used. A commercially available graphite-coated tape from Elexcel Corporation Ltd. was used as the negative electrode. A 2032 coin cell was manufactured using positive and negative composite electrodes, a polypropylene separator (Celgard), and their respective electrolytes. All cells were assembled in an argon-filled glove box with oxygen and water levels below 1.0 ppm, and their electrochemical testing was performed using a Maccor 4000 battery test apparatus.

[0149] III.2) NCM622 / Graphite and NCM811 / Graphite Pouch Batteries The positive electrode for electrochemical cycle experiments in pouch batteries was prepared by coating an aluminum foil (thickness = 17 μm) with a slurry containing a cathode active material suspended in N-methyl-2-pyrrolidinone (NMP), carbon black, and a polyvinylidene fluoride (PVdF) binder using a roll coater. The electrode tape was dried in a hot air chamber, then dried under vacuum at 130°C for 8 hours, and finally pressed using a roll press. The cathode active material used was Li(Ni 0.8 Co 0.1 Mn 0.1 )O2(NCM811) or Li(Ni 0.6 Co 0.2 Mn 0.2The material is either O2 (NCM622). For the negative electrode, a slurry aqueous solution was prepared by mixing graphite and carbon black with CMC (carboxymethylcellulose) and SBR (styrene-butadiene rubber). The resulting slurry was coated onto copper foil (thickness = 9 μm) using a roll coater and dried in a hot air chamber (80°C to 120°C). The load of the resulting electrode was approximately 10 mg / cm². 2 It was found that the electrodes were pressed to an approximate thickness of 72 μm using a roll press. Pouch batteries (250 mAH) containing a separator stacked between the cathode and anode along with the NCM positive electrode and graphite negative electrode were assembled in an Ar-filled glove box. Subsequently, all batteries were filled with electrolytes as described in Table 2 in an argon-filled glove box with oxygen and water levels of 1.0 ppm or less, and their electrochemical tests were performed in a Maccor 4000 battery test system.

[0150] IV. Evaluation of Electrochemical Cells IV.1) Evaluation of cycle and battery resistance of HE-NCM / Graphite 2032 coin full cell at 25°C The battery was charged to a voltage of 4.7V with a constant current of 0.067C and discharged to a discharge voltage of 2.0V with a constant current of 0.067C at 25°C (activation cycle 1). Immediately afterward, the battery was charged to a voltage of 4.6V with a constant current of 0.1C at 25°C. The battery was further charged at 4.6V until the current reached 0.05C, and then discharged to a discharge voltage of 2.0V with a constant current of 0.1C (cycle 2). The same procedure as cycle 2 was repeated once (cycle 3). Subsequently, the battery was charged to a voltage of 4.6V with a constant current of 0.1C and discharged to a discharge voltage of 2.0V with a constant current of 0.1C (cycle 4). The charge capacity of this cycle is used as a baseline value for the next cycle (cycle 5), in which the battery is charged to 40% of the charge capacity of the next cycle (state of charge 40%) with a constant current of 0.1C. Once the battery reached 40% SOC, a 0.2C current cutoff was applied for 10 seconds, and the DC internal resistance (DCIR) was measured.

[0151] In cycles 6 and 7, the battery was charged to a voltage of 4.6V at 25°C with a constant current of 0.2C. The battery was further charged at 4.6V until the current reached 0.05C, and then discharged to a discharge voltage of 2.0V with a constant current of 0.5C. Next, the battery was charged to a voltage of 4.6V with a constant current of 0.7C, and then charged at 4.6V until the current reached 0.05C. While maintaining these charging conditions, the battery was discharged to a discharge voltage of 2.0V with constant currents of 1C (twice, cycles 8 to 9), 2C (twice, cycles 10 to 11), and 3C (twice, cycles 12 to 13). The discharge capacity recorded in cycle 13 is expressed as a percentage of the discharge capacity obtained in cycle 3 (see the discharge capacity ratio 3C / 0.1C(%) in Table 3).

[0152] Following the change in discharge capacity, a long-duration cycle was performed by charging to a voltage of 4.6V with a constant current of 0.7C, charging at 4.6V until the current reached 0.05C, and discharging to a discharge voltage of 2.0V with a constant current of 1C (Cycle 14). The discharge capacity measured in Cycle 14 was recorded as the initial discharge capacity at 1C. This charge-discharge procedure was repeated at least 200 times, or until the measured charge capacity was 70% or less of the charge capacity of Cycle 14. During the long-duration cycling experiment, DC internal resistance (DCIR) measurements were taken at 40% SOC every 100 cycles. The latter was achieved by repeating the cycling sequence described for Cycles 2 to 5 every 100 1C cycles. The results of various embodiments are shown in Table 3.

[0153] [Table 3]

[0154] The discharge capacity and battery resistance of batteries containing oligomeric silyl phosphonates are equivalent to or significantly better than those of monomeric additives, and oligomeric additives have the advantage of being less volatile. This facilitates the preparation and handling of the electrolyte composition, and the maintenance of a constant additive concentration during the filling of the battery with the electrolyte composition. Typically, before filling the battery with the liquid electrolyte, a vacuum is applied to the battery to ensure good filling of the battery with the liquid electrolyte composition and good wetting of all parts.

[0155] IV.2 Cycle evaluation of pouch batteries containing NCM622 and 811 cathodes and graphite anodes IV.2.1) Formation A pouch full of batteries containing an NCM622 or NCM811 cathode and a graphite anode was charged to a voltage of 3.7V or for up to 2 hours with a constant current of 0.1C. The batteries were then stored at 45°C for 17 hours, followed by degassing, and initial volume measurements were performed in water at ambient temperature via Archimedes assay.

[0156] IV.2.2) High-temperature storage of pouch-full batteries containing NCM622 / / graphite and NCM811 / / graphite at 60°C After the formation procedure was completed, the battery was charged to 4.2V at ambient temperature and stored at 60°C for 14 days. The amount of gas (mL) generated during storage was determined by Archimedes assay in water at ambient temperature, and the results are summarized in Table 6. The final charge (CCCV charge, 0.2C, 4.2V, 0.015C cutoff) and discharge (CC discharge, 0.2C, 3.0V cutoff) capacities were measured after the storage test. The capacity retention rate after cycling is expressed as the ratio of the final discharge capacity to the initial discharge capacity. The battery resistance after cycling was determined by charging to 50% SOC and measuring the DC internal resistance (DCIR) by applying current interruption. Results from various examples are shown in Tables 4 and 5. The electrochemical battery of the present invention exhibits a significantly lower gas generation amount compared to the comparative example battery.

[0157] [Table 4]

[0158] Table 5

Claims

1. An electrolyte composition, At least one aprotic organic solvent; At least one conductive salt comprising at least one lithium salt; At least one silyl phosphonate ester comprising the structure of formula (I); 【Chemistry 1】 During the ceremony, T is, 【Chemistry 2】 and 【Transformation 3】 Selected from, p is an integer from 0 to 6, (CH ２ ) ｐ one or more CH ２ The group may be substituted with O, (CH ２ ) ｐ One or more H are C １ ~C ４ It may also be substituted with alkyl; R １ is independently selected from H, F, Cl, R ４ , OR ４ , OSi(R ５ ), ３ , OSi(OR ４ ), ３ , and OP(O)(OR ４ )R ５ ; R ４ These are, respectively, C １ ~C １０ Alkyl, C ３ ~C ７ (hetero)cycloalkyl, C ２ ~C １０ Alkenil, C ２ ~C １０ Alkinyl, C ５ ~C ７ (Hetero)aryl, and C ６ ~C １３ Selected independently from (hetero)aralkyl; R ４ Each of these may be independently substituted with one or more substituents selected from CN and F; One or more alkyl, alkenyl, and alkynyl CH ２ The basis is that these are R ４ If present and not directly bonded to a Si atom or O atom, it may be substituted with O; R ３ and R ５ H, F, C １ ~C １０ Alkyl, C ３ ~C ７ (hetero)cycloalkyl, C ２ ~C １０ Alkenil, C ２ ~C １０ Alkinyl, C ５ ~C ７ (Hetero)aryl and C ６ ~C １３ (Hetero)aralkyls are independently selected, each of which may optionally be substituted with one or more groups selected from the group consisting of CN and F; and One or more alkyl, alkenyl, and alkynyl CH ２ The basis is that these are R ３ and / or R ５ If present and not directly bonded to P, it may be substituted with O; The electrolyte composition is characterized by containing at least one silyl phosphonate ester in an amount of 0.01 to 10% by mass based on the total mass of the electrolyte composition.

2. R １ These are H, F, Cl, and C, respectively. １ ~C １０ Alkyl and OC １ ~C １０ Independently selected from alkyl, C １ ~C １０ Alkyl and / or OC １ ~C １０ The alkyl group may be substituted with one or more substituents selected from CN and F, and the C is not directly bonded to a Si atom or an O atom. １ ~C １０ Alkyl and / or OC １ ~C １０ One or more alkyl CH groups ２ The electrolyte composition according to claim 1, wherein the group may be substituted with O.

3. R ３ H and C may each be substituted with one or more F and / or CN. １ ~C １０ A carbon atom that is independently selected from alkyl groups and is not directly bonded to the P atom. １ ~C １０ One or more alkyl CH groups ２ The electrolyte composition according to claim 1, wherein the group may be substituted with oxygen.

4. The structure of the above formula (I) is, 【Chemistry 4】 An electrolyte composition according to any one of claims 1 to 3, selected from the above.

5. The electrolyte composition according to claim 1, wherein the at least one aprotic organic solvent is selected from fluorinated and non-fluorinated cyclic and acyclic organic carbonates, fluorinated and non-fluorinated ethers and polyethers, fluorinated and non-fluorinated cyclic ethers, fluorinated and non-fluorinated cyclic and acyclic acetals and ketals, fluorinated and non-fluorinated orthocarboxylic acid esters, fluorinated and non-fluorinated esters and diesters of cyclic and acyclic carboxylic acids, fluorinated and non-fluorinated cyclic and acyclic sulfones, fluorinated and non-fluorinated cyclic and acyclic nitriles and dinitriles, fluorinated and non-fluorinated cyclic and acyclic phosphates, and mixtures thereof.

6. The electrolyte composition according to claim 1, wherein the at least one aprotic organic solvent is selected from fluorinated and non-fluorinated ethers and polyethers, fluorinated and non-fluorinated cyclic and acyclic organic carbonates, and mixtures thereof.

7. An electrochemical battery comprising the electrolyte composition described in claim 1.

8. The electrochemical battery according to claim 7, wherein the electrochemical battery is a lithium battery, a double-layer capacitor, or a lithium-ion capacitor.

9. Furthermore, the electrochemical battery according to claim 7, comprising a hydrofluoric acid scavenger, a water scavenger, or a combination thereof.

10. The electrochemical battery according to claim 9, comprising the hydrofluoric acid scavenger, water scavenger, or combination thereof in an amount of 0.005 to 25% by mass based on the total mass of the electrolyte composition.

11. A method for manufacturing an electrochemical battery, A step of providing the electrolyte composition together with the positive electrode and the negative electrode. The electrolyte composition includes, Aprotic organic solvents; A conductive salt comprising at least one lithium salt; and Equation (I) 【Transformation 5】 Silyl phosphonate esters containing the structure, Includes, Here in equation (I), T is, 【Transformation 6】 and 【Transformation 7】 Selected from, p is an integer from 0 to 6, (CH ２ ) ｐ one or more CH ２ The group may be substituted with O, (CH ２ ) ｐ One or more H are C １ ~C ４ It may also be substituted with alkyl; R １ These are H, F, Cl, and R, respectively. ４ , OR ４ OSi(R) ５ ) ３ , OSi(OR ４ ) ３ , and OP(O)(OR ４ ) R ５ Selected independently from; R ４ is independently selected from C １ -C １０ alkyl, C ３ -C ７ (hetero)cycloalkyl, C ２ -C １０ alkenyl, C ２ -C １０ alkynyl, C ５ -C ７ (hetero)aryl, and C ６ -C １３ (hetero)aralkyl; R ４ Each of these may be independently substituted with one or more substituents selected from CN and F; One or more alkyl, alkenyl, and alkynyl CH ２ The basis is that these are R ４ If present and not directly bonded to a Si atom or O atom, it may be substituted with O; R ３ and R ５ H, F, C １ ~C １０ Alkyl, C ３ ~C ７ (hetero)cycloalkyl, C ２ ~C １０ Alkenil, C ２ ~C １０ Alkinyl, C ５ ~C ７ (Hetero)aryl and C ６ ~C １３ (Hetero)aralkyls are independently selected, each of which may optionally be substituted with one or more groups selected from the group consisting of CN and F; and One or more alkyl, alkenyl, and alkynyl CH ２ The basis is that these are R ３ and / or R ５ If present and not directly bonded to P, it may be substituted with O, and The electrolyte composition contains at least one silyl phosphonate ester in an amount of 0.01 to 10% by mass based on the total mass of the electrolyte composition, and A step of including the electrolyte composition in an electrochemical battery, A method that includes this.

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