Patent Application
20190348714
The present invention relates to the use of compounds of formula (I)
wherein R1 to R5 are defined as described as below, in electrolyte compositions, to electrolyte compositions containing one or more compounds of formula (I) for electrochemical cells and to electrochemical cells comprising such electrolyte compositions.
Storing electrical energy is a subject of still growing interest. Efficient storage of electric energy allows electric energy to be generated when it is advantageous and to be used when needed. Secondary electrochemical cells are well suited for this purpose due to their reversible conversion of chemical energy into electrical energy and vice versa (rechargeability). Secondary lithium batteries are of special interest for energy storage since they provide high energy density and specific energy due to the small atomic weight of the lithium ion, and the high cell voltages that can be obtained (typically 3 to 5 V) in comparison with other battery systems. For that reason, these systems have become widely used as a power source for many portable electronics such as cellular phones, laptop computers, mini-cameras, etc. They are also increasingly used as power supply in automobiles.
In secondary lithium batteries like lithium ion batteries organic carbonates, ethers, esters and ionic liquids are used as sufficiently polar solvents for solvating the conducting salt(s). Most state of the art lithium ion batteries in general comprise not a single solvent but a solvent mixture of different organic aprotic solvents.
Besides solvent(s) and conducting salt(s) an electrolyte composition usually contains further additives to improve certain properties of the electrolyte composition and of the electrochemical cell comprising said electrolyte composition. Common additives are for example flame retardants, overcharge protection additives and film forming additives which react during first charge/discharge cycle on the electrode surface thereby forming a film on the electrode. The film protects the electrode from direct contact with the electrolyte composition.
Due to their versatile applicability, electrochemical cells like lithium batteries are often used at elevated temperatures e.g. arising in a car exposed to sunlight. At elevated temperatures decomposition reactions in the electrochemical cell take place faster and the electrochemical properties of the cell degrade faster e.g. shown by accelerated capacity fading, reduced cycle life and increased gas generation in the electrochemical cell.
JP 2015-088279 A1 describes electrolyte solutions containing an additive for increasing cycle life and improving internal resistance. The additive contains a P(O) group which is substituted by one or two substituent containing a functionalized group selected from OC(O)R, OP(O)R and OS(O)2R.
US 2011/0064998 A1 discloses additives for electrolyte compositions for lithium batteries wherein the additive has a carboxylic acid ester group and inter alia a sulfonic acid ester group. The additive is used to increase the high and the low temperature cycling properties of the lithium batteries.
US 2011/0223489 A1 refers to non-aqueous secondary batteries comprising an electrolyte including an additive having an acetylene group and a methyl sulfonyl group which may be linked by a carboxylic ester group. This additive is used as SEI surface film building additive to reduce decomposition of the electrolytic solution during storage at high temperature.
US 2014/0030610 A1 relates to non-aqueous electrolyte solutions with improved electrochemical characteristics at high temperatures. The electrolyte solutions contain an organic phosphorous compound which comprises a carboxylic ester group.
US 2002/0192564 A1 describes a lithium secondary battery comprising a phosphate or phosphite ester as additive for improving the cycling characteristics wherein the ester may be substituted by a carboxylic acid containing group.
Despite the different additives known for improving the performance of electrochemical cells like secondary lithium batteries, there is still the need for additives and electrolyte compositions which help to improve the performance of the electrochemical cells further on. In particular, the development of lithium batteries with higher energy density by using cathode materials with higher energy density and/or higher working voltage like high energy NCMs and high voltage spinels require suitable additives. It is an object of the present invention to provide additives for electrolyte compositions and electrolyte compositions with good electrochemical properties like long cycle life, and good storage stability, in particular at elevated temperatures which are also suited for use in high energy lithium batteries. It is a further object of the invention to provide electrochemical cells with good electrochemical properties like long cycle life, and good storage stability, also at elevated temperatures.
This object is achieved by an electrolyte composition containing
The problem is further solved by the use of compounds of formula (I) in electrolyte compositions, and by electrochemical cells comprising such electrolyte compositions.
Electrochemical cells comprising electrolyte compositions containing a compound of formula (I) show good properties at elevated temperature like good cycling performance and reduced gas generation after storage.
In the following the invention is described in detail.
The electrolyte composition according to the present invention contains
The electrolyte composition preferably contains at least one aprotic organic solvent as component (i), more preferred at least two aprotic organic solvents (i). According to one embodiment the electrolyte composition may contain up to ten aprotic organic solvents.
The at least one aprotic organic solvent (i) is preferably 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 acetales and ketales, fluorinated and non-fluorinated orthocarboxylic acids esters, fluorinated and non-fluorinated cyclic and acyclic esters and diesters of 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.
The aprotic organic solvent(s) (i) may be fluorinated or non-fluorinated, e.g. they may be non-fluorinated, partly fluorinated or fully fluorinated. “Partly fluorinated” means, that one or more H of the respective molecule are substituted by a F atom. “Fully fluorinated” means that all H of the respective molecule are substituted by a F atom. The at least one aprotic organic solvent may be selected from fluorinated and non-fluorinated aprotic organic solvents, i.e. the electrolyte composition may contain a mixture of fluorinated and non-fluorinated aprotic organic solvents.
Examples of fluorinated and non-fluorinated cyclic carbonates are ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate (BC), wherein one or more H may be substituted by F and/or a C1 to C4 alkyl group like 4-methyl ethylene carbonate, monofluoroethylene carbonate (FEC), and cis- and trans-difluoroethylene carbonate. Preferred cyclic carbonates are ethylene carbonate, monofluoroethylene carbonate, and propylene carbonate, in particular ethylene carbonate.
Examples of fluorinated and non-fluorinated acyclic carbonates are di-C1-C10-alkylcarbonates, wherein each alkyl group is selected independently from each other and wherein one or more H may be substituted by F. Preferred are fluorinated and non-fluorinated di-C1-C4-alkylcarbonates. Examples are diethyl carbonate (DEC), ethyl methyl carbonate (EMC), 2,2,2-trifluoroethyl methyl carbonate (TFEMC), dimethyl carbonate (DMC), trifluoromethyl methyl carbonate (TFMMC), and methylpropyl carbonate. Preferred acyclic carbonates are diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC).
In one embodiment of the invention the electrolyte composition contains mixtures of optionally fluorinated acyclic organic carbonates and cyclic organic carbonates at a ratio by weight of from 1:10 to 10:1, preferred of from 3:1 to 1:1.
Examples of fluorinated and non-fluorinated acyclic ethers and polyethers are fluorinated and non-fluorinated di-C1-C10-alkylethers, di-C1-C4-alkyl-C2-C6-alkylene ethers, and polyethers, and fluorinated ethers of formula R′—(O—CFpH2-p)q—R″ wherein R′ is a C1-C10 alkyl group or a C3-C10 cycloalkyl group, wherein one or more H of an alkyl and/or cycloalkyl group are substituted by F; R″ is H, F, a C1-C10 alkyl group, or a C3-C10 cycloalkyl group, wherein one or more H of an alkyl and/or cycloalkyl group are substituted by F; p is 1 or 2; and q is 1, 2 or 3.
According to the invention each alkyl group of the fluorinated and non-fluorinated di-C1-C10-alkylethers is selected independently from the other wherein one or more H of an alkyl group may be substituted by F. Examples of fluorinated and non-fluorinated di-C1-C10-alkylethers are di-methylether, ethylmethylether, diethylether, methylpropylether, diisopropylether, di-n-butylether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (CF2HCF2CH2OCF2CF2H), and 1H,1H,5H-perfluoropentyl-1,1,2,2-tetrafluoroethylether (CF2H(CF2)3CH2OCF2CF2H).
Examples of fluorinated and non-fluorinated di-C1-C4-alkyl-C2-C6-alkylene ethers are 1,2-di-methoxyethane, 1,2-diethoxyethane, diglyme (diethylene glycol dimethyl ether), triglyme (triethyleneglycol dimethyl ether), tetraglyme (tetraethyleneglycol dimethyl ether), and diethylengly-coldiethylether wherein one or more H of an alkyl or alkylene group may be substituted by F.
Examples of suitable fluorinated and non-fluorinated polyethers are polyalkylene glycols wherein one or more H of an alkyl or alkylene group may be substituted by F, preferably poly-C1-C4-alkylene glycols and especially polyethylene glycols. Polyethylene glycols may comprise up to 20 mol % of one or more C1-C4-alkylene glycols in copolymerized form. Polyalkylene glycols are preferably dimethyl- or diethyl-end-capped polyalkylene glycols. The molecular weight Mw of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g/mol. The molecular weight Mw of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be up to 5 000 000 g/mol, preferably up to 2 000 000 g/mol.
Examples of fluorinated ethers of formula R′—(O—CFpH2-p)q—R″ are 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (CF2HCF2CH2OCF2CF2H), and 1H,1H,5H-perfluoropentyl-1,1,2,2-tetrafluoroethylether (CF2H(CF2)3CH2OCF2CF2H).
Examples of fluorinated and non-fluorinated cyclic ethers are 1,4-dioxane, tetrahydrofuran, and their derivatives like 2-methyl tetrahydrofuran wherein one or more H of an alkyl group may be substituted by F.
Examples of fluorinated and non-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 methyl dioxolane wherein one or more H may be substituted by F.
Examples of fluorinated and non-fluorinated acyclic orthocarboxylic acid esters are tri-C1-C4 alkoxy methane, in particular trimethoxymethane and triethoxymethane wherein one or more H of an alkyl group may be substituted by F. Examples of suitable 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 wherein one or more H may be substituted by F.
Examples of fluorinated and non-fluorinated acyclic esters of carboxylic acids are ethyl and methyl formiate, ethyl and methyl acetate, ethyl and methyl proprionate, and ethyl and methyl butanoate, and esters of dicarboxylic acids like 1,3-dimethyl propanedioate wherein one or more H may be substituted by F. An example of a cyclic ester of carboxylic acids (lactones) is γ-butyrolactone. Examples of fluorinated and non-fluorinated diesters of carboxylic acids are malonic acid dialkyl esters like malonic acid dimethyl ester, succinic acid dialkyl esters like succinic acid dimethyl ester, glutaric acid dialkyl esters like glutaric acid dimethyl ester, and adipinic acid dialkyl esters like adipinic acid dimethyl ester, wherein one or more H of an alkyl group may be substituted by F.
Examples of fluorinated and non-fluorinated cyclic and acyclic sulfones are ethyl methyl sulfone, dimethyl sulfone, and tetrahydrothiophene-S,S-dioxide (sulfolane), wherein one or more H of an alkyl group may be substituted by F.
Examples of fluorinated and non-fluorinated cyclic and acyclic nitriles and dinitriles are adipodinitrile, acetonitrile, propionitrile, and butyronitrile wherein one or more H may be substituted by F.
Examples of fluorinated and non-fluorinated cyclic and acyclic phosphates are trialkyl phosphates wherein one or more H of an alkyl group may be substituted by F like trimethyl phosphate, triethyl phosphate, and tris(2,2,2-trifluoroethyl)phosphate.
More preferred the aprotic organic solvent(s) are selected from fluorinated and non-fluorinated ethers and polyethers, fluorinated and non-fluorinated cyclic and acyclic organic carbonates, fluorinated and non-fluorinated cyclic and acyclic esters and diesters of carboxylic acids and mixtures thereof. Even more preferred the aprotic organic solvent(s) are selected from fluorinated and non-fluorinated ethers and polyethers, and fluorinated and non-fluorinated cyclic and acyclic organic carbonates, and mixtures thereof.
According to another embodiment, the electrolyte composition contains at least one solvent selected from fluorinated cyclic carbonate like 1-fluoro ethyl carbonate.
According to another embodiment the electrolyte composition contains at least one fluorinated cyclic carbonate, e.g. 1-fluoro ethyl carbonate and at least one non-fluorinated acyclic organic carbonate, e.g. dimethyl carbonate, diethyl carbonate or ethyl methyl carbonate.
The inventive electrolyte composition contains at least one conducting salt (ii). The electrolyte composition functions as a medium that transfers ions participating in the electrochemical reaction taking place in an electrochemical cell. The conducting salt(s) (ii) present in the electrolyte are usually solvated in the aprotic organic solvent(s) (i). Preferably the conducting salt is a lithium salt.
The conducting salt(s) (ii) may be selected from the group consisting of
Suited 1,2- and 1,3-diols from which the bivalent group (ORIIO) is derived may be aliphatic or aromatic and may be selected, e.g., from 1,2-dihydroxybenzene, propane-1,2-diol, butane-1,2-diol, propane-1,3-diol, butan-1,3-diol, cyclohexyl-trans-1,2-diol and naphthalene-2,3-diol which are optionally are substituted by one or more F and/or by at least one straight or branched non fluorinated, partly fluorinated or fully fluorinated C1-C4 alkyl group. An example for such 1,2- or 1,3-diole is 1,1,2,2-tetra(trifluoromethyl)-1,2-ethane diol.
“Fully fluorinated C1-C4 alkyl group” means, that all H-atoms of the alkyl group are substituted by F.
Suited 1,2- or 1,3-dicarboxlic acids from which the bivalent group (ORIIO) is derived may be aliphatic or aromatic, for example oxalic acid, malonic acid (propane-1,3-dicarboxylic acid), phthalic acid or isophthalic acid, preferred is oxalic acid. The 1,2- or 1,3-dicarboxlic acids are optionally substituted by one or more F and/or by at least one straight or branched non-fluorinated, partly fluorinated or fully fluorinated C1-C4 alkyl group.
Suited 1,2- or 1,3-hydroxycarboxylic acids from which the bivalent group (ORIIO) is derived may be aliphatic or aromatic, for example salicylic acid, tetrahydro salicylic acid, malic acid, and 2-hydroxy acetic acid, which are optionally substituted by one or more F and/or by at least one straight or branched non-fluorinated, partly fluorinated or fully fluorinated C1-C4 alkyl group. An example for such 1,2- or 1,3-hydroxycarboxylic acids is 2,2-bis(trifluoromethyl)-2-hydroxy-acetic acid.
Examples of Li[B(RI)4], Li[B(RI)2(ORIIO)] and Li[B(ORIIO)2] are LiBF4, lithium difluoro oxalato borate and lithium dioxalato borate.
Preferably the at least one conducting salt (ii) is selected from LiPF6, LiAsF6, LiSbF6, LiCF3SO3, LiBF4, lithium bis(oxalato) borate, lithium difluoro(oxalato) borate, LiClO4, LiN(SO2C2F5)2, LiN(SO2CF3)2, LiN(SO2F)2, and LiPF3(CF2CF3)3, more preferred LiPF6, LiBF4, and LiPF3(CF2CF3)3, more preferred the conducting salt is selected from LiPF6 and LiBF4, and the most preferred conducting salt is LiPF6.
The at least one conducting salt is usually present at a minimum concentration of at least 0.1 m/l, preferably the concentration of the at least one conducting salt is 0.5 to 2 mol/l based on the entire electrolyte composition.
The electrolyte composition of the present invention contains at least one compound of formula (I) as component (iii)
wherein
The term “C1-C10 alkyl” as used herein means a straight or branched saturated hydrocarbon group with 1 to 10 carbon atoms having one free valence, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, 2,2-dimethylpropyl, n-hexyl, 2-ethyl hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, and the like. Preferred are C1-C6 alkyl, more preferred are C1-C4 alkyl, even more preferred are methyl, ethyl, and n- and isopropyl and most preferred are methyl and ethyl.
The term “C3-C6 (hetero)cycloalkyl” as used herein means a saturated 3- to 6-membered hydrocarbon cycle having one free valence wherein one or more of the C-atoms of the saturated cycle may be replaced independently from each other by a heteroatom selected from N, S, O and P. Examples of C3 to C6 cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, preferred is cyclohexyl. Examples of C3 to C6 hetero cycloalkyl are oxiranyl, tetrahydrofuryl, pyrrolidyl, piperidyl and morpholinyl.
The term “C2-C10 alkenyl” as used herein refers to an unsaturated straight or branched hydrocarbon group with 2 to 10 carbon atoms having one free valence. Unsaturated means that the alkenyl group contains at least one C—C double bond. C2-C6 alkenyl includes for example ethenyl, propenyl, 1-n-butenyl, 2-n-butenyl, iso-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, and the like. Preferred are C2 to C6 alkenyl groups, even more preferred are C2-C4 alkenyl groups, more preferred are ethenyl and propenyl, most preferred is 1-propen-3-yl, also called allyl.
The term “C2 to C10 alkynyl” as used herein refers to an unsaturated straight or branched hydrocarbon group with 2 to 10 carbon atoms having one free valence, wherein the hydrocarbon group contains at least one C—C triple bond. C2-C6 alkynyl includes for example ethynyl, propynyl, 1-n-butinyl, 2-n-butynyl, iso-butinyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octynyl, 1-nonynyl, 1-decynyl, and the like. Preferred are C2 to C6 alkynyl, even more preferred are C2-C4 alkynyl, more preferred are ethynyl and 1-propyn-3-yl (propargyl).
The term “C5 to C7 (hetero)aryl” as used herein denotes an aromatic 5- to 7-membered hydrocarbon cycle or condensed cycles having one free valence wherein one or more of the C-atoms of the aromatic cycle(s) may be replaced independently from each other by a heteroatom selected from N, S, O and P. Examples of C5-C7 (hetero)aryl are pyrrolyl, furanyl, thiophenyl, pyridinyl, pyranyl, thiopyranyl, and phenyl. Preferred is phenyl.
The term “C6-C13 (hetero)aralkyl” as used herein denotes an aromatic 5- to 7-membered hydrocarbon cycle substituted by one or more C1-C6 alkyl wherein one or more of the C-atoms of the aromatic cycle may be replaced independently from each other by a heteroatom selected from N, S, O and P. The C6-C13 (hetero)aralkyl group contains in total 6 to 13 C- and heteroatoms and has one free valence. The free valence may be located in the aromatic cycle or in a C1-C6 alkyl group, i.e. C6-C13 (hetero)aralkyl group may be bound via the (hetero)aromatic part or via the alkyl part of the group. Examples of C6-C13 (hetero)aralkyl are methylphenyl, 2-methylpyridyl, 1,2-dimethylphenyl, 1,3-dimethylphenyl, 1,4-dimethylphenyl, ethylphenyl, 2-propylphenyl, benzyl, 2-CH2-pyridyl, and the like.
R1 is selected from C1-C10 alkyl, C3-C6 (hetero)cycloalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C5-C7 (hetero)aryl, and C6-C13 (hetero)aralkyl which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl which are not directly bound to the O-atom may be replaced by O. Preferably R1 is selected from C1-C10 alkyl, C2-C10 alkenyl, and C2-C10 alkynyl, which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl which are not directly bound to the O-atom may be replaced by O; more preferred R1 is selected from C1-C6 alkyl, C2-C6 alkenyl, and C2-C6 alkynyl, which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl which are not directly bound to the O-atom may be replaced by O. Examples of R1 are methyl, ethyl, n-propyl, i-propyl, —CH2CH2ON, —CH2CH2CH2ON, CH2CF3, —CH2CH2CF3, —CH2CHCH2, —CH2CCH, phenyl, benzyl, cyclohexyl and the like. Preferred examples of R1 are methyl, ethyl, n-propyl, i-propyl, —CH2CH2ON, —CH2CH2CH2ON, and —CH2CCH
R2 is selected from H and C1-C6 alkyl, preferably R2 is selected from H and C1-C4 alkyl, e.g. R2 is H, methyl, ethyl, i-propyl, n-propyl, n-butyl or t-butyl, more preferred R2 is selected from H and methyl.
R3 is selected from C1-C10 alkyl, C3-C6 (hetero)cycloalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C5-C7 (hetero)aryl, and C6-C13 (hetero)aralkyl which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl which are not directly bound to the S-atom may be replaced by O. Preferably R3 is selected from C1-C10 alkyl, C2-C10 alkenyl, and C2-C10 alkynyl, which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl which are not directly bound to the S-atom may be replaced by O. Examples of R3 are methyl, ethyl, n-propyl, i-propyl, —CH2CH2ON, —CH2CH2CH2ON, CH2CF3, —CH2CH2CF3, —CH2CHCH2, —CH2CCH, phenyl, benzyl, cyclohexyl and the like. According to one embodiment R3 is C1-C6 alkyl, e.g. methyl.
R4 and R5 may each independently be selected from R6 and OR6. In this case R4 and R5 may be same or different. It is also possible, that R4 and R5 may be joint forming a 5- to 6-membered heterocycle together with the P-atom.
R6 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C5-C7 (hetero)aryl, and C6-C13 (hetero)aralkyl which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl which are not directly bound to the P-atom may be replaced by O. Preferably R6 is selected from C1-C6 alkyl, C2-C6 alkenyl, and C2-C6 alkynyl, which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl which are not directly bound to the P-atom may be replaced by O; even more preferred R6 is selected from C1-C6 alkyl like methyl, ethyl, n-propyl, i-propyl, n-butyl and t-butyl. According to one embodiment R6 is selected from C1-C4 alkyl, e.g. methyl.
In case R4 and R5 are each independently preferably selected from OR6; more preferred R4 and R5 are each independently selected from OC1-C6 alkyl, OC2-C6 alkenyl, and OC2-C6 alkynyl which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl which is not directly bound to the P-atom may be replaced by O, even more preferred R4 and R5 are each independently OC1-C6 alkyl. According to one embodiment R4 and R5 are each independently OC1-C4 alkyl, e.g. both are OCH3.
In case R4 and R5 are joint and form a 5- to 6-membered heterocycle together with the P-atom R4 and R5 are preferably selected from —(CH2)a— with a being 4 or 5 and —O—(CH2)b—O— with b being 2 or 3 wherein one or more H of —(CH2)a— and —O—(CH2)b—O— may be replaced by other groups, e.g. by groups selected from F and fluorinated and non-fluorinated C1-C4 alkyl like CH3, CF3 and CH2CF3. Preferably R4 and R5 form a 5-membered heterocycle with the P-atom, in particular preferred R4 and R5 are selected from —O—(CH2)2—O— and form a 5-membered heterocycle with the P-atom.
Preferred compounds of formula (I) are compounds of formula (I) wherein
R1 is selected from C1-C10 alkyl, C2-C10 alkenyl, and C2-C10 alkynyl, which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl which is not directly bound to the O-atom may be replaced by O;
R2 is selected from H and methyl;
R3 is selected from C1-C10 alkyl, C2-C10 alkenyl, and C2-C10 alkynyl, which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl not directly bound to the S-atom may be replaced by O; and
R4 and R5 are each independently selected from OC1-C6 alkyl, OC2-C6 alkenyl, and OC2-C6 alkynyl which may be substituted by one or more substituents selected from CN and F and wherein one or more CH2-groups of alkyl, alkenyl and alkynyl which is not directly bound to the P-atom may be replaced by O, preferably from OC1-C6 alkyl or R4 and R5 are jointly selected from —O—(CH2)b—O— with b being 2 or 3 and form a 5- or 6-membered heterocycle with the P-atom.
Preferred compounds of formula (I) are
The preparation of the compounds of formula (I) is known to the person skipped in the art. A description of their preparation may be found in X. Zhou et al., Adv. Synth. Catal. 351 (2009). pages 2567 to 2572 and M. T. Corbett et al., Angew. Chem. Int. Ed. 51 (2012), pages 4685 to 4689.
Usually the electrolyte composition contains in total at least 0.01 wt.-% of the compound(s) of formula (I), based on the total weight of electrolyte composition, preferably at least 0.05 wt.-%, and more preferred at least 0.1 wt.-%, based on the total weight of electrolyte composition. The upper limit of the total concentration of compound(s) of formula (I) in the electrolyte composition is usually 10 wt.-%, based on the total weight of electrolyte composition, preferably 5 wt.-%, and more preferred the upper limit of the total concentration of the compound(s) of formula (I) is 3 wt.-%, based on the total weight of electrolyte composition. Usually the electrolyte composition contains in total 0.01 to 10 wt.-%, of the compound(s) of formula (I), based on the total weight of electrolyte composition, preferably 0.05 to 5 wt.-%, and more preferably 0.1 to 3 wt.-%.
A further object of the present invention is the use of compounds of formula (I) in electrochemical cells, e.g. in the electrolyte composition used in the electrochemical cell. In the electrolyte composition the compounds of formula (I) are usually used as additive, preferably as film forming additives and/or as anti-gassing additives. Preferably the compounds of formula (I) are used in lithium batteries, e.g. as additive for electrolyte compositions, more preferred in lithium ion batteries, even more preferred in electrolyte compositions for lithium ion batteries.
If the compounds of formula (I) are used as additives in the electrolyte compositions, they are usually added in the desired amount to the electrolyte composition. They are usually used in the electrolyte composition in the concentrations described above and as described as preferred.
The electrolyte composition according to the present invention optionally contains at least one further additive (iv). The additive(s) (iv) may be selected from SEI forming additives, flame retardants, overcharge protection additives, wetting agents, HF and/or H2O scavenger, stabilizer for LiPF6 salt, ionic solvation enhancer, corrosion inhibitors, gelling agents, and the like. The one or more additives (iv) are different from the compounds of formula (I). The electrolyte composition may contain at least one additive (iv) or two, three or more.
Examples of flame retardants are organic phosphorous compounds like cyclophosphazenes, organic phosphoramides, organic phosphites, organic phosphates, organic phosphonates, organic phosphines, and organic phosphinates, and fluorinated derivatives thereof.
Examples of cyclophosphazenes are ethoxypentafluorocyclotriphosphazene, available under the trademark Phoslyte™ E from Nippon Chemical Industrial, hexamethylcyclotriphosphazene, and hexamethoxycyclotriphosphazene, preferred is ethoxypentafluorocyclotriphosphazene. An example of an organic phosphoramide is hexamethyl phosphoramide. An example of an organic phosphite is tris(2,2,2-trifluoroethyl) phospite. Examples of organic phosphates are trimethyl phosphate, trimethyl phosphate, tris(2,2,2-trifluoroethyl)phosphate, bis(2,2,2-trifluoroethyl)methyl phosphate, and triphenyl phosphate Examples of organic phosphonates are dimethyl phosphonate, ethyl methyl phosphonate, methyl n-propyl phosphonate, n-butyl methyl phosphonate, diethyl phosphonate, ethyl n-proply phosphonate, ethyl n-butyl phosphonate, di-n-propyl phosphonate, n-butyl n-propyl phosphonate, di-n-butyl phosphonate, and bis(2,2,2-trifluoroethyl) methyl phosphonate. An example of an organic phosphine is triphenyl phosphine. Examples of organic phosphinates are dimethyl phosphonate, diethyl phosphinate, di-n-propyl phosphinate, trimethyl phosphinate, trimethyl phosphinate, and tri-n-propyl phosphinate.
Examples of HF and/or H2O scavenger are optionally halogenated cyclic and acyclic silylamines.
Examples of overcharge protection additives are cyclohexylbenzene, o-terphenyl, p-terphenyl, and biphenyl and the like, preferred are cyclohexylbenzene and biphenyl.
Examples of gelling agents are polymers like polyvinylidene fluoride, polyvinylidene-hexafluoropropylene copolymers, polyvinylidene-hexafluoropropylene-chlorotrifluoroethylene copolymers, Nafion, polyethylene oxide, polymethyl methacrylate, polyacrylonitrile, polypropylene, polystyrene, polybutadiene, polyethylene glycol, polyvinylpyrrolidone, polyaniline, polypyrrole and/or polythiophene. These polymers are added to the electrolytes in order to convert liquid electrolytes into quasi-solid or solid electrolytes and thus to improve solvent retention, especially during ageing.
SEI-forming additives are film forming additives. An SEI forming additive according to the present invention is a compound which decomposes on an electrode to form a passivation layer on the electrode which prevents degradation of the electrolyte and/or the electrode. In this way, the lifetime of a battery is significantly extended. Preferably the SEI forming additive forms a passivation layer on the anode. An anode in the context of the present invention is understood as the negative electrode of a battery. Preferably, the anode has a reduction potential of 1 Volt or less against lithium such as a lithium intercalating graphite anode. In order to determine if a compound qualifies as anode film forming additive, an electrochemical cell can be prepared comprising a graphite electrode and a metal counter electrode, and an electrolyte containing a small amount of said compound, typically from 0.1 to 10 wt.-% of the electrolyte composition, preferably from 0.2 to 5 wt.-% of the electrolyte composition. Upon application of a voltage between anode and lithium metal, the differential capacity of the electrochemical cell is recorded between 0.5 V and 2 V. If a significant differential capacity is observed during the first cycle, for example −150 mAh/V at 1 V, but not or essentially not during any of the following cycles in said voltage range, the compound can be regarded as SEI forming additive. SEI forming additives are known to the person skilled in the art.
According to one embodiment the electrolyte composition contains at least one SEI forming additive. More preferred the electrolyte composition contains at least one SEI forming selected from cyclic carbonates containing at least one double bond; fluorinated ethylene carbonates and its derivatives; cyclic esters of sulfur containing acids; oxalate containing compounds; and sulfur containing additives as described in detail in WO 2013/026854 A1, in particular the sulfur containing additives shown on page 12 line 22 to page 15, line 10.
The cyclic carbonates containing at least one double bond include cyclic carbonates wherein a double bond is part of the cycle like vinylene carbonate and its derivatives, e.g. methyl vinylene carbonate and 4,5-dimethyl vinylene carbonate; and cyclic carbonate wherein the double bond is not part of the cycle, e.g. methylene ethylene carbonate, 4,5-dimethylene ethylene carbonate, vinyl ethylene carbonate, and 4,5-divinyl ethylene carbonate. Preferred cyclic carbonates containing at least one double bond are vinylene carbonate, methylene ethylene carbonate, 4,5-dimethylene ethylene carbonate, vinyl ethylene carbonate, and 4,5-divinyl ethylene carbonate, most preferred is vinylene carbonate.
Examples of cyclic esters of sulfur containing acids include cyclic esters of sulfonic acid like propane sultone and its derivatives, methylene methane disulfonate and its derivatives, and propene sultone and its derivatives; and cyclic esters derived from sulfurous acid like ethylene sulfite and its derivatives. Preferred cyclic esters of sulfur containing acids are propane sultone, propene sultone, methylene methane disulfonate, and ethylene sulfite.
Oxalate comprising compounds include oxalates such as lithium oxalate; oxalato borates like lithium dimethyl oxalato borate and salts comprising a bis(oxalato)borate anion or a difluoro oxalato borate anion like lithium bis(oxalate) borate, lithium difluoro (oxalato) borate, ammonium bis(oxalato) borate, and ammonium difluoro (oxalato) borate; and oxalato phosphates including lithium tetrafluoro (oxalato) phosphate and lithium difluoro bis(oxalato) phosphate. Preferred oxalate comprising compounds for use as film forming additive are lithium bis(oxalato) borate and lithium difluoro (oxalato) borate.
Preferred SEI-forming additives are oxalato borates, fluorinated ethylene carbonates and its derivatives, cyclic carbonates containing at least one double bond, cyclic esters of sulfur containing acids, and the sulfur containing additives as described in detail in WO 2013/026854 A1. More preferred the electrolyte composition contains at least one additive selected from cyclic carbonates containing at least one double bond, fluorinated ethylene carbonate and its derivatives, cyclic esters of sulfur containing acids, and oxalato borates, even more preferred are oxalato borates, fluorinated ethylene carbonates and its derivatives, and cyclic carbonates containing at least one double bond. Particularly preferred SEI-forming additives are lithium bis(oxalato) borate, lithium difluoro oxalato borate, vinylene carbonate, methylene ethylene carbonate, vinylethylene carbonate, and monofluoroethylene carbonate.
If the electrolyte composition contains a SEI forming additive (iv) it is usually present in a concentration of from 0.1 to 10 wt.-%, preferably of from 0.2 to 5 wt.-% of the electrolyte composition.
A compound added as additive (iv) may have more than one effect in the electrolyte composition and the device comprising the electrolyte composition. E.g. lithium oxalato borate may be added as additive enhancing the SEI formation but it may also be added as conducting salt.
According to one embodiment of the present invention the electrolyte composition contains at least one additive (iv). The minimum total concentration of the further additive(s) (iv) is usually 0.005 wt.-%, preferably the minimum concentration is 0.01 wt.-% and more preferred the minimum concentration is 0.1 wt.-%, based on the total weight of electrolyte composition. The maximum total concentration of the additive(s) (iv) is usually 25 wt.-%, based on the total weight of electrolyte composition.
A preferred electrolyte composition contains
(i) at least 74.99 wt.-% of at least one organic aprotic solvent;
(ii) 0.1 to 25 wt.-% of at least one conducting salt;
(iii) 0.01 to 10 wt.-% of at least one compound of formula (I); and
(iv) 0 to 25 wt.-% of at least one additive,
based on the total weight of the electrolyte composition.
The electrolyte composition is preferably non-aqueous. In one embodiment of the present invention, the water content of the electrolyte composition is preferably below 100 ppm, based on the weight of the respective inventive formulation, more preferred below 50 ppm, most preferred below 30 ppm. The water content may be determined by titration according to Karl Fischer, e.g. described in detail in DIN 51777 or IS0760: 1978.
In one embodiment of the present invention, the HF-content of the electrolyte composition is preferably below 100 ppm, based on the weight of the respective inventive formulation, more preferred below 50 ppm, most preferred below 30 ppm. The HF content may be determined by titration.
The electrolyte composition is preferably liquid at working conditions; more preferred it is liquid at 1 bar and 25° C., even more preferred the electrolyte composition is liquid at 1 bar and −15° C., in particular the electrolyte composition is liquid at 1 bar and −30° C., even more preferred the electrolyte composition is liquid at 1 bar and −50° C. Such liquid electrolyte compositions are particularly suitable for outdoor applications, for example for use in automotive batteries.
The electrolyte compositions of the invention are prepared by methods which are known to the person skilled in the field of the production of electrolytes, generally by dissolving the conductive salt(s) (ii) in the corresponding mixture of solvent(s) (i) and adding one or more compounds of formula (I) (iii) and optionally one or more additives (iv), as described above.
The electrolyte compositions may be used in electrochemical cells, preferred they are used in a lithium battery, a double layer capacitor, or a lithium ion capacitor, more preferred they are used in lithium batteries, even more preferred in secondary lithium cells and most preferred in secondary lithium ion batteries.
Another aspect of the invention are electrochemical cells comprising the electrolyte as described above or as described as preferred.
The electrochemical cell usually comprises
(A) an anode comprising at least one anode active material,
(B) a cathode comprising at least one cathode active material; and
(C) the electrolyte composition as described above.
The electrochemical cell may be a lithium battery, a double layer capacitor, or a lithium ion capacitor. The general construction of such electrochemical cell is known and is familiar to the person skilled in this art—for batteries, for example, in Linden's Handbook of Batteries (ISBN 978-0-07-162421-3).
Preferably the electrochemical cell is a lithium battery. The term “lithium battery” as used herein means an electrochemical cell, wherein the anode comprises lithium metal or lithium ions sometime during the charge/discharge of the cell. The anode may comprise lithium metal or a lithium metal alloy, a material occluding and releasing lithium ions, or other lithium containing compounds; e.g. the lithium battery may be a lithium ion battery, a lithium/sulphur battery, or a lithium/selenium sulphur battery. The lithium battery is preferably a secondary lithium battery, i.e. a rechargeable lithium battery.
In particular preferred the electrochemical device is a lithium ion battery, i.e. a secondary lithium ion electrochemical cell comprising a cathode comprising a cathode active material that can reversibly occlude and release lithium ions and an anode comprising an anode active material that can reversibly occlude and release lithium ions.
The electrochemical cell comprises a cathode (B) comprising at least one cathode active material. The at least one cathode active material comprises a material capable of occluding and releasing lithium ions and may be selected from lithium transition metal oxides and lithium transition metal phosphates of olivine structure. A compound or material occluding and releasing lithium ion is also called lithium ion intercalating compound.
Examples of lithium transition metal phosphates are LiFePO4, LiNiPO4, LiMnPO4, and LiCoPO4; examples of lithium ion intercalating lithium transition metal oxides are LiCoO2, LiNiO2, LiMnO2, mixed lithium transition metal oxides with layer structure, manganese containing spinels, and lithium intercalating mixed oxides of Ni, Al and at least one second transition metal.
Examples of mixed lithium transition metal oxides which contain Mn and at least one second transition metal are lithium transition metal oxides with layered structure of formula (II)
wherein
a is in the range of from 0.05 to 0.9, preferred in the range of 0.1 to 0.8,
b is in the range of from zero to 0.35,
c is in the range of from 0.1 to 0.9, preferred in the range of 0.2 to 0.8,
d is in the range of from zero to 0.2,
e is in the range of from zero to 0.3, preferred in the range of >zero to 0.3, more preferred in the range of 0.05 to 0.3,
with a+b+c+d=1, and
M being one or more metals selected from Na, K, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, Nb, Zr, and Zn.
Cobalt containing compounds of formula (II) are also named NCM.
Mixed lithium transition metal oxides with layered structure of formula (II) wherein e is larger than zero are also called overlithiated.
Preferred mixed lithium transition metal oxides with layered structure of formula (II) are compounds forming a solid solution wherein 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 wherein one or more metal M as defined above may be present. The one or more metals M are also called “dopants” or “doping metal” since they are usually present at minor amounts, e.g. at maximum 10 mol-% M or at maximum 5 mol-% M or at maximum 1 mol.-% based on the total amount of metal except lithium present in the transition metal oxide. In case one or more metals M are present, they are usually present in an amount of at least 0.01 mol-% or at least 0.1 mol-% based on the total amount of metal except lithium present in the transition metal oxide. These compounds are also expressed by formula (IIa)
wherein M′ is Ni and at least one metal selected from Mn and Co;
z is 0.1 to 0.8,
and wherein one or more metals selected from Na, K, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, Nb, Zr, and Zn may be present.
Electrochemically, the Ni and if present Co atoms in the LiM′O2 phase participate in reversible oxidation and reduction reactions leading to Li-ions deintercalation and intercalation, respectively, at voltages below 4.5 V vs. Li+/Li, while the Li2MnO3 phase participates only in oxidation and reduction reactions at voltages equal or above 4.5 V vs. Li+/Li given that Mn in the Li2MnO3 phase is in its +4 oxidation state. Therefore, electrons are not removed from the Mn atoms in this phase but from the 2p orbitals of oxygen ions, leading to the removal of oxygen for the lattice in the form of O2 gas at least in the first charging cycling.
These compounds are also called HE-NCM due to their higher energy densities in comparison to usual NCMs. Both HE-NCM and NCM have operating voltages of about 3.0 to 3.8 V against Li/Li+, but high cut off voltages have to be used both for activating and cycling of HE-NCMs to actually accomplish full charging and to benefit from their higher energy densities. Usually the upper cut-off voltage for the cathode during charging against Li/Li+ is of at least 4.5 V for activating the HE-NCM, preferably of at least 4.6 V, more preferred of at least 4.7 V and even more preferred of at least 4.8 V. The term “upper cut-off voltage against Li/Li+ during charging” of the electrochemical cell means the voltage of the cathode of the electrochemical cell against a Li/Li+ reference anode which constitute the upper limit of the voltage at which the electrochemical cell is charged. Examples of HE-NCMs are 0.33Li2MnO3.0.67Li(Ni0.4Co0.2Mn0.4)O2, 0.42Li2MnO3.0.58Li(Ni0.4Co0.2Mn0.4)O2, 0.50Li2MnO3.0.50Li(Ni0.4Co0.2Mn0.4)O2, 0.40Li2MnO3.0.60Li(Ni0.8Co0.1Mn0.1)O2, and 0.42Li2MnO3.0.58Li(Ni0.6Mn0.4)O2.
Examples of manganese-containing transition metal oxides with layer structure of formula (II) wherein d is zero are LiNi0.33Mn0.67O2, LiNi0.25Mn0.75O2, LiNi0.35Co0.15Mn0.5O2, LiNi0.21Co0.08Mn0.71O2, LiNi0.22Co0.12Mn0.66O2, LiNi0.8Co0.1Mn0.1O2, LiNi0.6Co0.2Mn0.2O2, and LiNi0.5Co0.2Mn0.3O2. It is preferred that the transition metal oxides of general formula (II) wherein d is zero do not contain further cations or anions in significant amounts.
Examples of manganese-containing transition metal oxides with layer structure of formula (II) wherein d is larger than zero are 0.33Li2MnO3.0.67Li(Ni0.4Co0.2Mn0.4)O2, 0.42Li2MnO3.0.58Li(Ni0.4Co0.2Mn0.4)O2, 0.50Li2MnO3.0.50Li(Ni0.4Co0.2Mn0.4)O2, 0.40Li2MnO3.0.60Li(Ni0.8Co0.1Mn0.1)O2, and 0.42Li2MnO3.0.58Li(Ni0.6Mn0.4)O2 wherein one or more metal M selected from Na, K, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, Nb, Zr, and Zn may be present. The one or more doping metal is preferably present up to 1 mol-%, based on the total amount of metal except lithium present in the transition metal oxide.
Other preferred compounds of formula (II) are Ni-rich compounds, wherein the content of Ni is at least 50 mol. % based on the total amount of transition metal present. This includes compounds of formula (IIb)
wherein
a is in the range of from 0.5 to 0.9, preferred in the range of 0.5 to 0.8,
b is in the range of from zero to 0.35,
c is in the range of from 0.1 to 0.5, preferred in the range of 0.2 to 0.5,
d is in the range of from zero to 0.2,
e is in the range of from zero to 0.3,
with a+b+c+d=1, and
M being one or more metals selected from Na, K, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, Nb, Zr, and Zn.
Examples of Ni-rich compounds of formula (IIb) are Li[Ni0.8Co0.1Mn0.1]O2 (NCM 811), Li[Ni0.6Co0.2Mn0.2]O2 (NCM 622), and Li[Ni0.5Co0.2Mn0.3]O2 (NCM 523).
Further examples of mixed lithium transition metal oxides containing Mn and at least one second transition metal are manganese-containing spinels of formula (III)
wherein
s is 0 to 0.4,
t is 0 to 0.4, and
M is Mn and at least one further metal selected from Co and Ni, preferably M is Mn and Ni and optionally Co, i.e. a part of M is Mn and another part of Ni, and optionally a further part of M is selected from Co.
The cathode active material may also be selected from lithium intercalating mixed oxides containing Ni, Al and at least one second transition metal, e.g. from lithium intercalating mixed oxides of Ni, Co and Al. Examples of mixed oxides of Ni, Co and Al are compounds of formula (IV)
wherein
h is 0.7 to 0.9, preferred 0.8 to 0.87, and more preferred 0.8 to 0.85;
i is 0.15 to 0.20; and
j is 0.02 to 10, preferred 0.02 to 1, more preferred 0.02 to 0.1, and most preferred 0.02 to 0.03.
The cathode active material may also be selected from LiMnPO4, LiNiPO4 and LiCoPO4. These phosphates show usually olivine structure. Usually upper cut-off voltages of at least 4.5 V have to be used for charging these phosphates.
Preferably the at least one cathode active material is selected from mixed lithium transition metal oxides containing Mn and at least one second transition metal; lithium intercalating mixed oxides containing Ni, Al and at least one second transition metal; LiMnPO4; LiNiPO4; and LiCoPO4.
The cathode may further comprise electrically conductive materials like electrically conductive carbon and usual components like binders. Compounds suited as electrically conductive materials and binders are known to the person skilled in the art. For example, the cathode may comprise carbon in a conductive polymorph, for example selected from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances. In addition, the cathode may comprise one or more binders, for example one or more organic polymers like polyethylene, polyacrylonitrile, polybutadiene, polypropylene, polystyrene, polyacrylates, polyvinyl alcohol, polyisoprene and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth)acrylonitrile and 1,3-butadiene, especially styrene-butadiene copolymers, and halogenated (co)polymers like polyvinlyidene chloride, polyvinly chloride, polyvinyl fluoride, polyvinylidene fluoride (PVdF), polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and vinylidene fluoride and polyacrylnitrile.
The anode comprised within the lithium batteries of the present invention comprises an anode active material that can reversibly occlude and release lithium ions or is capable to form an alloy with lithium. For example, carbonaceous material that can reversibly occlude and release lithium ions can be used as anode active material. Carbonaceous materials suited are crystalline carbon materials such as graphite materials like natural graphite, graphitized cokes, graphitized MCMB, and graphitized MPCF; amorphous carbon such as coke, mesocarbon microbeads (MCMB) fired below 1500° C., and mesophase pitch-based carbon fiber (MPCF); hard carbon and carbonic anode active material (thermally decomposed carbon, coke, graphite) such as a carbon composite, combusted organic polymer, and carbon fiber.
Further anode active materials are lithium metal and materials containing an element capable of forming an alloy with lithium. Non-limiting examples of materials containing an element capable of forming an alloy with lithium include a metal, a semimetal, or an alloy thereof. It should be understood that the term “alloy” as used herein refers to both alloys of two or more metals as well as alloys of one or more metals together with one or more semimetals. If an alloy has metallic properties as a whole, the alloy may contain a nonmetal element. In the texture of the alloy, a solid solution, a eutectic (eutectic mixture), an intermetallic compound or two or more thereof coexist. Examples of such metal or semimetal elements include, without being limited to, tin (Sn), lead (Pb), aluminum (Al), 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). Metal and semimetal elements of Group 4 or 14 in the long-form periodic table of the elements are preferable, and especially preferable are titanium, silicon and tin, in particular silicon. Examples of tin alloys include ones having, as a second constituent element other than tin, 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). Examples of silicon alloys include ones having, as a second constituent element other than silicon, 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.
A further possible anode active material are silicon based materials. Silicon based materials include silicon itself, e.g. amorphous and crystalline silicon, silicon containing compounds, e.g. SiOx with 0<x<1.5 and Si alloys, and compositions containing silicon and/or silicon containing compounds, e.g. silicon/graphite composites and carbon coated silicon containing materials. Silicon itself may be used in different forms, e.g. in the form of nanowires, nanotubes, nanoparticles, films, nanoporous silicon or silicon nanotubes. The silicon may be deposited on a current collector. Current collector may be selected from coated metal wires, a coated metal grid, a coated metal web, a coated metal sheet, a coated metal foil or a coated metal plate. Preferably, current collector is a coated metal foil, e.g. a coated copper foil. Thin films of silicon may be deposited on metal foils by any technique known to the person skilled in the art, e.g. by sputtering techniques. One method of preparing thin silicon film electrodes are described in R. Elazari et al.; Electrochem. Comm. 2012, 14, 21-24.
Other possible anode active materials are lithium ion intercalating oxides of Ti, e.g. Li4Ti5O12.
Preferably the anode active material is selected from carbonaceous material that can reversibly occlude and release lithium ions, particular preferred are graphite materials. In another preferred embodiment the anode active is selected from silicon based materials that can reversibly occlude and release lithium ions, preferably the anode comprises a SiOx material or a silicon/carbon composite. In a further preferred embodiment the anode active is selected from lithium ion intercalating oxides of Ti.
The anode and cathode may be made by preparing an electrode slurry composition by dispersing the electrode active material, a binder, optionally a conductive material and a thickener, if desired, in a solvent and 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. Preferred the current collector is a metal foil, e.g. a copper foil or aluminum foil.
The inventive lithium batteries may contain further constituents customary per se, for example separators, housings, cable connections etc. The housing may be of any shape, for example cuboidal or in the shape of a cylinder, the shape of a prism or the housing used is a metal-plastic composite film processed as a pouch. Suited separators are for example glass fiber separators and polymer-based separators like polyolefin separators.
Several inventive lithium batteries may be combined with one another, for example in series connection or in parallel connection. Series connection is preferred. The present invention further provides for the use of inventive lithium ion batteries as described above in devices, especially in mobile devices. Examples of mobile devices are vehicles, for example automobiles, bicycles, aircraft, or water vehicles such as boats or ships. Other examples of mobile devices are those which are portable, for example computers, especially laptops, telephones or electrical power tools, for example from the construction sector, especially drills, battery-driven screwdrivers or battery-driven staplers. But the inventive lithium ion batteries can also be used for stationary energy stores.
Even without further statements, it is assumed that a skilled person is able to utilize the above description in its widest extent. Consequently, the preferred embodiments and examples are to be interpreted merely as a descriptive enclosure which in no way has any limiting effect at all.
To a solution of dimethyl phosphite (25.8 g, 230 mmol, 1.0 eq) and triethylamine (70.6 g, 691 mmol, 3.0 eq) in toluene (800 ml) 47% ethyl glyoxylate in toluene (50.0 g, 230 mmol, 1.0 eq) was added at ice bath temperature, and the mixture was stirred at room temperature for 1 h. Methanesulfonyl chloride (26.6 g, 114 mmol, 1.0 eq) was added to the obtained mixture at ice bath temperature and stirred at room temperature for 1 h. The solvent content of the reaction mixture was reduced under reduced pressure and the precipitate was removed by filtration and washed by a mixture of hexane/dichloromethane (1/1). The solvent of the mother liquid was removed under reduced pressure and the crude product was purified by silica gel chromatography (hexanes/ethyl acetate (EtOAc)). The obtained oil was re-purified by distillation to give the product as a color less oil (36 g, 53% yield).
To a mixture of dimethyl phosphite (108 g, 970 mmol, 1.0 eq) and titanium(IV) isopropoxide (2.76 g, 9.70 mmol, 1 mol %) methyl pyruvate (102 g, 970 mmol, 1.0 eq) was added at ice bath temperature. The reaction temperature was increased to 40° C. for 2 h. The reaction mixture was diluted by dichloromethane (970 ml), and triethylamine (109 g, 1067 mmol, 1.1 eq) was added at ice bath temperature. Methanesulfonyl chloride (123 g, 1067 mmol, 1.1 eq) was added to the obtained reaction mixture at ice bath temperature, and the obtained suspension was stirred at room temperature for 15 h. The solvent content of the reaction mixture was reduced under reduced pressure and the precipitate was removed by filtration and washed by dichloromethane. The solvent of the mother liquid was removed under reduced pressure and the obtained solid was washed and filtrated by diethyl ether (Et2O). The crude product was purified by silica gel chromatography (hexanes/EtOAc) to give the product as a white solid (50 g, 14% yield).
To a solution of 2-propyn-1-ol (34.4 g, 600 mmol, 1.1 eq) and pyruvic acid (50 g, 546 mmol, 1.0 eq) in toluene (1000 ml) p-toluenesulfonic acid (5.3 g, 27 mmol, 5 mol %) was added, and the mixture was refluxed under the Dean-Stark apparatus for 15 h. The reaction was quenched with water, extracted with EtOAc, washed with bine, and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the crude product was purified by silica gel chromatography (hexanes/EtOAc 1:1) to give propargyl pyruvate. The obtained propargyl pyruvate was used for the next step.
To a mixture of dimethyl phosphite (20.2 g, 180 mmol, 1.0 eq) and titanium(IV) isopropoxide (2.56 g, 9.0 mmol, 5 mol %) propargyl pyruvate (25 g, 180 mmol, 1.0 eq) was added at ice bath temperature. The reaction temperature was increased to room temperature for 2 h. The reaction mixture was diluted by dichloromethane (900 ml), and triethylamine (20.2 g, 198 mmol, 1.1 eq) was added at ice bath temperature. Methanesulfonyl chloride (20.8 g, 180 mmol, 1.0 eq) was added to the obtained reaction mixture at ice bath temperature, and the obtained suspension was stirred at room temperature for 15 h. The solvent content of the reaction mixture was reduced under reduced pressure and the precipitate was removed by filtration and washed by dichloromethane. The solvent of the mother liquid was removed under reduced pressure and the crude product was purified by silica gel chromatography (hexanes/EtOAc) to give the product as a clear oil (3.1 g, 5% yield).
To a solution of ethylene cyanohydrin (26.3 g, 363 mmol, 1.1 eq) and pyruvic acid (30 g, 330 mmol, 1.0 eq) in toluene (1000 ml) p-toluenesulfonic acid (3.0 g, 16 mmol, 5 mol %) was added, and the mixture was refluxed under the Dean-Stark apparatus for 15 h. The reaction was quenched with water, extracted with EtOAc, washed with bine, and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the crude product was purified by silica gel chromatography (hexanes/EtOAc 1:1) to give cyanoethyl pyruvate. The obtained cyanoethyl pyruvate was used for the next step.
To a mixture of dimethyl phosphite (5.33 g, 47.5 mmol, 1.0 eq) and titanium(IV) isopropoxide (0.14 g, 0.48 mmol, 1 mol %) cyanoethyl pyruvate (7.45 g, 47.5 mmol, 1.0 eq) was added at ice bath temperature. The reaction temperature was increased to room temperature for 2 h. The reaction mixture was diluted by dichloromethane (250 ml), and triethylamine (5.34 g, 52.3 mmol, 1.1 eq) was added at ice bath temperature. Methanesulfonyl chloride (5.50 g, 47.5 mmol, 1.0 eq) was added to the obtained reaction mixture at ice bath temperature, and the obtained suspension was stirred at room temperature for 15 h. The solvent content of the reaction mixture was reduced under reduced pressure and the precipitate was removed by filtration and washed by dichloromethane. The solvent of the mother liquid was removed under reduced pressure and the crude product was purified by silica gel chromatography (hexanes/EtOAc) to give the product as a clear oil (1.8 g, 10% yield).
To a solution of propargyl alcohol (56.63 g, 1.0 mol, 1.0 eq) and NaHCO3(252 g, 3.00 mol, 3.0 eq) in acetonitrile (1000 ml) was added bromoacetyl chloride (222 g, 1.20 mol, 1.2 eq) at ice bath temperature, and the mixture was stirred at room temperature for 10 min. The reaction was quenched with water, extracted with CH2Cl2, washed with bine, and dried over anhydrous MgSO4. The solvent was removed under reduced pressure and the crude product was purified by distillation to give the product as a color less oil (97 g, 97% yield). The obtained 2-propynyl bromoacetate was used for the next step.
To 2-propynyl bromoacetate (55.1 g, 0.31 mol, 1.0 eq) was added triethyl phosphite (62.7 g, 0.37 mol, 1.2 eq) at room temperature, and the mixture was stirred at 80° C. for 30 min. The reaction mixture was purified by distillation (0.1 Torr, 118° C.) to give the product as a color less oil (69 g, 95% yield).
To a solution of methanesulfonic acid (77.7 g, 800 mmol, 1.0 eq) in H2O (1000 ml) was added silver oxide (93.3 g, 398 mmol, 0.5 eq) at room temperature, and the mixture was stirred at 90° C. for 3 h. Dark black suspension was obtained. The solvent of the reaction mixture was reduced under the reduced pressure and the precipitation was removed by filtration. Acetone was added to the mother liquid and precipitations are washed by acetone to give a white solid. The obtained silver metylsulfonic acid salt was dried over reduced pressure and used further purification (161 g, 99% yield).
To a solution of silver metylsulfonic acid salt (161 g, 790 mmol, 1.0 eq) in acetonitrile (800 ml) was added iodoacetic acid (148 g, 790 mmol, 1.0 eq) at room temperature, and the mixture was stirred for 15 h. The solvent of the reaction mixture was reduced under the reduced pressure. AcOEt was added and the obtained suspension was filtrated. The mother solution was concentrated again under the reduced pressure. The solid was dissolved by EtOAc and hexane was added to make a suspension. The suspension was filtrated and washed by EtOAc/Hexane to give a white solid. The obtained mesyl-glycolic acid was dried over reduced pressure and used further purification (57.8 g, 47% yield).
To a suspension of mesyl-glycolic acid (28.3 g, 180 mmol, 1.0 eq), propargyl alcohol (30.6 g, 540 mmol, 3.0 eq) and 4-(dimethylamino)-pyridine (DMAP, 2.22, 18 mmol, 0.1 eq) in CH2Cl2 (1000 ml) was added 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCl, 42.3 g, 216 mmol, 1.2 eq) at ice bath temperature, and the mixture was stirred at room temperature for 15 h. The reaction was quenched with sat NH4Cl aq solution, extracted with water, washed with bine, and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the crude product was purified by silica gel chromatography (hexanes/EtOAc) to give the product. The obtained oil was purified again by distillation to give the desired molecule as a color less oil (19.5 g, 56% yield).
To a solution of dimethyl phosphite (11.2 g, 100 mmol, 1.0 eq) and acetoaldehyde (4.89 g, 100 mmol, 1.0 eq) in THF (500 ml) was added 1,8-diazabicycloundecene (DBU, 15.5 g, 100 mmol, 1.0 eq) at ice bath temperature, and the mixture was stirred at same temperature for 20 min. To the reaction mixture was added methanesulfonyl chloride (11.6 g, 100 mmol, 1.0 eq) at ice bath temperature, and the mixture was stirred at room temperature for 15 h. The reaction was quenched with water, extracted with AcOEt, washed with bine, and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the crude product was purified by silica gel chromatography (hexanes/EtOAc) to give the product as a color less oil (4.77 g, 20% yield).
A base electrolyte composition was prepared by dissolving 1.0 mol/L LiPF6 in a mixture of 30 vol.-% ethylene carbonate (EC) and 70 wt.-% of diethyl carbonate (DMC) and adding 1 wt.-% vinylene carbonate (VC) and 1.5 wt.-% fluoroethylene carbonate (FEC) (electrolyte sample 1). To this base electrolyte composition (Electrolyte Sample 1) 1 or 2 wt.-% of different comparative and inventive additives were added. The exact additives and concentrations are summarized in Table 1. In the Tables concentrations are given as wt.-% based on the total weight of the electrolyte composition.
An aqueous slurry was prepared by mixing graphite and carbon black with CMC (carboxymethyl cellulose) and SBR (styrene butadiene rubber). The obtained slurry was coated onto copper foil (thickness=9 μm) by using a roll coater and dried under hot air chamber (80° C. to 120° C.). The loading of the resulted electrode was found to be 10 mg/cm2. The electrodes were pressed by roll pressor yielding a density of 1.4 g/cm3.
A slurry was prepared by mixing NCM 622 (Li[Ni0.6Co0.2Mn0.2]O2) and carbon black with polyvinylidene fluoride (PVdF) in of N-methylpyrrolidinone (NMP). The obtained slurry was coated onto aluminum foil (thickness=17 μm) by using a roll coater and dried under hot air chamber and dried further under vacuum at 130° C. for 8 h. The loading of the resulted electrode was found to be 16.4 mg/cm2. The electrodes were pressed by roll pressor yielding a density of 3.4 g/cm3.
Pouch cells (250 mAh) were assembled in Ar-filled glove box, comprising NCM 622 cathode electrode and graphite anode electrode with a polyolefine separator superposed between cathode and anode. Thereafter, 0.7 micro L of the different electrolyte compositions were introduced into the laminate pouch cell and sealed in Ar-filled glove box.
The pouch full-cells were charged up to SOC (state of charge) of 10% at ambient temperature. A degassing process was applied to the cells before charge (CCCV charge, 0.2 C, 4.2 V cut off 0.015 C) and discharge (CC discharge, 0.2 C, 2.5 V cut-off) at ambient temperature. Afterwards the cells were charged again up to 4.2 V (CCCV charge, 0.2 C, 4.2 V cut off 0.015 C) and stored at 60° C. for 6 h. After this initial conditioning, capacity was measured by charge (CCCV charge, 0.2 C, 4.2 V, 0.015 C cut-off) and discharge (CC discharge, 0.2 C, 2.5 V cut-off).
After initial conditioning pouch full-cells were subjected to cycle test. The cells were charged in CC/CV mode up to 4.2 V with 1 C current and cut-off current of 0.015 C and discharged down to 2.5 V with 1 C at 45° C. The charge/discharge (one cycle) was repeated 250 times. The results are summarized in Table 2. “Discharge capacity after 250 cycles” is given in percentage based on the capacity of cell containing electrolyte sample 1 as 100%.
After initial conditioning the pouch full-cells were charged up to 4.2 V at ambient temperature and then stored at 60° C. for 30 days. The amount of generated gas was determined by Archimedes measurements in water at ambient temperature. The amounts of gas generated during the storage are summarized in Table 2. The percentage of generated gas is based on the gas amount generated in the cell containing electrolyte sample 1 as 100%.
As can be seen from the results of Table 2 the inventive electrolyte compositions show similar initial capacities and similar or even better discharge capacities after 250 cycles in regard to the comparative electrolyte compositions, but at the same time less gas generation after storage at 60° C. for 30 days.
| Number | Date | Country | Kind |
|---|---|---|---|
| 17151968.9 | Jan 2017 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2018/051107 | 1/17/2018 | WO | 00 |
