Classifications

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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
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  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
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  • H01M4/00—Electrodes
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  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/028—Positive electrodes
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  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
  • H01M2300/0028—Organic electrolyte characterised by the solvent
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
  • H01M2300/0028—Organic electrolyte characterised by the solvent
  • H01M2300/0034—Fluorinated solvents
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• Electrochemical cells comprising coated cathode active material and silyl ester phospho- nate as electrolyte additive
• the present invention relates to an electrochemical cell comprising a cathode active material 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; and lithium metal phosphates, wherein the outer surface of said particulate cathode active material is at least partially coated with an oxide selected from transition metal oxides, lanthanide oxides, and oxides of metals and half metals of groups 2, 13, and 14 of the periodic system; and an electrolyte composition containing at least one silyl ester phosphonate selected from compounds of formula (I)
• R 1 to R 6 , R 3a , and T are defined as below.
• 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.
• lithium ion batteries like lithium ion batteries organic carbonates, ethers, esters and ionic liquids are used as sufficiently polar solvents for solvating the conducting salt(s).
• organic carbonates, ethers, esters and ionic liquids are used as sufficiently polar solvents for solvating the conducting salt(s).
• lithium ion batteries in general comprise not a single solvent but a solvent mixture of different organic aprotic solvents.
• One problem occurring in lithium ion batteries is attributed to undesired reactions on the surface of the electrode active materials which lead to a deterioration of their
• electrochemical properties during the lifetime of the batteries e.g. an increase of the cell resistance, increased gas generation, and reduced capacity.
• Such reactions may be a decomposition of compounds present in the electrolyte composition, e.g. the solvent or conducting salt.
• 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, water and side-product scavengers, 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 to reduce direct contact between the electrolyte composition and the electrode active material.
• US 8,993,158 B2 discloses electrolyte compositions for use in lithium ion batteries comprising silyl ester group-containing phosphonic acid derivatives to inhibit increase of the battery resistance and deterioration of the battery performance in a high-temperature environment.
• US 2013/0164604 Al refers to the use of phosphite esters, phosphonate esters and bisphosphonate esters as additives in electrolyte compositions for lithium ion batteries.
• Another approach to improve the electrochemical properties of a lithium ion battery during its lifetime is the protection the surface of the cathode without hindering the lithium exchange during charging and discharging by coating the cathode active materials with, e.g., aluminium oxide or tin oxide, see, e.g., US 8,993,051.
• an electrochemical cell comprising
• an anode comprising at least one anode active material
• a cathode comprising at least one particulate cathode active material selected from mixed lithium transition metal oxides containing M n and at least one second transition metal; lithium intercalating mixed oxides containing Ni, Al and at least one second transition metal; and lithium metal phosphates, wherein the outer surface of said particulate cathode active material is at least partially coated with an oxide selected from transition metal oxides, lanthanide oxides, and oxides of metals and half metals of groups 2, 13, and 14 of the periodic system;
• R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from H, F,
• R 7 is selected from C j -C 8 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, and C 6 -C 13 (hetero)aralkyl which may be substituted by one or more substituents selected from OSi(CH 3 ) 3 and F; and
• R 8 is independently at each occurrence selected from FI, F, R 7 and OR 7 ; or wherein R 1 and R 4 are combined and jointly selected from O, CR 9 R 10 , and NR 11 and form a 6-membered cycle with the Si-O-P-O-Si group;
• R 9 and R 10 are selected independently from each other from FI, F, R 7 , OR 7 , and OSiR 8 3 ;
• R 11 is selected from FI and R 7 ;
• R 2 , R 3 , R 5 , R 6 , R 7 , and R 8 are independently from each other selected as defined above;
• p is an integer from 0 to 6 and one or more CH 2 groups of (CH 2 )p may be replaced by O and one or more H of (CH 2 )p may be replaced by Ci-C 4 alkyl;
• R la is selected independently at each occurrence from H, F, Cl, R 4a , OR 4a ,
• R 4a is independently at each occurrence selected from C J -C H , 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 which may be substituted by one or more substituents selected from CN and F and wherein one or more CFI 2 -groups of alkyl, alkenyl and alkynyl which are not directly bound to the Si-atom or the O-atom may be replaced by O;
• R 3a and R 5a are selected independently at each occurrence from H, F, C j -C/o 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
• the addition of the silyl ester phosphonates to the electrolyte composition used in combination with the at least partially coated cathode active material yields electrochem ical cells showing good capacity retention and an unexpected low increase of the cell re sistance during cycling at elevated temperatures.
• the inventive electrochemical cell comprises an electrolyte composition (C).
• an electrolyte composition is any composition that comprises free ions and as a result is electrically conductive.
• the electrolyte composition functions as a medium that transfers ions participating in the electrochemical reactions taking place in an
• electrochemical cell In case of a lithium battery the ion participating in the electrochemical reaction is usually the lithium ion.
• the most common electrolyte composition is an ionic solution, although molten electrolyte compositions and solid electrolyte compositions are likewise possible.
• An electrolyte composition of the invention is therefore an electrically conductive medium, primarily due to the presence of at least one substance which is present in a dissolved and/or molten state, i.e., an electrical conductivity supported by movement of ionic species.
• the conducting salt In liquid or gel electrolyte compositions the conducting salt is usually solvated in one or more aprotic organic solvents.
• the electrolyte composition contains at least one aprotic organic solvent (i).
• the at least one aprotic organic solvent may be selected from optionally fluorinated aprotic organic solvents, i.e. from fluorinated and non-fluorinated aprotic organic solvents.
• the electrolyte composition may contain a mixture of fluorinated and non-fluorinated aprotic organic solvents.
• 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 acetales and ketales, optionally fluorinated orthocarboxylic acids esters, optionally fluorinated cyclic and acyclic esters and diesters of carboxylic acids, optionally fluorinated cyclic and acyclic sulfones, optionally fluorinated cyclic and acyclic nitriles and dinitriles and optionally fluorinated cyclic and acyclic phosphates and mixtures thereof.
• optionally 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 an Ci to C 4 alkyl group, e.g. 4-methyl ethylene carbonate, monofluoroethylene carbonate (FEC), and cis- and trans-difluoroethylene carbonate.
• Preferred optionally fluorinated cyclic carbonates are ethylene carbonate, monofluoroethylene carbonate, and propylene carbonate, in particular ethylene carbonate.
• optionally fluorinated acyclic carbonates are di-C j -C/o-alkylcarbonates, wherein each alkyl group is selected independently from each other and wherein one or more H may be substituted by F.
• Preferred are optionally fluorinated di-C 1 -C 4 -alkylcarbonates. Examples are e.g. diethyl carbonate (DEC), ethyl methyl carbonate (EMC), 2,2,2-trifluoroethyl methyl carbonate (TFEMC), dimethyl carbonate (DMC), trifluoromethyl methyl carbonate
• TBM MC methylpropyl carbonate
• Preferred acyclic carbonates are diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC).
• 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.
• optionally fluorinated acyclic ethers and polyethers are optionally fluorinated di-C j -C j o-alkylethers, optionally fluorinated di-C 1 -C 4 -alkyl-C 2 -C 6 -alkylene ethers, optionally fluorinated polyethers, and fluorinated ethers of formula R’-(0-CF p H 2-p ) q -R” wherein R’ is a C J -C JO alkyl group or a C 3 -C 10 cycloalkyl group, wherein one or more H of an alkyl and/or cy cloalkyl group are substituted by F; R” is H, F, a C J -C JO alkyl group, or a C 3 -C 10 cycloalkyl group, wherein one or more H of an alkyl and/or cycloalkyl group are substituted by F; p is 1 or 2;
• each alkyl group of the optionally fluorinated d i-Ci-Ci 0 -a I ky leth - ers is selected independently from the other wherein one or more H of an alkyl group may be substituted by F.
• optionally fluorinated di-C j -C/o-alkylethers are di- methylether, ethylmethylether, diethylether, methylpropylether, diisopropylether, di-n-butyl- ether, 1,1,2,2-tetraf luoroethyl-2,2,3,3-tetraf luoropropyl ether (CF 2 HCF 2 CH 2 OCF 2 CF 2 H), and lH,lFH,5FH-perfluoropentyl-l,l,2,2-tetrafluoroethylether (CF 2 FI(CF 2 )3CFI 2 OCF 2 CF 2 FI).
• optionally fluorinated di-C 1 -C 4 -alkyl-C 2 -C 6 -alkylene ethers are 1,2-dimethoxye- thane, 1,2-diethoxyethane, diglyme (diethylene glycol dimethyl ether), triglyme (triethy leneglycol dimethyl ether), tetraglyme (tetraethyleneglycol dimethyl ether), and diethy- lenglycoldiethylether.
• suitable optionally fluorinated polyethers are polyalkylene glycols wherein one or more FI of an alkyl or alkylene group may be substituted by F, preferably poly-C j -C ⁇ alkylene glycols and especially polyethylene glycols.
• Polyethylene glycols may comprise up to 20 mol% of one or more C 1 -C 4 -alkylene glycols in copolymerized form.
• Polyalkylene glycols are preferably dimethyl- or diethyl- end-capped polyalkylene glycols.
• the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g/mol.
• the molecular weight M w 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.
• fluorinated ethers of formula R’-(0-CF p PI 2-p ) q -R” are 1, 1,2,2-tetraf luoroethy I- 2,2,3,3-tetrafluoropropyl ether (CF 2 PICF 2 CPI 2 OCF 2 CF 2 PI), and lH,lFH,5FH-perfluoropentyl- 1,1,2,2-tetrafluoroethylether (CF 2 PKCF 2 ) 3 CPI 2 OCF 2 CF 2 PI).
• optionally fluorinated cyclic ethers are 1,4-dioxane, tetrahydrofuran, and their derivatives like 2-methyl tetrahydrofuran wherein one or more FI of an alkyl group may be substituted by F.
• 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 methyl dioxolane wherein one or more FI may be substituted by F.
• optionally fluorinated acyclic orthocarboxylic acid esters are tri-C 1 -C 4 alkoxy methane, in particular trimethoxymethane and triethoxymethane.
• suitable cyclic orthocarboxylic acid esters are l,4-dimethyl-3,5,8-trioxabicyclo[2.2.2]octane and 4- ethyl-l-methyl-3,5,8-trioxabicyclo[2.2.2]octane wherein one or more FI may be substituted by F.
• optionally 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 FI may be substituted by F.
• An example of a cyclic ester of carboxylic acids (lactones) is g-butyrolactone.
• optionally fluorinated cyclic and acyclic sulfones are ethyl methyl sulfone, dimethyl sulfone, and tetrahydrothiophene-S,S-dioxide (sulfolane).
• optionally fluorinated cyclic and acyclic nitriles and dinitriles are adipodinitrile, acetonitrile, propionitrile, and butyronitrile wherein one or more FI may be substituted by F.
• optionally fluorinated cyclic and acyclic phosphates are trialkyl phosphates wherein one or more FI of an alkyl group may be substituted by F like trimethyl phosphate, triethyl phosphate, and tris(2,2,2-trifluoroethyl)phosphate.
• aprotic organic solvent(s) are 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 preferred the aprotic organic solvent(s) are selected from optionally fluorinated ethers and polyethers, and optionally fluorinated cyclic and acyclic organic carbonates, and mixtures thereof.
• the electrolyte composition contains at least solvent selected from fluorinated ethers and polyethers, e.g. compounds of formula fluorinated ethers of formula R’-(0-CF p FI 2-p ) q -R” as defined above like CF 2 FICF 2 CFI 2 OCF 2 CF 2 FI or
• the electrolyte composition contains at least one solvent selected from fluorinated cyclic carbonate like 1-fluoro ethyl carbonate.
• the electrolyte composition contains at least one solvent selected from fluorinated cyclic carbonate, e.g. 1-fluoro ethyl carbonate, and at least one solvent selected from fluorinated ethers and polyethers, e.g. compounds of formula fluorinated ethers of formula R’-(0-CF r FI 2-r ) s -R” as defined above like
• 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.
• fluorinated cyclic carbonate e.g. 1-fluoro ethyl carbonate
• non-fluorinated acyclic organic carbonate e.g. dimethyl carbonate, diethyl carbonate or ethyl methyl carbonate.
• the electrolyte composition (C) contains at least one lithium ion containing 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 lithium ion containing conducting salt(s) (ii) present in the electrolyte composition are usually solvated in the aprotic organic solvent(s) (i). Examples of lithium ion containing conducting salts are
• (OR"0) is a bivalent group derived from a 1,2- or 1,3-diol, a 1,2- or 1,3-dicarboxlic acid or a 1,2- or 1,3-hydroxycarboxylic acid, wherein the bivalent group forms a 5- or 6- membered cycle via the both oxygen atoms with the central B-atom;
• n is an integer in the range from 1 to 20.
• Suited 1,2- and 1,3-diols from which the bivalent group (OR"0) 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-l,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 C j -C 4 alkyl group.
• An example for such 1,2- or 1,3-diole is 1,1, 2, 2-tetra(trifluoromethyl)-l, 2-ethane diol.
• “Fully fluorinated C j -C 4 alkyl group” means, that all Fl-atoms of the alkyl group are substituted by F.
• Suited 1,2- or 1,3-dicarboxlic acids from which the bivalent group (OR"0) 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 acid are optionally substituted by one or more F and/or by at least one straight or branched non fluorinated, partly fluorinated or fully fluorinated C j -C 4 alkyl group.
• Suited 1,2- or 1,3-hydroxycarboxylic acids from which the bivalent group (OR"0) 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 C j -C 4 alkyl group.
• An example for such 1,2- or 1,3-hydroxycarboxylic acids is 2,2- bis(trifluoromethyl) -2- hydroxy-acetic acid.
• Li[B(R') 4 ], Li[B(R') 2 (OR"0)] and Li[B(OR”0) 2 ] are Li BF 4 , lithium difluoro oxalato borate and lithium dioxalato borate.
• the at least one lithium ion containing conducting salt is selected from Li PF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 S0 3 , Li BF 4 , lithium bis(oxalato) borate, UCI0 4 , LiN (S0 2 C 2 F 5 ) 2 ,
• the conducting salt is selected from LiPF 6 , LiN (S0 2 F) 2 , and Li BF 4 , and the most preferred conducting salt is LiPF 6 .
• the lithium conducting salt(s) are usually present at a minimum concentration of at least 0.1 mol/l, preferably the concentration of the ion containing conducting salt(s) is 0.5 to 2 mol/l based on the entire electrolyte composition.
• the electrolyte composition (C) contains at least silyl ester phosphonate selected from compounds of formula (I) and silyl ester phosphonate compounds containing the structure of formula (I I) as defined above and described in detail below.
• the silyl ester phosphonates are also referred to as component (iii) of the electrolyte composition (C).
• C j -Cg alkyl as used herein means a straight or branched saturated hydrocarbon group with 1 to 6 carbon atoms having one free valence, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, 2,2-di methylpropyl, n-hexyl, and the like.
• C 2 -C 6 alkenyl refers to an unsaturated straight or branched hydrocarbon group with 2 to 6 carbon atoms having one free valence. Unsaturated means that the alkenyl group contains at least one C-C double bond.
• C 2 -C 6 alkenyl includes for example ethenyl, 1-propenyl, 2-propenyl, 1-n-butenyl, 2-n-butenyl, iso-butenyl, 1-pentenyl, 1-hexenyl, and the like.
• C 2 to C 6 alkynyl refers to an unsaturated straight or branched hydrocarbon group with 2 to 6 carbon atoms having one free valence, wherein the hydrocarbon group contains at least one C-C triple bond.
• C 2 -C 6 alkynyl includes for example ethynyl, propynyl, 1-n-butinyl, 2-n-butynyl, iso-butinyl, 1-pentynyl, 1-hexynyl, and the like.
• Preferred are C 2 -C 4 alkynyl, more preferred are ethynyl and l-propyn-3-yl (propargyl).
• C 5 to C 7 (hetero)aryl 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 C 5 -C 7 (hetero)aryl are pyrrolyl, furanyl, thiophenyl, pyridinyl, pyranyl, thiopyranyl, and phenyl. Preferred is phenyl.
• C 6 -C 13 (hetero)aralkyl denotes an aromatic 5- to 7-membered hy drocarbon cycle substituted by one or more C j -Cg alkyl wherein one or more of the C-atoms of the aromatic cycle may be replaced independently from each other by a heteroatom se lected from N, S, O and P.
• the C 6 -C 13 (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 cy cle or in a Ci-C 6 alkyl grou p, i.e.
• C 6 -C 13 (hetero)aralkyl grou p may be bou nd via the (het- ero)aromatic part or via the alkyl part of the group.
• Exam ples of C 6 -C 13 (hetero)aralkyl are methylphenyl, 2-methylpyridyl, 1,2-dimethylphenyl, 1,3-dimethylphenyl, 1,4-dimethylphenyl, ethyl phenyl, 2-propylphenyl, benzyl, 2-CH 2 -pyridyl, and the like.
• R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from H, F, R 7 , OR 7 , and OSi(R 8 ) 3 wherein it is possible that R 1 and R 4 are combined and jointly selected from O, CR 9 R 10 , and N R 11 and form a 6-membered cycle with the Si-O-P-O-Si group of the com pou nd of formula (I), preferably R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from H, F, R 7 , OR 7 , and OSi(R 8 ) 3 .
• R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are selected independently from each other, and may be same or different, or may partially be same and partially different.
• R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from R 7 , OR 7 , and OSi(R 8 ) 3 , more preferred R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other se lected from R 7 and OR 7 , even more preferred R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from R 7 , most preferred R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from 0 3 -0 6 alkyl, which may be substituted by one or more substituents selected from OSi(CH 3 ) 3 and F, in particu lar preferred R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are inde pendently from each other selected from 0 4 -0 4 alkyl.
• R 7 is selected from 0 4 -0 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 5 -C 7 (hetero)aryl, and C 6 -C 13 (hetero)aralkyl which may be substituted by one or more substituents selected from
• R 7 is selected from 0 4 -0 6 alkyl, C 2 -C 6 alkenyl, and C 2 -C 6 alkynyl, which may be substituted by one or more substituents selected from OSi(CH 3 ) 3 and F
• R 7 is selected from 0 4 -0 6 alkyl and C 2 -C 6 alkenyl, which may be substituted by one or more substituents selected from OSi(CH 3 ) 3 and F
• even more preferred R 7 is selected from C j -Cg alkyl, which may be substituted by one or more substituents selected from OSi(CH 3 ) 3 and F
• most preferred R 7 is selected from Ci-C 4 alkyl.
• R 8 is independently at each occurrence selected from H, F, R 7 and OR 7 , preferably R 8 is in dependently at each occu rrence selected from R 7 and OR 7 , even more preferred R 8 is inde pendently at each occu rrence selected from R 7 and most preferred R 8 is independently at each occurrence selected from 0 4 -0 4 alkyl.
• R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from H, F, R 7 , OR 7 , and OSi(R 8 ) 3 ; wherein R 8 is independently at each occurrence selected from H, F, R 7 and OR 7 ; and R 7 is selected from 0 4 -0 6 alkyl, which may be substi tuted by one or more substituents selected from OSi(CH 3 ) 3 and F, preferably R 1 , R 2 , R 3 , R 4 ,
• R 5 , and R 6 are independently from each other selected from R 7 , OR 7 , and OSi(R 8 ) 3 ; wherein R 8 is independently at each occu rrence selected from R 7 and OR 7 ; and R 7 is selected from C j -Cg alkyl, which may be substituted by one or more substituents selected from OSi (CFH 3 ) 3 and F.
• X is selected from 0, CR 9 R 10 , and N R 11 ;
• R 9 and R 10 are selected independently from each other from H, F, R 7 , OR 7 , and OSiR 8 3 ;
• R 11 is selected from H and R 7 ;
• R 2 , R 3 , R 5 , R 6 , R 8 and R 9 are selected as defined above and as defined as preferred.
• X is selected from 0 and CR 9 R 10 , and more preferred X is 0.
• R 9 and R 10 are selected independently from each other from H, F, R 7 , OR 7 , and OSiR 8 3 , preferably R 9 and R 10 are selected independently from each other from H, R 7 , and OR 7 , more preferred R 9 and R 10 are selected independently from each other from FI and R 7 , even more preferred R 9 and R 10 are selected independently from each other from FI and 0 3 -0 6 alkyl, most preferred R 9 and R 10 are H.
• R 11 is selected from FI and R 7 , preferably R 11 is preferably selected from H, 0 3 -0 6 alkyl, and C 5 -C 7 (hetero)aryl, more preferred R 11 is 0 4 -0 4 alkyl.
• R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from H, F, R 7 , OR 7 , and OSi(R 8 ) 3
• R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from H, F, R 7 , OR 7 , and OSi(R 8 ) 3 wherein R 7 is selected from 0 4 -0 6 alkyl, C 2 -C 6 alkenyl, and C 5 -C 7 (hetero)aryl, which may be substituted by one or more substituents se lected from OSi (CFH 3 ) 3 and F, and R 8 is selected from R 7 and OR 7 .
• R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from H, F, R 7 , OR 7 , and OSi(R 8 ) 3 wherein R 7 is 0 3 -0 6 alkyl, which may be substituted by one or more substituents selected from OSi(CPI 3 ) 3 and F, and R 8 is selected from R 7 and OR 7 .
• Even more preferred R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from R 7 , OR 7 , and OSi(R 8 ) 3 wherein R 7 is C j -Cg alkyl and R 8 is selected from R 7 and OR 7 .
• R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from CrC 6 alkyl which may be substituted by one or more substituents selected from OSi(CPI 3 ) 3 and F, in particular preferred R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently from each other selected from 0 4 -0 4 alkyl.
• a preferred example of compounds of formula (I) is bis(trimethylsilyl) phosphite.
• the electrolyte composition (C) con tains at least one compounds of formula (I) as described above or as described as pre ferred.
• R la is selected independently at each occurrence from H, F, Cl, R 4a , OR 4a , OSi(R 5a ) 3 ,
• R 4a is independently at each occurrence selected from C J -C JO 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 which may be substituted by one or more substituents selected from CN and F and wherein one or more CFI 2 -groups of alkyl, alkenyl and alkynyl which are not directly bound to the Si-atom or the O-atom may be replaced by O.
• R 4a is independently at each occurrence selected from C J -C JO alkyl, which may be substituted by one or more substituents selected from CN and F and wherein one or more CPI 2 -groups of alkyl, alkenyl and alkynyl which are not directly bound to the Si-atom or the O-atom may be replaced by O, more preferred R 4a is independently at each occurrence selected from Ci-C 4 alkyl, which may be substituted by one or more substituents selected from CN and F.
• R 4a may be selected from methyl, ethyl, n-propyl, i-propyl, phenyl, cyclohexyl, CF 3 , CF 2 CF 3 or CPI 2 CN.
• R 5a is selected independently at each occurrence from FI, F, C J -C JO alkyl, C 3 -C 7 (hetero)cy- cloalkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 5 -C 7 (hetero)aryl, and C 6 -C 13 (hetero)aralkyl which may be substituted by one or more substituents selected from CN and F and wherein one or more CPI 2 -groups of alkyl, alkenyl and alkynyl which are not directly bound to the P-atom may be replaced by O, preferably R 5a is selected independently at each occurrence from FI,
• R 5a is selected independently at each occurrence from FI and C J -C JO alkyl, which may be substituted by one or more F and/or CN, even more preferred R 5a is selected independently at each occurrence from FI and Ci-C 4 alkyl, which may be substituted by one or more F and/or CN.
• R 5a may be selected from FI, F, methyl, ethyl, n-propyl, i- propyl, phenyl, cyclohexyl, CF 3 , CF 2 CF 3 or CPI 2 CN.
• R la is selected independently at each occurrence from FI, F, Cl, C J -C JO alkyl, and OC J -C JO alkyl, wherein alkyl may be substituted by one or more substituents selected from CN and F and wherein one or more CPI 2 -groups of alkyl which are not directly bound to the Si-atom or O-atom may be replaced by O, even more preferred R la is selected independently from C J -C JO alkyl which may be substituted by one or more substituents selected from CN and F, in particular preferred R la is selected independently from C j -C 4 alkyl which may be substituted by one or more substituents selected from CN and F.
• R la is for exam ple selected independently at each occu rrence from H, F, Cl, methyl, methoxy, ethyl, ethoxy, n-propyl, n- propoxy, i-propyl, i-propoxy, phenyl, phenoxy, CF 3 , OCF 3 , CF 2 CF 3 , OCF 2 CF 3 , and CFI 2 CN, preferably are selected from methyl, ethyl, i-propyl and n-propyl.
• R 3a is selected independently at each occurrence from H, F, C J -C JO alkyl, C 3 -C 7 (hetero)cy- cloal kyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 5 -C 7 (hetero)aryl, and C 6 -C 13 (hetero)aralkyl which may be substituted by one or more substituents selected from CN and F and wherein one or more CFI 2 -groups of alkyl, alkenyl and alkynyl which are not directly bound to the P-atom may be replaced by 0, preferably R 3a is selected independently at each occurrence from H,
• R 3a is selected independently at each occu rrence from FI and Ci-C 4 alkyl, which may be substi tuted by one or more F and/or CN.
• R 3a may for example be selected from H, F, methyl, ethyl, n-propyl, i-propyl, cyclohexyl, phenyl, CF 3 , CF 2 CF 3 , CPI 2 CPI 2 OCPI 3 , CFH 2 CFH 2 OCH 3 , and CPI 2 CN.
• R 3a being H.
• T is selected from an .
• p is an integer from 0 to 6 and may be 1,
• One or more CFH 2 groups of (CH 2 ) p may be replaced by 0, resu lting e.g. in CFH 2 -0-CFH 2 or CFH 2 -0-CFH 2 -0-CH 2 . I n case more than one CFH 2 group is replaced by 0, the Ch-I 2 groups replaced by 0 are not adjacent.
• One or more FI of (CH 2 ) p may be replaced by C 4 - C 4 alkyl. Exam ples for (CH 2 ) p wherein one or more FI are replaced by Ci-C 4 alkyl are
• silyl ester phosphonate com pou nds containing the structu re of formula (I I) are used wherein
• R la is selected independently at each occurrence from H, F, Cl, C J -C JO alkyl, and OC J -C JO alkyl, wherein alkyl may be substituted by one or more substituents selected from CN and F and wherein one or more CPI 2 -groups of alkyl which are not directly bou nd to the Si-atom or O-atom may be replaced by 0; and
• R 3a is selected independently at each occurrence from FI and C J -C JO alkyl, which may be substituted by one or more F and/or CN and wherein one or more CPI 2 -groups of alkyl which are not directly bound to the P-atom may be replaced by 0.
• Examples of structures of formula (II) are the following structures (II.1) to (11.6)
• the silyl ester phosphonate compounds containing the structure of formula (II) are terminated by phosphonate groups selected from -P ⁇ R ⁇ -OC j -Cg alkyl, more preferred by phosphonate groups selected from -R(0)R 33 -00 ! -0 4 alkyl and in particular preferred by phosphonate groups selected from -P(0)R 3a -0CH 3 and -P(0)R 3a -0CH 2 CH 3 . It is particularly preferred, that the silyl ester phosphonate compounds containing the structure of formula (II) are directly terminated by the afore-mentioned phosphonate groups. According to one embodiment the silyl ester phosphonate contains the structure of formula
• Q 1 is a chemical bond or a monomeric or oligomeric group containing one or more monomeric units of formula (lll.l) and Q 2 is a chemical bond or a monomeric or oligomeric group containing one or more monomeric units of formula (III.2)
• T* is independently at each occurrence Si or Si-(CH 2 ) P -Si, wherein p is an integer of 0 to 6,
• p is selected from 0, 1, 2, 3, 4, 5, and 6, and one or more CH 2 groups of (CH 2 ) P may be replaced by 0 and one or more H of (CH 2 )p may be replaced by Ci-C 4 alkyl, and
• -* is a continuation of the silylester phosphonate backbone by branching
• R 1 and R 3 are defined as described above and as described as preferred.
• the monomeric units of Q 1 and Q 2 may be arranged in any way, e.g. randomly or in blocks or in alternating order.
• Q 1 and/or Q 2 comprise at least one monomeric unit of formula (lll.l) or of formula (III.2), respectively, which is no branching or crosslinking unit, i.e. wherein T* is
• Si or Si-(CH 2 ) P -Si and p is an integer of 0 to 6 and one or more CH 2 groups of (CH 2 ) P may be replaced by 0 and one or more H of (CH 2 )p may be replaced by C/-C 4 alkyl, and wherein in case T* is Si, q 1 is zero and q 2 is 2, and in case T* is Si-(CH 2 ) P -Si, q 1 is zero and q 2 is 4.
• silyl ester phosphonate has the formula (IV)
• Q 1 , Q 2 , T and R 3a are defined as described above;
• R 6a and R 7a are selected independently from R 8a , Si(OR 8a ) 3 and Si(R 9a ) 3 ;
• R 8a is selected independently at each occurrence from Ci-Ci 0 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 which may be substituted by one or more substituents selected from CN and F and wherein one or more CH 2 -groups of alkyl, alkenyl and alkynyl which are not directly bound to an O- or an Si-atom may be replaced by O; and
• R 9a is selected independently at each occurrence from H, F, Cl, C J -C JO alkyl, C 3 -C 7
• (hetero)aralkyl which may be substituted by one or more substituents selected from CN and F and wherein one or more CFI 2 -groups of alkyl, alkenyl and alkynyl which are not directly bou nd to an O-atom may be replaced by O.
• R 6a and R 7a are independently selected from C J -C JO alkyl, S OC J -C JO a I ky l) 3 and Si (R 9a ) 3 wherein R 9a is selected independently at each occurrence from FI, F, Cl, and C J -C JO alkyl, more preferred R 9a is selected from FI, F, Cl and 0 3 -0 4 alkyl.
• R 6a and R 7a may e.g. be selected from methyl, ethyl, n-propyl, i-propyl, Si (CH 3 ) 3 , Si (OCFH 3 ) 3 , Si(CH 3 ) 2 CI and Si (CH 3 )CI 2 .
• R 6 and R 7 are independently selected from 0 3 -0 4 alkyl, i.e. the silyl ester phosphonates are terminated by alkoxy grou ps like methoxy, ethoxy, n-propoxy and n-butoxy, in particu larly preferred are methoxy and ethoxy terminated silyl ester phosphonates.
• silyl ester phosphonate may have the formula (V)
• R la , R 3a , R 6a , R 7a , T, T*, q 1 and q 2 are defined as above and as preferred;
• r 1 and r 2 are independently integers from 0 to 300.
• silyl ester phosphonate compounds containing the structu re of formula (I I) may be used as mixtu res of different silyl ester phosphonate com pou nds with different molecu lar weights, in particular as mixtu res of a monomeric silyl ester phosphonate compound containing the structu re of formu la (I I) which does not contain a repeating monomeric unit and at least one oligomeric or polymeric silyl ester phosphonate com pou nd which contains the structu re of formu la (I I) and one or more repeating monomeric u nits, e.g.
• silyl ester phosphonate compounds containing the structure of formula (I I) may be prepared in analogy. Depending on the starting materials linear compounds or compounds with branching points or cross- linking function are obtainable.
• silyl ester phosphonates Depending on the start ing compounds, the molar ratios and the reaction conditions different silyl ester phospho nates and often mixtures of monomeric silylester phosphonate and one or more oligomeric and polymeric silyl ester phosphonates with different molecular weights are obtained.
• a de tailed description of silyl ester phosphonate compounds containing the structure of formula (II) and their use as additives in electrolyte compositions for electrochemical cells can be found in the not yet published international patent application PCT/EP2018/084385.
• the electrolyte composition (C) con tains at least one silyl ester phosphonate compound containing a structure of formula (II) as described above or described as preferred.
• the electrolyte composition may contain one silylester phosphonate, it may contain more than one silyl ester phosphonate, e.g. two, three or more.
• the electrolyte composition contains in total at least 0.01 wt.-% of the at least one silyl ester phosphonate, based on the total weight of electrolyte composition, preferably at least 0.02 wt.-%, and more preferred at least 0.1 wt.-%, based on the total weight of electro lyte composition.
• the maximum value of the total concentration of the silyl ester phospho nates in the electrolyte composition is usually 30 wt.-%, based on the total weight of elec trolyte composition, preferably 10 wt.-%, more preferred the upper limit of the total concen tration of the silyl ester phosphonates is 5 wt.-%, and even more preferred 3 wt.-%, based on the total weight of electrolyte composition.
• the electrolyte composition contains in total 0.01 to 30 wt.-%, of the at least one silyl ester phosphonate, based on the total weight of electrolyte composition, preferably 0.02 to 10 wt.-%, more preferably 0.1 to 5 wt.- % and most preferred 0.1 to 3 wt.-%.
• the silyl ester phosphonate(s) contained in the electrolyte composition may react with one or more components present in the electrolyte composition like the lithium ion containing conducting salt, e.g. a silyl ester phosphonate containing a OSiR 3 group may form com plexes with fluorine ligand containing complex salts like Li PF 6 , Li BF 4 or lithium difluoro(oxa- lato) borate.
• fluorine ligand containing complex salts like Li PF 6 , Li BF 4 or lithium difluoro(oxa- lato) borate.
• the electrolyte composition (C) may contain one or more further additives (iv) different from the silyl ester phosphonates.
• the at least one further additive different from the silyl ester phosphonates may be selected from polymers, film forming additives, flame retardants, overcharging additives, wetting agents, H F and/or H 2 0 scavenger, stabilizer for LiPF g salt, ionic solvation enhancer, corrosion inhibitors, and gelling agents.
• the minimum 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 concentration of the at least further additive is usually 25 wt.-%.
• Polymers may be selected from polyvinylidene fluoride, polyvinylidene-hexafluoropropylene copolymers, polyvi nylidene- hexafluoropropylene-chlorotrifluoroethylene copolymers, National, polyethylene oxide, polymethyl methacrylate, polyacrylonitrile, polypropylene, polystyrene, polybutadiene, polyethylene glycol, polyvinylpyrrolidone, polyaniline, polypyrrole and/or polythiophene. Polymers may be added to a formulation according to the present invention in order to convert liquid formulations into quasi-solid or solid electrolytes and thus to improve solvent retention, especially during ageing. In this case they function as gelling agents.
• flame retardants are organic phosphorous compounds like cyclophosphazenes, phosphoramides, alkyl and/or aryl tri-substituted phosphates, alkyl and/or aryl di- or tri- substituted phosphites, alkyl and/or aryl di- substituted phosphonates, alkyl and/or aryl tri- substituted phosphines, and fluorinated derivatives thereof.
• organic phosphorous compounds like cyclophosphazenes, phosphoramides, alkyl and/or aryl tri-substituted phosphates, alkyl and/or aryl di- or tri- substituted phosphites, alkyl and/or aryl di- substituted phosphonates, alkyl and/or aryl tri- substituted phosphines, and fluorinated derivatives thereof.
• H F and/or H 2 0 scavenger are optionally halogenated cyclic and acyclic silylamines.
• overcharge protection additives are cyclohexylbenzene, o-terphenyl, p-ter- phenyl, and biphenyl and the like, preferred are cyclohexylbenzene and biphenyl.
• An SEI forming additive 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. I n this way, the lifetime of a battery is significantly extended.
• 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.
• the anode has a reduction potential of 1 Volt or less against lithium such as a lithium intercalating graphite anode.
• 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.
• 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.
• the electrolyte composition preferably contains at least one SEI forming additive.
• SEI forming additives are known to the person skilled in the art. More preferred the electrolyte composition contains at least one SEI forming selected from vinylene carbonate and its derivatives such as vinylene carbonate and methylvinylene carbonate; fluorinated ethylene carbonate and its derivatives such as monofluoroethylene carbonate, cis- and trans-difluorocarbonate; organic sultones such as propylene sultone, propane sultone and their derivatives; ethylene sulfite and its derivatives; oxalate comprising compounds such as lithium oxalate, oxalato borates including dimethyl oxalate, lithium bis(oxalate) borate, lithium difluoro (oxalato) borate, and ammonium bis(oxalato) borate, and oxalato phosphates including lithium tetrafluoro (o
• a compound added may have more than one effect in the electrolyte composition and the electrochemical cell comprising the electrolyte composition.
• E.g. lithium oxalato borate may be added as additive enhancing the SEI formation but can also function as conducting salt.
• the electrolyte composition (C) is preferable non-aqueous.
• 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 DI N 51777 or ISO760: 1978.
• the minimum water content of electrolyte compositions may be selected from 3 ppm, preferably 5 ppm.
• 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 deter mined 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 composition (A) may be prepared by methods which are known to the person skilled in the field of the production of electrolytes, generally by dissolving the lithium conductive salt(s) (i) in the corresponding solvent or solvent mixture (ii) and adding component(s) (iii) and optionally further additive(s) (iv), as described above.
• a further embodiment of the present invention refers to electrochemical cells as defined above wherein the electrolyte composition is obtainable by adding at least one silyl ester phosphonate selected from compounds of formula (I) and silyl ester phosphonate compounds containing the structure of formula (II) to a mixture of at least one solvent or solvent mixture (ii) and lithium ion containing conducting salt(s) (i) and optionally one or more further additive(s) (iv), as described above.
• the electrochemical cell comprising the electrolyte composition (A) may be a lithium battery, a double layer capacitor, or a lithium ion capacitor.
• the general construction of such electrochemical devices is known and is familiar to the person skilled in this art - for batteries.
• the inventive 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.
• the lithium battery is preferably a secondary lithium battery, i.e. a rechargeable lithium battery.
• the electrochemical cell is a lithium ion battery, i.e. a secondary lithium ion electrochemical cell comprising a cathode (A) comprising a cathode active material that can reversibly occlude and release lithium ions and an anode (B) comprising an anode active material that can reversibly occlude and release lithium ions.
• a cathode A
• a cathode active material that can reversibly occlude and release lithium ions
• an anode comprising an anode active material that can reversibly occlude and release lithium ions.
• Anode (A) comprises an anode active material that can reversibly occlude and release lithium ions or is capable to form an alloy with lithium.
• I n particular carbonaceous material that can reversibly occlude and release lithium ions can be used as anode active material.
• Carbonaceous materials suited are crystalline carbon such as a graphite materials, more particularly, natural graphite, graphitized cokes, graphitized MCM B, and graphitized MPCF; amorphous carbon such as coke, mesocarbon microbeads (MCM B) 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.
• a preferred carbonaceous material is graphite.
• anode active materials are lithium metal and lithium metal alloys, i.e. materials containing an element capable of forming an alloy with lithium.
• 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.
• metal or semimetal elements examples include, without being limited to, titanium (Ti), tin (Sn), lead (Pb), aluminum, indium (I n), 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.
• 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).
• 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.
• silicon containing materials include silicon itself, e.g. amorphous and crystalline silicon, silicon containing compounds, e.g. SiO x 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.
• 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.
• anode active materials are lithium ion intercalating oxides of Ti.
• the anode active material comprises carbonaceous material that can reversibly occlude and release lithium ions, particularly preferred the carbonaceous material that can reversibly occlude and release lithium ions is selected from crystalline carbon, hard carbon and amorphous carbon, and particularly preferred is graphite. It is also preferred that the anode active material comprises silicon containing materials. It is further preferred that the anode active material comprises lithium ion intercalating oxides of Ti.
• the inventive electrochemical cell comprises a cathode (B) comprising at least one particulate cathode active material 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; and lithium metal phosphates, wherein the outer surface of said particulate cathode active material is at least partially coated with an oxide selected from transition metal oxides, lanthanide oxides, and oxides of metals and half metals of groups 2, 13, and 14 of the periodic system.
• Exam ples of mixed lithiu m transition metal oxides containing M n and at least one second transition metal are lithium transition metal oxides with layered structure of formu la (VI)
• a is in the range of from 0.05 to less than 1,
• b is in the range of from zero to 0.35
• c is in the range of from 0.01 to 0.9
• d is in the range of from zero to 0.2
• e is in the range of from zero to 0.3
• M being one or more metals selected from Na, K, B, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, N b, Zr, and Zn.
• Cobalt containing compounds of formula (VI) are also named NCM.
• Lithiu m transition metal oxides with layered structu re of formu la (VI) wherein e is larger than zero are also called overlithiated.
• Preferred lithiu m transition metal oxides with layered structure of formu la (VI) are compou nds forming a solid solution wherein a LiM’0 2 phase in which M’ is Ni, and optionally one or more transition metals selected from Co and M n and a Li 2 M n0 3 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 maximu m 10 mol-% M or at maximu m 5 mol-% M or at maximu m 1 mol.-% based on the total amou nt of metal except lithium present in the transition metal oxide.
• These com pou nds are also expressed by formula (VI.2) z LiMO 2 ⁇ (1-z) Li 2 M n0 3 (VI.1) wherein M’ is Ni and at least one metal selected from M n and Co;
• z is 0.1 to 0.8
• metals selected from Na, K, B, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, N b, Zr, and Zn may be present.
• the Ni and if present Co atoms in the LiMO 2 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 Li 2 M n0 3 phase participates only in oxidation and reduction reactions at voltages equal or above 4.5 V vs. Li + /Li given that Mn in the Li 2 Mn0 3 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 0 2 gas at least in the first charging cycling.
• HE-NCM 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.
• 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 0.33Li 2 MnO 3» 0.67Li(Ni 0.4 Co 0.2 Mn 0.4 )O 2 , 0.42Li 2 MnO 3» 0.58Li(Ni 0.4 Co 0.2 Mn 0.4 )O 2 ,
• Examples of manganese-containing transition metal oxides with layer structure of formula (II) wherein d is zero are LiNi 033 Mn 067 O 2 , LiNi 025 Mn 0 5 O 2 , LiNi 035 Co 0.15 Mn 05 O 2 ,
• 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 0.33Li 2 MnO 3» 0.67Li(Ni 04 Co 0.2 Mn 04 )O 2 ,
• 0.40Li 2 MnO 3 0.60Li(Ni 08 Co 0.1 Mn 01 )O 2
• 0.42Li 2 MnO 3 0.58Li(Ni 06 Mn 04 )O 2
• 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.
• 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 (VI.3)
• a is in the range of from 0.5 to 0.95, preferred in the range of 0.6 to 0.95,
• b is in the range of from zero to 0.35
• c is in the range of from 0.0.025 to 0.5, preferred in the range of 0.025 to 0.4,
• d is in the range of from zero to 0.2
• e is in the range of from zero to 0.3
• M being one or more metals selected from Na, K, B, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, Nb, Zr, and Zn.
• Preferred lithium transition metal oxides with layered structure are such of structure (VI.3) Lii +e [(Ni ai Co bi M n cl ) 1-dl M dl ] 1-e 0 2 (VI.3)
• al is in the range of from 0.6 to 0.95
• bl is in the range of from 0.025 to 0.2
• cl is in the range of from 0.025 to 0.2
• dl is in the range of from zero to 0.1
• e is in the range of from zero to 0.2
• Ni-rich compounds of formula (I) are Li[Ni 08 Co 0.1 Mn 0 1 ]O 2 (NCM 811),
• mixed lithium transition metal oxides containing Mn and at least one second transition metal are manganese-containing spinels of formula (VII)
• s 0 to 0.4
• t 0 to 0.4
• 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 (VIII)
• h is 0.7 to 0.9, preferred 0.8 to 0.87, and more preferred 0.8 to 0.85;
• i 0.15 to 0.20
• 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 lithium metal phosphates like LiMnP0 4 , Li N i P0 4 and LiCoP0 4 . These phosphates show usually olivine structure and usually upper cut-off voltages of at least 4.5 V have to be used for charging.
• the outer surface of the particulate cathode active material is at least partially coated with an oxide selected from transition metal oxides, lanthanide oxides, and oxides of metals and half metals of groups 2, 13, and 14 of the periodic system.
• transition metal oxides are scandium oxide, yttria, titania, zirconia, vanadium oxide, niobium oxide, tantalum oxide, molybdenum oxide, zinc oxide, and cobalt oxide.
• lanthanide oxides are lanthanum oxide, ceria, praseodymium oxide, neodymium oxide, samarium oxide, and gadolinium oxide.
• oxides of metals of group 2 are calcium oxide, strontium oxide, and barium oxide.
• oxides of metals and half metals of group 13 are boron oxide, aluminum oxyhydroxide, alumina, and gallium oxide.
• oxides of metals and half metals of group 14 are silicon oxide, germanium oxide, and tin oxide.
• the cathode active material may be coated with an oxide selected from scandium oxide, yttria, titania, zirconia, vanadium oxide, niobium oxide, tantalum oxide, molybdenum oxide, zinc oxide, cobalt oxide, lanthanum oxide, ceria, praseodymium oxide, neodymium oxide, samarium oxide, gadolinium oxide, calcium oxide, strontium oxide, barium oxide, boron oxide, aluminum oxyhydroxide, alumina, gallium oxide silicon oxide, germanium oxide, tin oxide, and mixtures thereof.
• an oxide selected from scandium oxide, yttria, titania, zirconia, vanadium oxide, niobium oxide, tantalum oxide, molybdenum oxide, zinc oxide, cobalt oxide, lanthanum oxide, ceria, praseodymium oxide, neodymium oxide, samarium oxide, gadolinium oxide, calcium oxide, stront
• the cathode active material is at least partially coated with an oxide selected from boron oxide, aluminum oxyhydroxide, alumina, zirconia, titania, cobalt oxide and mixtures thereof, more preferred the oxide forming the coating is selected from aluminum oxyhydroxide, alumina, cobalt oxide and mixtures thereof, and in particular preferred from aluminum oxyhydroxide, alumina, and mixtures thereof.
• an oxide selected from boron oxide, aluminum oxyhydroxide, alumina, zirconia, titania, cobalt oxide and mixtures thereof, more preferred the oxide forming the coating is selected from aluminum oxyhydroxide, alumina, cobalt oxide and mixtures thereof, and in particular preferred from aluminum oxyhydroxide, alumina, and mixtures thereof.
• the term“partially coated” as used in the context with the present invention takes into ac count that in practice it may be difficult to prepare particles coated by the oxide layer with out any defects in said oxide layer.
• the term“partially coated” as used herein means that at least 80% of the particles of a batch of particulate material being coated, and to at least 75% of the surface of each particle being coated, for example 75 to 99.99% and preferably 80 to 90%.
• the thickness of such coating may be very low, for example 0.1 to 5 nm. In other embodi ments, the thickness may be in the range of from 6 to 15 nm. In further embodiments, the thickness of such coating is in the range of from 16 to 50 nm.
• the thickness in this context refers to an average thickness determined mathematically by calculating the amount of thickness per particle surface and assuming a 100% conversion of the starting materials used for preparing the coating.
• non-coated parts of particles do not react during the preparation of the coating due to specific chemical properties of the particles, for example density of chemically reactive groups such as, but not limited to hy droxyl groups, oxide moieties with chemical constraint, or to adsorbed water.
• the cathode active material has an average par ticle diameter (D50) in the range of from 3 to 20 m m, preferably from 5 to 16 pm, wherein D50 is defined as the diameter at which 50% of the mass of a sample is comprised of smaller particle.
• D50 is defined as the diameter at which 50% of the mass of a sample is comprised of smaller particle.
• the average particle diameter can be determined, e. g., by light scattering or LASER diffraction or electroacoustic spectroscopy.
• the particles are usually composed of agglomerates from primary particles, and the above particle diameter refers to the second ary particle diameter.
• the cathode active material has a BET surface in the range of from 0.1 to 1 m 2 /g.
• the BET surface may be determined by nitrogen adsorption after outgassing of the sample at 200° C for 30 minutes or more and beyond this accordance with DI N ISO 9277:2010.
• the partially coated particulate cathode active material used according to the invention may be prepared by the following process:
• step (d) repeating the sequence of steps (b) and (c) twice to ten times, wherein in the last se quence of steps (b) and (c), the moisture may be at least partially substituted by ozone,
• step (e) optionally performing a post-treatment by heating the material obtained after the last step (d) at a temperature from 200 to 800° C.
• the particulate cathode active material provided in step (a) may contain a certain amount of residual moisture, e.g. water which is adsorbed from the surrounding air during handling of the cathode active material. It is preferred to provide a particulate cathode active material having a residual moisture content in the range of from 50 to 1000 ppm, more preferably from 100 to 400 ppm, but it is also possible to use cathode active material having a higher or lower moisture content.
• the residual moisture content of the cathode active material may be determined by Karl-Fischer titration.
• step (a) It is possible to conduct a heat treatment step between step (a) and (b), e.g. to reduce the moisture content of the particulate cathode active material provided in step (a).
• Such heat treatment may comprise keeping the particulate cathode active material for 10 minutes to 24 h at a temperature of from 100 to 300 ° C.
• step (b) said cathode active material is treated with a suited precursor compound like an organic metal or half metal compound or a metal or half metal halide.
• the precursor com pound is hereinafter also called“precursor”.
• the precursor is selected to yield the desired metal or half metal oxide layer on the particulate cathode active material.
• organic metal or half metal compounds examples include metal or half metal alkox- ides, alkyl metal or half metal compounds, metal or half metal amides, and organic chelato metal complexes.
• the alkyl metal or half metal compound, metal or half metal alkoxide or metal or half metal amide, respectively, may be selected from AI(R A ) 3 , AI(R A ) 2 OH, AIR A (OH) 2 , MHR ⁇ - y H y , AI(OR b ) 3 , M 1 (OR a ) 4 , M 1 [NR b ) 2 ] 4 , B(OR b ) 3 , and methyl alumoxane, wherein
• R A are different or equal and selected from C j -Cg-alkyl, straight-chain or branched,
• R B are different or equal and selected from Ci-C 4 -alkyl, straight-chain or branched, and M 1 is Ti or Zr, with Ti being preferred.
• Metal and half metal alkoxides may be selected from Ci-C 4 -alkoxides of aluminum, boron, and transition metals. Preferred transition metals are titanium and zirconium.
• alkoxides are methanolates, hereinafter also referred to as methoxides, ethanolates, herein after also referred to as ethoxides, propanolates, hereinafter also referred to as propoxides, and butanolates, hereinafter also referred to as butoxides.
• propoxides are n-propoxides and iso-propoxides.
• Specific examples of butoxides are n-butoxides, iso- butoxides, sec. -butoxides and tert.-butoxides. Combinations of alkoxides are feasible as well.
• Preferred examples of metal Ci-C 4 -alkoxides are Ti[OCH(CH 3 ) 2 ] 4 , Ti(OC 4 H 9 ) 4 , Zr(OC 4 H 9 ) 4 , Zr(OC 2 H 5 ) 4 , B(OCH 3 ) 3 , AI(OCH 3 ) 3 , AI(OC 2 H 5 ) 3 , AI(0-n-C 3 H 7 ) 3 , AI(0-iso-C 3 H 7 ) 3 , Al(0-sec.- C 4 H 9 ) 3 , and AI(0C 2 H 5 )(0-sec.-C 4 H 9 ) 2 .
• aluminum alkyl compounds are trimethyl aluminum, triethyl aluminum, triisobu tyl aluminum, and methyl alumoxane.
• Metal amides are sometimes also referred to as metal imides.
• metal amides are Zr[N(C 2 H 5 ) 2 )] 4 , Zr[N(CH 3 ) 2 ] 4 , Zr[(CH 3 )N(C 2 H 5 )] 4 and Ti[N(CH 3 ) 2 ] 4 .
• organic chelato metal complexes are Cobalt(l l) acetylacetonate (Co(acac) 2 ), Cobalt(l ll) acetylacetonate Co(acac) 3 , and bis(2,2,6,6-tetramethyl-3,5-heptanedionato)co- balt(l l) (Co(thd) 2 ).
• metal and half metal halides are BBr 3 , BCI 3 , Col 2 , TiCI 4 , and ZrCI 4 .
• Particularly preferred precursors are selected from metal and half metal C 1 -C 4 -alkoxides and metal and half metal alkyl compounds and organic chelato metal complexes, and even more preferred is trimethyl aluminum.
• the amount of the precursor is in the range of 0.1 to 1 g/kg particulate cathode active material.
• the amount of the precursor is calculated to amount to 80 to 200% of a monomolecular layer on the particulate cathode ac tive material per cycle.
• Step (b) may be performed at a temperature in the range of from 15 to 1000° C, preferably 15 to 500° C, more preferably 20 to 350° C, and even more preferably 50 to 220° C. It is preferred to select a temperature in step (b) at which the precursor is in the gas phase.
• Step (b) is usually carried out at normal pressure but may as well be carried out at reduced or elevated pressure, e.g. at a pressure in the range of from 5 mbar to 1 bar above normal pressure or in the range of 100 to 1 mbar below normal pressure.
• normal pressure is 1 atm or 1013 mbar.
• Step (b) of the inventive process as well as step (c) may be carried out in the same or in different vessels.
• the duration of step (b) is preferably in the range of from 1 second to 2 hours, preferably 1 second up to 10 minutes.
• step (c) the material obtained in step (b) is treated with moisture.
• Step (c) is usually car ried out at a temperature in the range of from 50 to 250° C and may be carried out at nor mal pressure but step (c) may as well at reduced or elevated pressure.
• step (c) may be carried out at a pressure in the range of from 5 mbar to 1 bar above normal pres sure or at a pressure in the range of from 150 mbar to 560 mbar above normal pressure.
• Steps (b) and (c) may be carried out at the same pressure or at different pressures, pre ferred is at the same pressure.
• Said moisture may be introduced, e.g., by treating the material obtained in accordance with step (b) with moisture saturated inert gas, for example with moisture saturated nitrogen or moisture saturated noble gas, for example argon.
• Saturation may refer to normal conditions or to the reaction conditions in step (c).
• Step (c) may be performed in a rotary kiln, in a free fall mixer, in a continuous vibrating bed or a fluidized bed.
• the duration of step (c) is usually in the range of from 1 second to 2 hours, preferably 1 second up to 5 minutes.
• the reactor in which the coating process is carried out may be flushed or purged with an in ert gas between steps (b) and (c), for example with dry nitrogen or with dry argon. Suitable flushing - or purging - times are 1 second to 10 minutes. It is preferred that the amount of inert gas is sufficient to exchange the contents of the reactor of from one to 15 times.
• flushing or purging the production of by-products such as separate particles of reac tion product of the precursor with water can be avoided.
• by-products are methane and alumina or trimethyl aluminum that is not deposited on the particulate material, the latter being an undesired by-product.
• Said flushing may also take place after step (c), thus before another step (b).
• steps (b) and (c) may be carried out in a fixed bed reactor, in a fluidized bed reac tor, in a continuous vibrating bed, in a forced flow reactor, in a rotary kiln or in a mixer, for example in a compulsory mixer or in a free-fall mixer.
• fluidized bed reactors are spouted bed reactors.
• compulsory mixers are ploughshare mixers, paddle mix ers and shovel mixers.
• Preferred are ploughshare mixers.
• Preferred ploughshare mixers are installed horizontally, the term horizontal referring to the axis around which the mixing ele ment rotates.
• the coating process is carried out in a shovel mixing tool, in a pad dle mixing tool, in a Becker blade mixing tool and, most preferably, in a ploughshare mixer in accordance with the hurling and whirling principle.
• Free fall mixers are using the gravita tional force to achieve mixing.
• steps (b) and (c) of the inventive process are carried out in a drum or pipe-shaped vessel that rotates around its horizontal axis. More preferred, steps (b) and (c) are carried out in a rotating vessel that has baffles.
• Repetition may include repeating a sequence of steps (b) and (c) each time under exactly the same conditions or under modified conditions but still within the range of the above def initions.
• each step (b) may be performed under exactly the same conditions, or, e.g., each step (b) may be performed under different temperature conditions or with a different duration, for example 120° C, then 10° C and 160 ° C each from 1 second to 1 hour.
• Step (d) includes repeating the sequence of steps (b) and (c) twice to 10 times. It is possi ble to substitute the moisture at least partially by ozone in the last sequence of steps (b) and (c). In this case it is preferred that in step (c) no humidity is applied, and moisture is fully replaced by ozone. Ozone may be generated from oxygen under conditions known per se, and therefore, the ozone usually is applied in the presence of oxygen. In case of the ap plication of ozone in the last step (c) it is preferred that no nitrogen is present.
• step (e) It is possible to perform a post-treatment by heating the material obtained after the last step (d) at a temperature from 200 to 400° C, preferred are 250 to 350° C, also referred to as step (e).
• Step (e) may be carried out in an atmosphere of inert gas, for example nitrogen or a noble gas such as argon.
• inert gas has a water content in the range of from 50 to 400 ppm, preferably 100 to 200 ppm, and a carbon dioxide content ion the range of from 50 to 400 ppm.
• the C0 2 content may be determined by, e.g., optical methods using infrared light.
• Step (e) may have a duration in the range of from 10 seconds to 2 hours, preferred are 10 minutes to 2 hours. It is preferred to carry out step (e) at normal pressure.
• Step (e) may be performed in a rotary kiln. It is possible to perform step (e) in the same vessel as step (c).
• Cathode (B) may comprise further components like binders and electrically conductive materials such as electrically conductive carbon.
• cathode (B) 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.
• binders used in cathode (B) are organic polymers like polyethylene,
• PVdF polyvinylidene fluoride
• Anode (A) and cathode (B) 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 electrochemical cells 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 or Nafion separators.
• inventive electrochemical cells 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 electrochemical cells as described above in devices, especially in mobile devices.
• 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.
• inventive electrochemical cells can also be used for stationary energy stores.
• cathode active material The following cathode active material were used:
• CAM 1 Aluminum-doped Li L02 (Ni 0.6 Co 0.2 Mn 0.2 ) 0.98 O 2 (NCM622) having an average particle size D50 of 9.3 pm determined using the technique of laser diffraction in a Mastersize 3000 instrument from Malvern I nstruments. Al-content was determined by ICP analytics (induc tively coupled plasma mass spectrometry) and corresponded to 815 ppm. Residual moisture content at 250 ° C was determined to be 645 ppm.
• CAM 2 Material obtained by coating 1500 g of CAM 1, which were inside a fluidized bed re actor under vacuum conditions.
• the fluidized bed reactor was heated by an external heating jacket to 180 ° C and kept at 180 ° C for 1080 min. Afterwards the powder was kept at 180 ° C.
• Trimethylaluminum (TMA) in the gaseous state was introduced into the fluidized bed reactor through a filter plater by opening a valve to a precursor reservoir which was kept at 50° C, containing TMA in liquid form. The flow was diluted by nitrogen as carrier gas. After this the reactor was purged with nitrogen.
• the electrolyte compositions were prepared by dissolving 1.0 M LiPF 6 in a mixture of ethyl carbonate (EC, BASF) and diethyl carbonate (DEC, BASF).
• the additives vinylene carbonate (VC), bis(trimethylsilyl) phosphite (Al), and oligomeric silyl-H-phosphonate (A2) were added to the base electrolyte compositions as indicated in Table 1.“wt.%” refers to the total weight of the electrolyte composition. All solvents were dry (water content ⁇ 3 ppm). All electrolyte compositions were prepared and stored in an Ar-filled glovebox having oxygen and water level below 1.0 ppm. Additive (A2) was prepared as described for additive Ml of the not yet published international patent application PCT/EP2018/084385.
• N MP N-methyl-2-pyrrolidinone
• all slurries were prepared on the basis of at least 30 g of cathode active material and the amount of NMP employed was such that the total solid content (CAM + SuperC65 L + SFG6L + PVdF) was ca. 65 %.
• the electrode tapes were dried in a hot-air chamber and finally pressed using a roll pressor.
• Commercial graphite-coated tapes from Elexcel Corporation Ltd. were used as negative electrodes.
• the positive, negative composite electrodes and a polypropylene sepa rator (Celgard) were used to manufacture single layer pouch cells. Thereafter, all cells were filled with electrolyte, as described in Table 1, in an argon-filled glove box having oxygen and water levels below 1.0 ppm and their electrochemical testing carried out in a Maccor 4000 battery-test system.
• Pouch cells prepared comprising a NCM622 cathode prepared according to l ll.l and graph ite anode were charged at a constant current of 0.1 C to a voltage of 4.25 V (CC charge). Af ter degassing the cells, they were discharged at 0.1 C (3.0 V cut-off) (Cycle 1). Immediately after, the cells were charged at 25 ° C at a constant current of 0.1 C to a voltage of 4.25 V (CC) and discharged at 0.1 C (3.0 V cut-off) (Cycle 2).
• the cells were charged at a constant current of 0.5 C to a voltage of 4.25 V, charged at 4.25 V (CCCV) for either 60 minutes or until the current drops below 0.02 C and then the cells were discharged to a dis charge voltage of 3 V at a constant current of 0.5 C (4 times, cycles 3 to 7).
• the cells were further cycled using the same charge conditions as in cycle 3 but using a discharge current of 1 C (2 times, cycles 7 to 8), 2 C (2 times, cycles 9 to 10) and 3 C (2 times, cycles 11 to 12). Finally, the cells were charged and discharged 10 times following the same procedure as that used in cycle 3.
• the cells were transferred to a climate chamber and kept at a constant temperature of 45 ° C. After a 12-hour equilibration time, the cells were charged at a constant current of 1 C to a voltage of 4.25 V, charged at 4.25 V (CCCV) for either 60 minutes or until the current drops below 0.02 C and then the cells were discharged to a discharge voltage of 3 V at a constant current of 1 C (100 times).
• CCCV 4.25 V

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