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1. (WO2018054933) ELECTROCHEMICAL CELLS COMPRISING BIFUNCTIONAL PHOSPHONIC ACID SILYLESTERS
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Claims

An electrochemical cell comprising

(A) an anode comprising at least one anode active material,

(B) a cathode comprising at least one 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; LiNiPC ; LiMnPC ; and LiCoPC ;

(C) an electrolyte composition containing

(i) at least one aprotic organic solvent;

(ii) at least one lithium ion containing conducting salt;

(iii) a compound of formula (I)

H

0=P— OSiR R R

OSiR R5R6

(I)

wherein

R1, R2, R3, R4, R5, and R6 are independently from each other selected from H, F, R7, OR7, and OSi(R8)3;

R7 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 OSi(CH3)3 and F; and

R8 is independently at each occurrence selected from H, F, R7 and OR7; R9 and R10 are selected independently from each other from H, F, R7, OR7, and OSiR83;

R11 is selected from H and R7; and

R2, R3, R5, R6, R7, and R8 are independently from each other selected as defined above; and

(iv) optionally one or more additives.

The electrochemical cell according to claim 1 , wherein the cathode active material is selected from lithium transition metal oxides with layered structure of formula (II)

Lil+e(NiaCObMncMd)l-e02

(II)

wherein

a is in the range of from 0.05 to 0.9,

b is in the range of from zero to 0.35,

c is in the range of from 0.1 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,

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.

The electrochemical cell according to claim 1 , wherein the cathode active material is selected from manganese-containing spinels of formula (III)

(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.

The electrochemical cell according to claim 1 , wherein the cathode active material is selected from lithium intercalating mixed oxides containing Ni, Al and at least one second transition metal.

The electrochemical cell according to claim 1 , wherein the cathode active material is selected from LiNiPC , LiMnPC , and LiCoP04.

The electrochemical cell according to claim 1 , wherein the cathode active material is selected from lithium transition metal oxides with layered structure of formula (I la)

z LiM'02 » (1 -z) Li2Mn03

(Ma)

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.

The electrochemical cell according to any of claims 1 to 6, wherein the electrolyte composition (C) contains 0.01 to 30 wt.-%of the compound of formula (I) based on the total weight of the electrolyte composition.

The electrochemical cell according to any of claims 1 to 7, wherein R1, R2, R3, R4, R5, and R6 are independently from each other selected from Ci-C4 alkyl.

The electrochemical cell according to any of claims 1 to 8, wherein the compound of formula (I) is bis(trimethylsilyl) phosphite.

10. The electrochemical cell according to any of claims 1 to 9, wherein the aprotic organic solvent (i) is selected from optionally fluorinated cyclic and acyclic organic carbonates, optionally fluorinated 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, optionally fluorinated cyclic and acyclic phosphates, and mixtures thereof.

1 1 . The electrochemical cell according to any of claims 1 to 10, wherein the aprotic organic solvent (i) is selected from optionally fluorinated ethers and polyethers, optionally fluorinated cyclic and acyclic organic carbonates, and mixtures thereof.

12. The electrochemical cell according to any of claims 1 to 1 1 , wherein the electrolyte

composition contains at least one additive (iv) selected from film forming additives, flame retardants, overcharging additives, wetting agents, HF and/or H2O scavenger, stabilizer for LiPF6 salt, ionic solvation enhancer, corrosion inhibitors, and gelling agents.

13. The electrochemical cell according to any of claims 1 to 12, wherein anode active material is selected from lithium metal, lithium metal alloys, carbonaceous materials, lithium ion intercalating oxides of Ti and/or silicon containing materials.

14. The electrochemical cell according to any of claims 1 to 13, wherein anode active material is selected from silicon containing materials.

15. Use of compounds of formula (I)

H

0=P— OSiR R R

' ._,4_5_6

OSiR R R

(I)

wherein

R1, R2, R3, R4, R5, and R6 are independently from each other selected from H, F, R7, OR7, and OSi(R8)3;

R7 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C5-C7 (hetero)aryl, and Ce- Ci3 (hetero)aralkyl which may be substituted by one or more substituents selected from OSi(CH3)3 and F; and

R8 is independently at each occurrence selected from H, F, R7 and OR7;

R9 and R10 are selected independently from each other from H, F, R7, OR7, and OSiR83; R11 is selected from H and R7; and

R2, R3, R5, R6, R7, and R8 are independently from each other selected as defined above;

as cathode active additive in electrolyte compositions for electrochemical cells.

Use of compounds of formula (I)

H

0=P— OSiR R R

OSiR R5R6

(I)

wherein

R1 , R2, R3, R4, R5, and R6 are independently from each other selected from H, F, R7, OR7, and OSi(R8)3;

R7 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C5-C7 (hetero)aryl, and Ce- Ci3 (hetero)aralkyl which may be substituted by one or more substituents selected from OSi(CH3)3 and F; and

R8 is independently at each occurrence selected from H, F, R7 and OR7;

R9 and R10 are selected independently from each other from H, F, R7, OR7, and OSiR83;

R11 is selected from H and R7; and

R2, R3, R5, R6, R7, and R8 are independently from each other selected as defined above;

in electrolyte compositions for electrochemical cells for lowering the gas generation in the electrochemical cells.