阅读说明：本技术 包含经涂覆的阴极活性材料和作为电解质添加剂的甲硅烷基膦酸酯电化学电池 (Electrochemical cell comprising coated cathode active material and silyl phosphonate as electrolyte additive ) 是由 M·A·门德斯阿古德洛 M·阿尔夫 H·佐默 J·哈格 H·沃尔夫 J·D·赫克尔 于 2019-03-08 设计创作，主要内容包括：本发明涉及一种电化学电池,其包含选自如下的阴极活性材料：含有Mn和至少一种第二过渡金属的混合锂过渡金属氧化物；含有Ni、Al和至少一种第二过渡金属的锂插层混合氧化物；以及锂金属磷酸盐,其中所述颗粒状阴极活性材料的外表面至少部分涂覆有选自过渡金属氧化物、镧系元素氧化物以及周期系统第2、13和14族的金属和半金属的氧化物的氧化物；以及包含至少一种选自式(I)化合物和含有式(II)结构的甲硅烷基膦酸酯化合物的甲硅烷基膦酸酯的电解质组合物。<Image he="323" wi="700" file="DDA0002676860730000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to an electrochemical cell comprising a cathode active material selected from the group consisting of: a mixed lithium transition metal oxide containing Mn and at least one second transition metal; comprisesA lithium intercalation mixed oxide having Ni, Al and at least one second transition metal; and lithium metal phosphate, wherein the outer surface of the particulate cathode active material is at least partially coated with an oxide selected from the group consisting of transition metal oxides, lanthanide oxides, and oxides of metals and semi-metals of groups 2, 13, and 14 of the periodic system; and an electrolyte composition comprising at least one silyl phosphonate selected from compounds of formula (I) and silyl phosphonate compounds comprising a structure of formula (II).)

1. An electrochemical cell, comprising:

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

(B) a cathode comprising at least one particulate cathode active material selected from the group consisting of: a mixed lithium transition metal oxide containing Mn and at least one second transition metal; lithium intercalated mixed oxides containing Ni, Al and at least one second transition metal; and lithium metal phosphate, wherein the outer surface of the particulate cathode active material is at least partially coated with an oxide selected from the group consisting of transition metal oxides, lanthanide oxides, and oxides of metals and semi-metals of groups 2, 13, and 14 of the periodic system;

(C) an electrolyte composition comprising:

(i) at least one aprotic organic solvent;

(ii) at least one lithium ion-containing conductive salt;

(iii) at least one silyl phosphonate selected from compounds of formula (I) and silyl phosphonate compounds comprising a structure of formula (II):

wherein

R¹、R²、R³、R⁴、R⁵And R⁶Are independently selected from H, F, R⁷、OR⁷And OSi (R)⁸)₃；

R⁷Is selected from C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₅-C₇(hetero) aryl and C₆-C₁₃(hetero) aralkyl which may be substituted by one or more groups selected from OSi (CH)₃)₃And substituent of F; and

R⁸independently at each occurrence selected from H, F, R⁷And OR⁷；

Or wherein R is¹And R⁴Combined and selected collectively from O, CR⁹R¹⁰And NR¹¹And forms a 6-membered ring with the Si-O-P-O-Si group;

R⁹and R¹⁰Are independently selected from H, F, R⁷、OR⁷And OSiR⁸ ₃；

R¹¹Selected from H and R⁷(ii) a And

R²、R³、R⁵、R⁶、R⁷and R⁸Independently of each other, selected as defined above;

wherein T is selected from

p is an integer of 0 to 6, (CH)₂) One or more CH of p₂The radical being replaceable by O and (CH)₂) One or more of H of p may be replaced by C₁-C₄Alkyl substitution;

R^1aindependently at each occurrence selected from H, F, Cl, R^4a、OR^4a、OSi(R^5a)₃、OSi(OR^4a)₃And OP (O) (OR)^4a)R^5a；

R^4aIndependently at each occurrence is selected from C₁-C₁₀Alkyl radical, C₃-C₇(hetero) cycloalkyl, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₅-C₇(hetero) aryl and C₆-C₁₃(hetero) aralkyl which may be substituted by one or more substituents selected from CN and F and in which one or more CH groups of alkyl, alkenyl and alkynyl groups not directly bonded to Si atom or O atom₂The group may be replaced by O;

R^3aand R^5aIndependently at each occurrence selected from H, F, C₁-C₁₀Alkyl radical, C₃-C₇(hetero) cycloalkyl, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₅-C₇(hetero) aryl and C₆-C₁₃(hetero) aralkyl which may be substituted by one or more substituents selected from CN and F and in which one or more CH groups are alkyl, alkenyl and alkynyl groups which are not directly bonded to the P atom₂The group may be replaced by O; and

(iv) optionally one or more additives.

2. The electrochemical cell according to claim 1, wherein the oxide forming the coating on the particulate material is selected from the group consisting of scandia, yttria, titania, zirconia, vanadia, niobia, tantalum oxide, molybdenum oxide, zinc oxide, cobalt oxide, lanthanum oxide, ceria, praseodymia, neodymia, samaria, gadolinia, calcia, strontia, baria, boria, aluminum oxyhydroxide, alumina, gallia, silica, germania, tin oxide, and mixtures thereof.

3. An electrochemical cell according to claim 1 or 2, wherein the particulate cathode active material is at least partially coated with an oxide selected from the group consisting of aluminum oxyhydroxide, alumina, zirconia, titania, cobalt oxide, and mixtures thereof.

4. An electrochemical cell according to any one of claims 1 to 3, wherein the particulate cathode active material is selected from lithium transition metal oxides having a layered structure of formula (VI):

Li_1+e(Ni_aCo_bMn_cM_d)_1-eO₂(VI)

wherein

a is from 0.05 to less than 1,

b is 0 to 0.35 of a,

c is 0.01 to 0.9,

d is 0 to 0.2 of the total weight of the alloy,

e is 0 to 0.3 of the total weight of the composition,

wherein a + b + c + d is 1, and

m is one or more metals selected from the group consisting of Na, K, B, Al, Mg, Ca, Cr, V, Mo, Ti, Fe, W, Nb, Zr, and Zn.

5. The electrochemical cell according to any one of claims 1 to 4, wherein the particulate cathode active material is selected from lithium transition metal oxides having a layered structure of formula (VI.3):

Li_1+e[(Ni_a1Co_b1Mn_c1)_1-d1M_d1]_1-eO₂(VI.3)

wherein

a1 is 0.6-0.95,

b1 is 0.025-0.2,

c1 is 0.025-0.2,

d1 is 0 to 0.1,

e is 0-0.2.

6. The electrochemical cell according to any of claims 1 to 5, wherein the electrolyte composition (C) contains 0.01 to 30 wt. -%, based on the total weight of the electrolyte composition, of at least one silyl phosphonate selected from compounds of formula (I) and silyl phosphonate compounds containing the structure of formula (II).

7. An electrochemical cell according to any one of claims 1 to 6, wherein electrolyte composition (C) comprises at least one silyl phosphonate compound comprising a structure of formula (II) wherein R^1aIndependently at each occurrence, selected from H, F, Cl, C₁-C₁₀Alkyl and OC₁-C₁₀Alkyl, wherein the alkyl may be substituted with one or more substituents selected from CN and F, and wherein one or more CH groups of the alkyl group are not directly bonded to a Si atom or an O atom₂The group may be replaced by O; and R^3aIndependently at each occurrence selected from H and C₁-C₁₀Alkyl which may be substituted by one or more F and/or CN and in which one or more CH of alkyl which is not directly bonded to a P atom₂The group may be replaced by O.

8. An electrochemical cell according to any one of claims 1 to 7, wherein electrolyte composition (C) comprises at least one silyl phosphonate compound comprising a structure of formula (II) selected from the group consisting of:

9. electrochemical cell according to any of claims 1 to 6, wherein the electrolyte composition (C) contains at least one compound selected from the group consisting of wherein R¹、R²、R³、R⁴、R⁵And R⁶Independently of one another, from C₁-C₄Alkyl silyl phosphonates of compounds of formula (I).

10. The electrochemical cell according to any of claims 1 to 6, wherein the electrolyte composition (C) contains bis (trimethylsilyl) phosphite.

11. The electrochemical cell according to any one of claims 1 to 10, wherein the aprotic organic solvent (i) is selected from the group consisting of optionally fluorinated cyclic and acyclic organic carbonates, optionally fluorinated acyclic ethers and polyethers, optionally fluorinated cyclic ethers, optionally fluorinated cyclic and acyclic acetals and ketals, optionally fluorinated orthocarboxylic esters, optionally fluorinated cyclic and acyclic esters and diesters of carboxylic acids, optionally fluorinated cyclic and acyclic sulfones, optionally fluorinated cyclic and acyclic nitriles, optionally fluorinated cyclic and acyclic phosphates, and mixtures thereof.

12. Electrochemical cell according to any of claims 1 to 11, wherein the aprotic organic solvent (i) is selected from optionally fluorinated ethers and polyethers, optionally fluorinated cyclic and acyclic organic carbonates and mixtures thereof.

13. Electrochemical cell according to any of claims 1 to 12, wherein the electrolyte composition comprises at least one additive selected from the group consisting of film forming additives, flame retardants, overcharge additives, wetting agents, HF and/or H₂O scavenger, LiPF₆(iii) salt stabilizers, ionic solvation enhancers, corrosion inhibitors and gelling agent additives (iv).

14. The electrochemical cell according to any one of claims 1 to 13, wherein the cathode active material is selected from lithium metal, lithium metal alloys, carbonaceous materials, lithium ion intercalated oxides of Ti and/or silicon containing materials.

15. The electrochemical cell according to any one of claims 1-14, wherein the cathode active material is selected from silicon-containing materials.