US 12,603,275 B2Granted

Electrochemical cells comprising coated cathode active material and silyl ester phosphonate as electrolyte additive

AssigneeBASF SE

InventorsManuel Alejandro Mendez Agudelo, Maraike Ahlf, Heino Sommer, Jacob Haag, Hannes Wolf, Johannes David Hoecker

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Abstract

An electrochemical cell has 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 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; and an electrolyte composition containing at least one silyl ester phosphonate of formula (I) and at least one silyl ester phosphonate of formula (II)

Claims18

Dependent claims

An electrochemical cell, comprising

(A) an anode comprising an anode active material;
(B) a cathode comprising at least one selected from the group consisting of:
(a) a particulate cathode active material comprising mixed lithium transition metal oxide comprising Mn and at least a second transition metal,
(b) a particulate cathode active material comprising lithium intercalating mixed oxide comprising Ni and Al and a second transition metal, and
(c) a particulate cathode active material comprising a lithium metal phosphate, an outer surface of the particulate cathode active material of (a), (b), and (c) being at least partially coated with an oxide comprising a transition metal, lanthanide, and/or a metal or half metal of groups 2, 13, and/or 14 of the periodic table;
(C) an electrolyte composition comprising:
(i) an aprotic organic solvent;
(ii) a lithium ion containing conducting salt;
and
(iii) a silyl ester phosphonate of formula (I), or a silyl ester phosphonate compound containing the structure of formula (II), or an oligomeric silyl ester phosphonate of formula (IX):
wherein
in formula (I) R1, R2, R3, R4, R5, and R6 are independently H, F, R7, OR7, or OSi (R8)3, R7 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C5-C7 (hetero)aryl, or C6-C13 (hetero)aralkyl, optionally substituted by one or more OSi(CH3)3 and/or F,
R8 is independently H, F, R7 or OR7,
or wherein R1 and R4 of Formula (I) are combined and jointly O, CR9R10 or NR11 to form a 6-membered cycle ring with the Si—O—P—O—Si group in Formula (I),
R9 and R10 are independently H, F, R7, OR7, or OSiR83,
R11 is H or R7, and
wherein in formula (II) T is
p is an integer in a range of from 1 to 6, one or more H of (CH2)p are optionally replaced by C1-C4 alkyl;
R1a is independently H, F, Cl, R4a, OR4a, OSi(R5a)3, OSi(OR4a)3, or OP(O)(OR4a)R5a,
R4a is independently C1-C10 alkyl, C3-C7 (hetero)cycloalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C5-C7 (hetero)aryl, or C6-C13 (hetero)aralkyl, optionally substituted by one or more CN and/or F, wherein one or more CH2-groups of the alkyl, alkenyl, and alkynyl not directly bound to the Si-atom or the O-atom are optionally replaced by O,
R3a and R5a are independently H, F, C1-C10 alkyl, C3-C7 (hetero)cycloalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C5-C7 (hetero)aryl, or C6-C13 (hetero)aralkyl, optionally substituted by one or more CN and/or F, wherein one or more CH2-groups of the alkyl, alkenyl, and alkynyl not directly bound to the P-atom optionally replaced by O, and
wherein in formula (IX) n is an integer from 1 to greater than 1;
wherein the electrolyte composition (C) comprises 0.01 to 30 wt % of the silyl ester phosphonate of formula (I) or formula (IX) or silyl ester phosphonate compound containing the structure of formula (II), based on total weight of the electrolyte composition (C).

20 more elements

An electrochemical cell, comprising

(A) an anode comprising an anode active material;
(B) a cathode comprising at least one selected from the group consisting of:
(a) a particulate cathode active material comprising mixed lithium transition metal oxide comprising Mn and a second transition metal,
(b) a particulate cathode active material comprising lithium intercalating mixed oxide comprising Ni and Al and a second transition metal, and
(c) a particulate cathode active material comprising a lithium metal phosphate,
an outer surface of the particulate cathode active material of (a), (b), and (c) being at least partially coated with an oxide comprising a transition metal, lanthanide, and/or a metal or half metal of groups 2, 13, and/or 14 of the periodic table;
(C) an electrolyte composition comprising:
(i) an aprotic organic solvent;
(ii) a lithium ion containing conducting salt;
and
(iii) a silyl ester phosphonate compound containing the structure of formula (II):
wherein
T is
p is an integer in a range of from 1 to 6, one or more H of (CH2)p are optionally replaced by C1-C4 alkyl;
R1a is independently H, F, Cl, R4a, OR4a, OSi(R5a)3, OSi(OR4a)3, or OP(O)(OR4a)R5a,
R4a is independently C1-C10 alkyl, C3-C7 (hetero)cycloalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C5-C7 (hetero)aryl, or C6-C13 (hetero)aralkyl, optionally substituted by one or more CN and/or F, wherein one or more CH2-groups of the alkyl, alkenyl, and alkynyl not directly bound to the Si-atom or the O-atom are optionally replaced by O,
R3a and R5a are independently H, F, C1-C10 alkyl, C3-C7 (hetero)cycloalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C5-C7 (hetero)aryl, or C6-C13 (hetero)aralkyl, optionally substituted by one or more CN and/or F, wherein one or more CH2-groups of the alkyl, alkenyl, and alkynyl not directly bound to the P-atom optionally replaced by O;
and
wherein the electrolyte composition (C) comprises 0.01 to 30 wt % of the silyl ester phosphonate compound containing the structure of formula (II), based on total weight of the electrolyte composition (C).

16 more elements

Dependencies are inferred from the claim text.

Facts

Application: 16/970,775Filed 8 Mar 2019
Priority: EP 1816165014 Mar 2018
Published: US 2021/0098782 A11 Apr 2021
Granted: 14 Apr 2026
Term ends: Not estimatedThe source records don’t support an estimate.

Classification25 codes

H01M 4/366
Composites: as layered products
C01G 53/50
Containing manganese: of the type n-, e.g. LiO2 or LiO2
C01G 53/502
Of the type n-, e.g. LiO2 or LiO2: containing lithium and cobalt
C01G 53/504
Containing lithium and cobalt: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5,…