# US 2019/0356013 A1 · Electrolyte additives in lithium-ion batteries

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- Number: US 2019/0356013 A1
- Document ID: US20190356013A1
- Status: Published application
- Kind: A1
- Application number: 16/525,627
- Filed: 2019-07-30
- Published: 2019-11-21
- Earliest claimed: 2016-04-07
- Assignees: StoreDot Ltd.
- Applicants: StoreDot Ltd.
- Inventors: Eran Sella; Shirel Cohen; Ido Herzog; Rony Schwarz
- Web page: https://patentgrep.com/patent/US20190356013A1

## CPC

- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 4/38: of elements or alloys
- H01M 4/386: {Silicon or alloys based on silicon}
- H01M 4/387: {Tin or alloys based on tin}
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 10/0569: characterised by the solvents
- H01M 10/0567: characterised by the additives
- H01M 2300/0037: Mixture of solvents
- H01M 2300/0051: Carbonates
- Y02E 60/10: Energy storage using batteries
- Y02T 10/70: Energy storage systems for electromobility, e.g. batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

Lithium ion batteries and electrolytes therefor are provided, which include electrolyte additives having dithioester functional group(s) that stabilize the SEI (solid-electrolyte interface) at the surfaces of the anode material particles, and/or stabilize the CEI (cathode electrolyte interface) at the surfaces of the cathode material particles, and/or act as oxygen scavengers to prevent cell degradation. The electrolyte additives having dithioester functional group(s) may function as polymerization controlling and/or chain transfer agents that regulate the level of polymerization of other electrolyte components, such as VC (vinyl carbonate) and improve the formation and operation of the batteries. The lithium ion batteries may have metalloid-based anodes—including mostly Si, Ge and/or Sn as anode active material particles.

## Claims

### Claim 1

A lithium ion battery comprising:
at least one anode comprising anode active material based on Si, Ge and/or Sn,
at least one cathode comprising cathode active material based on at least one formulation comprising lithium iron-phosphorus (LFP) oxide or lithium metal oxide (LiMeO), wherein Me is one or more metal selected from nickel, cobalt, manganese and aluminum and Li and O represent one or more respective lithium and oxygen atoms, and
electrolyte comprising:
solvent comprising at least one linear carbonate and/or ester and at least one cyclic carbonate and/or ester,
at least one dissolved lithium salt, and
at least one additive that is represented by Formula (I) or (Ib):
wherein:
Z1 is halide, alkyl, haloalkyl, aryl, alkenyl, alkynyl, cycloalkyl, heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy, NR1R2, benzyl, thiol, arylthiol, alkylthiol, heteroarylthiol, O(CH2)nC4H4S, amino pyridine, imidazole, cyclic amine, piperazine, N(CH2CH2)2N—C(═S)—S—Z2, a polymeric moiety or an oligomeric moiety;
Z2 is alkyl, haloalkyl, alkyl-C(═O)—O—R1, benzyl, aryl, cycloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, a polymeric moiety, CH(P(═O)(OR1)2)((C═O)OR2), CH2C6H5, (CH2)n(CO)NR1R2, (CH2)n(CO)NH(C5H4N), an oligomeric moiety or S—C(═S)—Z1;
R1 and R2 are each independently H, alkyl, haloalkyl, cycloalkyl, benzyl, aryl, heteroalicyclic, heteroaryl, polymeric moiety or an oligomeric moiety; if nitrogen (N) is adjacent to R1 and R2 then R1, R2 and the adjacent nitrogen may form a heteroaryl or a heteroalicyclic ring;
each of the alkyl, haloalkyl, aryl, benzyl, alkenyl, alkynyl, cycloalkyl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, heteroaryloxy, polymeric moiety, oligomeric moiety arylthiol, alkylthiol or heteroarylthiol of Z1, Z2, R1 or R2 is optionally substituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR1)2, trihalomethyl, S(═O)—R1, S(═O)2—R1, S(═O)2—NR1R2, halide, cycloalkyl, alkoxy, nitro, cyano, NR1R2, C(O)NR1R2, N(R1)C(═O)—R2, hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR1, C(═O)—R1, aryl, aryloxy, heteroaryloxy, (CH2CH2O)n or any combination thereof; and
n is an integer between 1 and 10.

### Claim 2 (depends on 1)

The lithium ion battery of claim 1, wherein Z2 is alkyl, haloalkyl, aryl, alkenyl, alkynyl, a polymeric moiety having a carbon chain or an oligomeric moiety having a carbon chain.

### Claim 3 (depends on 1)

The lithium ion battery of claim 1, wherein Z1 is heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy, NR1R2, thiol, arylthiol, alkylthiol, heteroarylthiol, a polymeric moiety with an electron donating group or an oligomeric moiety with an electron donating group.

### Claim 4 (depends on 3)

The lithium ion battery of claim 3, wherein Z1 is NR1R2.

### Claim 5 (depends on 3)

The lithium ion battery of claim 3, wherein Z2 is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl, a polymeric moiety having a carbon chain or an oligomeric moiety having a carbon chain.

### Claim 6 (depends on 1)

The lithium ion battery of claim 1, wherein the at least one additive is represented by at least one of the following compounds or their combinations:
wherein R103, R104 and R105 are each independently H, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy, O—P(═O)(OR1)2, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol, heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl, C(O)NR1R2, NR1R2, N(R1)C(═O)—R2, C(═O)—OR1, S(═O)—R1, S(═O)2—R1 or S(═O)2—NR1R2;
wherein each of the alkyl, haloalkyl, cycloalkyl, aryl, benzyl, heteroaryl, alkenyl, alkynyl, heteroalicyclic, alkoxy, alkylthiol, heteroarylthiol, aryloxy, heteroaryloxy or arylthiol of R1, R2, R103, R104 and R105 is optionally substituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR1)2, trihalomethyl, cyano, S(═O)—R1, S(═O)2—R1, S(═O)2—NR1R2, halide, cycloalkyl, alkoxy, nitro, NR1R2, C(O)NR1R2, N(R1)C(═O)—R2, hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR1, C(═O)—R1, aryl, aryloxy, heteroaryloxy, (CH2CH2O)n or any combination thereof, and/or with R1 and R2 as defined hereinabove;
n3 each is independently an integer between 0 and 10; and
n each is independently an integer between 1 and 10.

### Claim 7 (depends on 1)

The lithium ion battery of claim 1, comprising cathode active material based on at least one formulation comprising lithium iron-phosphorus (LFP) oxide, lithium Nickel-Manganese-Cobalt (NMC) oxide, modified Li-NMC oxide and/or lithium Nickel Cobalt Aluminum oxide (NCA).

### Claim 8 (depends on 1)

The lithium ion battery of claim 1, wherein the solvent comprises:
at least one of VC (vinylene carbonate) and FEC (fluoroethylene carbonate), and
at least one of DMC (dimethyl carbonate), DEC (diethyl carbonate), EMC (ethyl methyl carbonate), EC (ethylene carbonate), PC (propylene carbonate), EB (ethyl butyrate) and BA (butyl acetate).

### Claim 9

A lithium ion battery comprising:
at least one anode comprising anode active material based on Si, Ge and/or Sn,
at least one cathode comprising cathode active material based on at least one formulation comprising lithium iron-phosphorus (LFP) oxide or lithium metal oxide (LiMeO), wherein Me is one or more metal selected from nickel, cobalt, manganese and aluminum and Li and O represent one or more respective lithium and oxygen atoms, and
electrolyte comprising:
solvent comprising at least one linear carbonate and/or ester and at least one cyclic carbonate and/or ester,
at least one dissolved lithium salt, and
at least one additive represented by Formula (Ia) or (Ic):
wherein
R1 and R2 are each independently H, alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl, heteroaryl, polymeric moiety or an oligomeric moiety; if nitrogen (N) is adjacent to R1 and R2 then R1, R2 and the adjacent nitrogen may form a heteroaryl or a heteroalicyclic ring;
R3 is H, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy, O—P(═O)(OR1)2, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol, heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl, C(O)NR1R2, NR1R2, N(R1)C(═O)—R2, C(═O)—OR1, S(═O)—R1, S(═O)2—R1 or S(═O)2—NR1R2;
R4 is H, alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl;
each of the alkyl, haloalkyl, cycloalkyl, aryl, benzyl, heteroaryl, alkenyl, alkynyl, heteroalicyclic, alkoxy, alkylthiol, heteroarylthiol, aryloxy, heteroaryloxy or arylthiol of R1, R2, R3 or R4 is optionally substituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR1)2, trihalomethyl, cyano, S(═O)—R1, S(═O)2—R1, S(═O)2—NR1R2, halide, cycloalkyl, alkoxy, nitro, NR1R2, C(O)NR1R2, N(R1)C(═O)—R2, hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR1, C(═O)—R1, aryl, aryloxy, heteroaryloxy, (CH2CH2O)n or any combination thereof; and
n is an integer between 1 and 10.

### Claim 10 (depends on 9)

The lithium ion battery of claim 9, wherein the solvent comprises:
at least one of VC (vinylene carbonate) and FEC (fluoroethylene carbonate), and
at least one of DMC (dimethyl carbonate), DEC (diethyl carbonate), EMC (ethyl methyl carbonate), EC (ethylene carbonate), PC (propylene carbonate), EB (ethyl butyrate) and BA (butyl acetate).

### Claim 11 (depends on 9)

The lithium ion battery of claim 9, comprising cathode active material based on at least one formulation comprising lithium iron-phosphorus (LFP) oxide, lithium Nickel-Manganese-Cobalt (NMC), modified Li—NMC oxide and/or lithium Nickel Cobalt Aluminum oxide (NCA).