Electrolyte additives in lithium-ion batteries

Patent metadata

Field	Value
Publication number	US-11394046-B2
Application number	US-201916525627-A
Country	US
Kind code	B2
Filing date	Jul 30, 2019
Priority date	Apr 7, 2016
Publication date	Jul 19, 2022
Grant date	Jul 19, 2022

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 (vinylene 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.

First claim

The invention claimed is:

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 represented by Formula (Ia) or (Ic):

wherein
R 1 and R 2 are each independently H, alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl, heteroaryl, polymeric moiety or an oligomeric moiety; if nitrogen (N) is adjacent to R 1 and R 2 then R 1 , R 2 and the adjacent nitrogen may form a heteroaryl or a heteroalicyclic ring;
R 3 is H, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy, OP(═O)(OR 1 ) 2 , thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol, heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl, C(O)NR 1 R 2 , NR 1 R 2 , N(R 1 )C(═O)—R 2 , C(═O)—OR 1 , S(═O)—R 1 , S(═O) 2 —R 1 or S(═O) 2 —NR 1 R 2 ; R 4 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 R 1 , R 2 , R 3 or R 4 is optionally substituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR 1 ) 2 , trihalomethyl, cyano, S(═O)—R 1 , S(═O) 2 —R 1 , S(═O) 2 —NR 1 R 2 , halide, cycloalkyl, alkoxy, nitro, NR 1 R 2 , C(O)NR 1 R 2 , N(R 1 )C(═O)—R 2 , hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR 1 , C(═O)—R 1 , aryl, aryloxy, heteroaryloxy, (CH 2 CH 2 O) n or any combination thereof; and n is an integer between 1 and 10;
wherein the additive represented by each one of Formula (Ia) and Formula (Ic) is a polymerization controlling agent; and
wherein the at least one cyclic carbonate consists of Vinylene Carbonate and wherein the polymerization controlling agent regulates a level of polymerization of the Vinylene Carbonate.

2. The lithium ion battery of claim 1 , wherein the solvent comprises:
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).

3. 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), modified Li—NMC oxide and/or lithium Nickel Cobalt Aluminum oxide (NCA).

4. The lithium ion battery of claim 1 wherein n ranges between 9 and 10.

5. The lithium ion battery of claim 1 wherein n ranges between 7 and 8.

6. The lithium ion battery of claim 1 wherein the at least one or more polymerization controlling agents have a concentration of 0.57 percent.

7. The lithium ion battery of claim 1 wherein the at least one or more polymerization controlling agents have a concentration of 1.1 percent.

Assignees

• Storedot Ltd

Inventors

• Sella Eran
• Cohen Shirel
• Herzog Ido
• Schwarz Rony

Classifications

• H01M4/386

  Silicon or alloys based on silicon · CPC title

• H01M2300/0037

  Mixture of solvents · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M10/0567

  characterised by the additives · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title