Electrolyte additives in lithium-ion batteries

Patent metadata

Field	Value
Publication number	US-2019356013-A1
Application number	US-201916525627-A
Country	US
Kind code	A1
Filing date	Jul 30, 2019
Priority date	Apr 7, 2016
Publication date	Nov 21, 2019
Grant date	—

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.

First 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:
Z 1 is halide, alkyl, haloalkyl, aryl, alkenyl, alkynyl, cycloalkyl, heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy, NR 1 R 2 , benzyl, thiol, arylthiol, alkylthiol, heteroarylthiol, O(CH 2 ) n C 4 H 4 S, amino pyridine, imidazole, cyclic amine, piperazine, N(CH 2 CH 2 ) 2 N—C(═S)—S—Z 2 , a polymeric moiety or an oligomeric moiety;
Z 2 is alkyl, haloalkyl, alkyl-C(═O)—O—R 1 , benzyl, aryl, cycloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, a polymeric moiety, CH(P(═O)(OR 1 ) 2 )((C═O)OR 2 ), CH 2 C 6 H 5 , (CH 2 ) n (CO)NR 1 R 2 , (CH 2 ) n (CO)NH(C 5 H 4 N), an oligomeric moiety or S—C(═S)—Z 1 ;
R 1 and R 2 are each independently H, alkyl, haloalkyl, cycloalkyl, benzyl, aryl, heteroalicyclic, 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;
each of the alkyl, haloalkyl, aryl, benzyl, alkenyl, alkynyl, cycloalkyl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, heteroaryloxy, polymeric moiety, oligomeric moiety arylthiol, alkylthiol or heteroarylthiol of Z 1 , Z 2 , R 1 or R 2 is optionally substituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR 1 ) 2 , trihalomethyl, S(═O)—R 1 , S(═O) 2 —R 1 , S(═O) 2 —NR 1 R 2 , halide, cycloalkyl, alkoxy, nitro, cyano, 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.

2 . The lithium ion battery of claim 1 , wherein Z 2 is alkyl, haloalkyl, aryl, alkenyl, alkynyl, a polymeric moiety having a carbon chain or an oligomeric moiety having a carbon chain.

3 . The lithium ion battery of claim 1 , wherein Z 1 is heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy, NR 1 R 2 , thiol, arylthiol, alkylthiol, heteroarylthiol, a polymeric moiety with an electron donating group or an oligomeric moiety with an electron donating group.

4 . The lithium ion battery of claim 3 , wherein Z 1 is NR 1 R 2 .

5 . The lithium ion battery of claim 3 , wherein Z 2 is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl, a polymeric moiety having a carbon chain or an oligomeric moiety having a carbon chain.

6 . 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 R 103 , R 104 and R 105 are each independently H, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy, O—P(═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 ;
wherein 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 103 , R 104 and R 105 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/or with R 1 and R 2 as defined hereinabove;
n 3 each is independently an integer between 0 and 10; and
n each is independently an integer between 1 and 10.

7 . 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).

8 . 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).

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
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, O—P(═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.

10 . The lithium ion battery of claim 9 , wherein the solvent comprises:
at least one of VC (vinylene carbonate) and FEC (fluoroethylene carbonate),

Assignees

• Storedot Ltd

Inventors

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

Classifications

• H01M10/0525 Primary

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · 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

• H01M2300/0037

  Mixture of solvents · CPC title