Electrolyte additives in lithium-ion batteries

Patent metadata

Field	Value
Publication number	US-11205796-B2
Application number	US-201916291031-A
Country	US
Kind code	B2
Filing date	Mar 4, 2019
Priority date	Apr 7, 2016
Publication date	Dec 21, 2021
Grant date	Dec 21, 2021

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

The invention claimed is:

1. A lithium ion battery comprising:
at least one anode comprising active material based on Si, Ge and/or Sn,
at least one cathode comprising 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 0 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):

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, 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, 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 1; and
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 or any combination thereof;
wherein Z i 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;
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;
and wherein the at least one additive is represented by:

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), EB (ethyl butyrate) and BA (butyl acetate).

3. A lithium ion battery comprising:
at least one anode comprising active material based on Si, Ge and/or Sn,
at least one cathode comprising 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 0 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):

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, 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, 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 1; and
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 or any combination thereof;
wherein the lithium ion battery further comprises at least one of VC (vinylene carbonate) and FEC (fluoroethylene carbonate); and

wherein the at least one additive is represented by:

4. A lithium ion battery comprising:
at least one anode comprising active material based on Si, Ge and/or Sn,
at least one cathode comprising 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 0 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):

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, 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, 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 1; and
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 or any combination thereof; and
wherein the at least one additive is represented by:

5. 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).

6. A lithium ion battery comprising:
at least one anode comprising active material based on Si, Ge and/or Sn,
at least one cathode compr

Assignees

• Storedot Ltd

Inventors

• Sella Eran
• ARMON Mor Shmuel

Classifications

• H01M10/0525 Primary

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

• H01M10/4235

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title