Electrolyte systems for silicon-containing electrodes

Patent metadata

Field	Value
Publication number	US-2019288273-A1
Application number	US-201815924980-A
Country	US
Kind code	A1
Filing date	Mar 19, 2018
Priority date	Mar 19, 2018
Publication date	Sep 19, 2019
Grant date	—

Abstract

A method of making an electrochemical cell comprising a silicon-containing anode includes forming a first electrochemical cell comprising the silicon-containing anode and a first electrolyte system, pre-lithiating the silicon-containing anode to produce a pre-lithiated anode in the first electrochemical cell, and forming a second electrochemical cell including the pre-lithiated anode and a second electrolyte system. The first electrolyte system includes a fluorinated solvent in an amount greater than 5 wt % and a first salt; and the second electrolyte system includes a hydrocarbon and a second salt. Forming the second electrochemical cell may include removing the first electrolyte system from the first electrochemical cell and introducing the second electrolyte to the emptied first electrochemical cell; or removing the pre-lithiated anode from the first electrochemical cell and constructing the second electrochemical cell with the pre-lithiated anode and the second electrolyte system.

First claim

What is claimed is:

1 . A method for making an electrochemical cell that cycles lithium ions, the electrochemical cell comprising a silicon-containing anode, the method comprising:
forming a first electrochemical cell comprising the silicon-containing anode and a first electrolyte system, wherein the first electrolyte system comprises a fluorinated solvent and a first salt, wherein the fluorinated solvent is present in the first electrolyte system in an amount greater than about 5 wt %; pre-lithiating the silicon-containing anode to produce a pre-lithiated anode in the first electrochemical cell; and forming a second electrochemical cell comprising the pre-lithiated anode and a second electrolyte system, wherein the second electrolyte system comprises a hydrocarbon solvent and a second salt.

2 . The method of claim 1 , wherein forming the second electrochemical cell comprises removing the first electrolyte system from the first electrochemical cell and introducing the second electrolyte into the emptied first electrochemical cell.

3 . The method of claim 1 , wherein forming the second electrochemical cell comprises removing the pre-lithiated anode from the first electrochemical cell and constructing the second electrochemical cell with the pre-lithiated anode and the second electrolyte system.

4 . The method of claim 1 , wherein the method further includes washing the pre-lithiated anode with the hydrocarbon solvent.

5 . The method of claim 4 , wherein the second electrolyte system includes a residual amount of the fluorinated solvent in an amount less than or equal to about 2 wt %.

6 . The method of claim 1 , wherein the fluorinated solvent comprises a solvent selected from the group consisting of: fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), trifluoropropylene carbonate (TFPC), methyl 2,2,2-trifluoroethyl carbonate, ethyl 2,2,2-trifluoroethyl carbonate, 2,2-difluoroethyl methyl carbonate, 2,2-difluoroethyl ethyl carbonate, 2,2-difluoroethylacetate, 2,2,2-trifluoroethylacetate, 1,1,2,2-tatrafluoroethyl 2,2,3,3-tetrafluoropropylether, and combinations thereof; and
wherein the hydrocarbon solvent comprises a solvent selected from the group consisting of: ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and combinations thereof, wherein the first salt and the second salt are independently selected from the group consisting of: lithium hexafluorophosphate (LiPF 6 ); lithium bis(fluorosulfonyl)imide (LiN(FSO 2 ) 2 ) (LiSFI); lithium bis(oxalato)borate (LiB(C 2 O 4 ) 2 ) (LiBOB); lithium difluorooxalatoborate (LiBF 2 (C 2 O 4 )); lithium perchlorate (LiClO 4 ); lithium tetrachloroaluminate (LiAlCl 4 ); lithium iodide (LiI); lithium bromide (LiBr); lithium thiocyanate (LiSCN); lithium tetrafluoroborate (LiBF 4 ); lithium tetraphenylborate (LiB(C 6 H 5 ) 4 ); lithium hexafluoroarsenate (LiAsF 6 ); lithium trifluoromethanesulfonate (LiCF 3 SO 3 ); bis(trifluoromethane)sulfonimide lithium salt (LiN(CF 3 SO 2 ) 2 ); and combinations thereof.

7 . The method of claim 1 , wherein the second electrochemical cell has a Coulombic capacity loss of about 25% after about 500 cycles.

8 . A method of making an electrochemical cell that cycles lithium ions, the electrochemical cell comprising an anode including a silicon-containing electroactive material, the method comprising:
introducing a first electrolyte system into the electrochemical cell, the first electrolyte system comprising a fluorinated solvent and a first salt, wherein the fluorinated solvent has a concentration in the first electrolyte system of greater than about 0.6 M; cycling the electrochemical cell to pre-lithiate the anode; removing the first electrolyte system from the electrochemical cell; and introducing a second electrolyte system into the electrochemical cell, the second electrolyte system comprising a hydrocarbon solvent and a second salt.

9 . The method of claim 8 , wherein the fluorinated solvent includes a cyclic fluorinated solvent selected from the group consisting of: fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), trifluoropropylene carbonate (TFPC), and combinations thereof.

10 . The method of claim 9 , wherein the fluorinated solvent further includes a linear fluorinated solvent selected from the group consisting of: methyl 2,2,2-trifluoroethyl carbonate, ethyl 2,2,2-trifluoroethyl carbonate, 2,2-difluoroethyl methyl carbonate, 2,2-difluoroethyl ethyl carbonate, 2,2-difluoroethylacetate, 2,2,2-trifluoroethylacetate, 1,1,2,2-tatrafluoroethyl 2,2,3,3-tetrafluoropropylether, and combinations thereof.

11 . The method of claim 8 , wherein the hydrocarbon solvent includes a cyclic hydrocarbon solvent selected from the group consisting of: ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), and combinations thereof.

12 . The method of claim 11 , wherein the hydrocarbon solvent further includes a linear hydrocarbon solvent selected from the group consisting of: dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and combinations thereof.

13 . The method of claim 8 , wherein the first salt and second salt are independently selected from the group consisting of: lithium hexafluorophosphate (LiPF 6 ); lithium bis(fluorosulfonyl)imide (LiN(FSO 2 ) 2 ) (LiSFI); lithium bis(oxalato)borate (LiB(C 2 O 4 ) 2 ) (LiBOB); lithium difluorooxalatoborate (LiBF 2 (C 2 O 4 )); lithium perchlorate (LiClO 4 ); lithium tetrachloroaluminate (LiAlCl 4 ); lithium iodide (LiI); lithium bromide (LiBr); lithium thiocyanate (LiSCN); lithium tetrafluoroborate (LiBF 4 ); lithium tetraphenylborate (LiB(C 6 H 5 ) 4 ); lithium hexafluoroarsenate (LiAsF 6 ); lithium trifluoromethanesulfonate (LiCF 3 SO 3 ); bis(trifluoromethane)sulfonimide lithium salt (LiN(CF 3 SO 2 ) 2 ); and combinations thereof; and wherein the first salt has a concentration in the first electrolyte system ranging from about 0.5 M to about 2.5 M, and the second salt has a concentration in the second electrolyte system ranging from about 0.5 M to about 2.5 M.

14 . The method of claim 8 , wherein the first electrolyte system is removed from the electrochemical cell by washing the anode with the hydrocarbon solvent at a temperature from about 10° C. to about 40° C.

15 . The method of claim 14 , wherein the fluorinated solvent has a concentration in the first electrolyte system of greater than about 3 M, and the second electrolyte system includes a residual amount of the fluorinated solvent in an amount less than or equal to about 0.3 M.

16 . The method of claim 8 , wherein the cycling is conducted from 2 to 7 cycles.

17 . A method of making a negative electrode for an electrochemical cell that cycles lithium ions, the method comprising:
pre-lithiating a negative electrode to produce a pre-lithiated negative electrode, wherein the negative electrode comprises a silicon-containing electroactive material and a first electrochemical cell comprises the negative electrode and a first electrolyte system, wherein the first electrolyte system comprises a fluorinated solvent and a first salt, and wherein the fluorinated solvent has a concentration in the first electrolyte system of greater than 3 M and the first salt has a concentration in the first electrolyte system of greater than 0.5 M; removing the pre-lithiated negative electrode from the first electrochemical cell; and constructing a second electrochemical cell, wherein the electrochemical cell comprises the pre

Assignees

• Gm Global Tech Operations Llc

Inventors

• Yang Li
• Verbrugge Mark W
• Cai Mei
• Jiang Meng

Classifications

• H01M10/0568

  characterised by the solutes · CPC title

• H01M2300/0037

  Mixture of solvents · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M4/0459 Primary

  Electrochemical doping, intercalation, occlusion or alloying · CPC title

• H01M2300/0028

  characterised by the solvent · CPC title