IP Library › Granted Patent US 12,230,753
Granted Patent B2
US 12,230,753 · App. 17/158,751 · Granted Feb 18, 2025

Electrolyte for electrochemical cells with a silicon-containing electrode

Inventors: Xingyi Yang (Sterling Heights, MI); Michael P. Balogh (Novi, MI); Xingcheng Xiao (Troy, MI); Joel G. Toner (Imlay City, MI)
Assignee: GM GLOBAL TECHNOLOGY OPERATIONS LLC
H01M10/0562H01M4/386H01M4/505H01M4/525H01M4/625H01M2004/027H01M2004/028H01M2220/20H01M2300/008
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,230,753
App. No.
17/158,751
Granted
Feb 18, 2025
Kind
B2
Abstract

An electrolyte composition for electrochemical cells including a silicon-containing electrode is provided herein as well as electrochemical cells including the electrolyte composition. The electrolyte composition includes a lithium salt, fluoroethylene carbonate (FEC), a linear carbonate, vinylene carbonate, and a fluorosilane additive. The FEC and the linear carbonate are present in the electrolyte composition in a ratio of about 1:3 v/v to about 1:9 v/v.

Claims (31)

1. An electrolyte composition for an electrochemical cell, the electrolyte composition comprising:

a lithium salt selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), 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 bis (oxalato) borate (LiB(C 2 O 4 ) 2 ) (LiBOB), lithium difluorooxalatoborate (LiBF 2 (C 2 O 4 )), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(trifluoromethane)sulfonylimide (LiN(CF 3 SO 2 ) 2 ), lithium bis(fluorosulfonyl)imide (LiN(FSO 2 ) 2 ) (LiSFl), and a combination thereof;

fluoroethylene carbonate (FEC) present in an amount of about 15 wt. % to about 30 wt. %, based on total weight of the electrolyte composition;

a linear carbonate selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethylcarbonate (EMC), and a combination thereof, wherein the linear carbonate is present in an amount about 50 wt. % to about 80 wt. %, based on total weight of the electrolyte composition, wherein the FEC and the linear carbonate are present in a ratio of about 1:3 v/v to about 1:9 v/v;

vinylene carbonate present in an amount of about 1 wt. % to about 5 wt. %, based on total weight of the electrolyte composition; and

a fluorosilane additive selected from the group consisting of (3-cyanopropyl) dimethylfluorosilane, (2-cyanoethyl) dimethylfluorosilane, (4-cyanobutyl) dimethylfluorosilane, and a combination thereof.

2. The electrolyte composition of claim 1 , wherein the fluorosilane additive is present in an amount of about 1 wt. % to about 5 wt. %, based on total weight of the electrolyte composition.

3. The electrolyte composition of claim 1 , wherein ethylene carbonate (EC) is not present.

4. An electrolyte composition for an electrochemical cell, the electrolyte composition comprising:

a lithium salt selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), 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 bis (oxalato) borate (LiB(C 2 O 4 ) 2 ) (LiBOB), lithium difluorooxalatoborate (LiBF 2 (C 2 O 4 )), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(trifluoromethane)sulfonylimide (LiN (CF 3 SO 2 ) 2 ), lithium bis(fluorosulfonyl)imide (LiN (FSO 2 ) 2 ) (LiSFl), and a combination thereof;

fluoroethylene carbonate (FEC) present in an amount of about 15 wt. % to about 30 wt. %, based on total weight of the electrolyte composition;

a linear carbonate selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethylcarbonate (EMC), and a combination thereof, wherein the linear carbonate is present in an amount about 50 wt. % to about 80 wt. %, based on total weight of the electrolyte composition, wherein the FEC and the linear carbonate are present in a ratio of about 1:3 v/v to about 1:9 v/v;

vinylene carbonate present in an amount of about 1 wt. % to about 5 wt. %, based on total weight of the electrolyte composition; and

a fluorosilane additive selected from the group consisting of (2-cyanoethyl) dimethylfluorosilane, (4-cyanobutyl) dimethylfluorosilane, and a combination thereof.

5. An electrochemical cell comprising:

a negative electrode comprising a first electroactive material comprising silicon;

a positive electrode comprising a second electroactive material, wherein the positive electrode is spaced apart from the negative electrode;

a porous separator disposed between confronting surfaces of the negative electrode and the positive electrode; and

an electrolyte infiltrating one or more of: the negative electrode, the positive electrode, and the porous separator,

wherein the liquid electrolyte comprises:

a lithium salt selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), 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 bis (oxalato) borate (LiB(C 2 O 4 ) 2 ) (LiBOB), lithium difluorooxalatoborate (LiBF 2 (C 2 O 4 )), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(trifluoromethane)sulfonylimide (LiN (CF 3 SO 2 ) 2 ), lithium bis(fluorosulfonyl)imide (LiN (FSO 2 ) 2 ) (LiSFl), and a combination thereof;

fluoroethylene carbonate (FEC) present in an amount of about 15 wt. % to about 30 wt. %, based on total weight of the electrolyte composition;

a linear carbonate selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethylcarbonate (EMC), and a combination thereof, wherein the linear carbonate is present in an amount about 50 wt. % to about 80 wt. %, based on total weight of the electrolyte composition, wherein the FEC and the linear carbonate are present in a ratio of about 1:3 v/v to about 1:9 v/v;

vinylene carbonate present in an amount of about 1 wt. % to about 5 wt. %, based on total weight of the electrolyte composition; and

a fluorosilane additive selected from the group consisting of (3-cyanopropyl) dimethylfluorosilane, (2-cyanoethyl) dimethylfluorosilane, (4-cyanobutyl) dimethylfluorosilane, and a combination thereof.

6. The electrochemical cell of claim 5 , wherein first electroactive material comprises silicon-containing particles having an average particle diameter of greater than or equal to about 1 μm, wherein the silicon-containing particles comprise silicon, carbon coated silicon, a silicon oxide, a lithium silicon alloy, a silicon tin alloy, a silicon iron alloy, a silicon aluminum alloy, a silicon cobalt alloy, or a combination thereof.

7. The electrochemical cell of claim 5 , wherein the fluorosilane additive is present in an amount of about 1 wt. % to about 5 wt. %, based on total weight of the electrolyte.

8. The electrochemical cell of claim 5 , wherein ethylene carbonate (EC) is not present in the electrolyte.

9. The electrochemical cell of claim 5 , the negative electrode further comprises an electrically conductive material, wherein the electrically conductive material comprises carbon black, acetylene black, graphite, carbon nanotubes, carbon fibers, carbon nanofibers, graphene, graphene nanoplatelets, graphene oxide, nitrogen-doped carbon, a metallic powder, a liquid metal, a conductive polymer, or a combination thereof.

10. The electrochemical cell of claim 5 , wherein the second electroactive material is selected from the group consisting of Li (1+x) Mn 2 O 4 , where 0.1≤x≤1; LiMn (2−x) Ni x O 4 , where 0≤x≤0.5; LiCoO 2 ; Li(Ni x Mn y CO z )O 2 , where 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1; LiNi (1−x−y) Co x M y O 2 , where 0<x<0.2, y<0.2, and M is Al, Mg, or Ti; LiFePO 4 , LiMn 2-x FexPO 4 , where 0<x<0.3; LiNiCoAIO 2 ; LIMPO 4 , where M is at least one of Fe, Ni, Co, and Mn; Li(Ni x Mn y Co 2 Al p )O 2 , where 0≤x≤1, 0≤y≤1, 0≤z≤1, 0≤P≤1, x+y+z+p=1 (NCMA); LiNiMnCoO 2 ; Li 2 FePO 4 F; LiMn 2 O 4 ; LiFeSiO 4 ; LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), LiMnO 2 (LMO), activated carbon, sulfur, and a combination thereof.

11. The electrochemical cell of claim 5 , wherein the electrochemical cell is a pouch cell.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 9, 2021
From: YANG, XINGYI; BALOGH, MICHAEL P.; XIAO, XINGCHENG; TONER, JOEL G.
To: GM GLOBAL TECHNOLOGY OPERATIONS LLC
Reel/Frame 055197/0191 →
Continuity (1)
Related Publication 20220238911A1 · Jul 28, 2022
References Cited (31)
US 8440350B1 · Verbrugge et al. · 2013 [cited by applicant]
US 8859144B2 · Xiao · 2014 [cited by applicant]
US 8999584B2 · Jiang et al. · 2015 [cited by applicant]
US 9005811B2 · Xiao et al. · 2015 [cited by applicant]
US 9093705B2 · Xiao et al. · 2015 [cited by applicant]
US 9142830B2 · Xiao et al. · 2015 [cited by applicant]
US 9302914B2 · Liu et al. · 2016 [cited by applicant]
US 9362551B2 · Sachdev et al. · 2016 [cited by applicant]
US 9379374B2 · Liu et al. · 2016 [cited by applicant]
US 9531004B2 · Xiao et al. · 2016 [cited by applicant]
US 9564639B2 · Huang · 2017 [cited by applicant]
US 9570752B2 · Huang et al. · 2017 [cited by applicant]
US 9577251B2 · Xiao et al. · 2017 [cited by applicant]
US 9780361B2 · Xiao et al. · 2017 [cited by applicant]
US 10062898B2 · Xiao · 2018 [cited by applicant]
US 10164245B2 · Huang · 2018 [cited by applicant]
US 20080241647A1 · Fukui · 2008 [cited by examiner]
US 20120202122A1 · Han · 2012 [cited by examiner]
US 20130177822A1 · Taki · 2013 [cited by examiner]
US 20170373349A1 · Braeunling · 2017 [cited by examiner]
US 20180205114A1 · Pauric et al. · 2018 [cited by applicant]
US 20200020948A1 · Huang et al. · 2020 [cited by applicant]
US 20200020949A1 · Huang · 2020 [cited by applicant]
US 20200119339A1 · Halalay et al. · 2020 [cited by applicant]
US 20200127292A1 · Halalay et al. · 2020 [cited by applicant]
US 20200220153A1 · Xiao et al. · 2020 [cited by applicant]
CN 113054246A · 2021 [cited by examiner]
CN 114792844A · 2022 [cited by applicant]
DE 102021130249A1 · 2022 [cited by applicant]
You et al., CN 113054246 A; Espacenet machine translation, 2021 (Year: 2021). [cited by examiner]
Yang, Li et al, “Evaluation of Electrolytes for Si-Based Negative Electrodes,” ECS Meeting Abstracts (2017), MA2017-01, 254; DOI: 10.1149/MA2017-01/3/254, 2 pages. [cited by applicant]