Silicon-containing electrochemical cells and methods of making the same

Patent metadata

Field	Value
Publication number	US-11626591-B2
Application number	US-202017039366-A
Country	US
Kind code	B2
Filing date	Sep 30, 2020
Priority date	Sep 30, 2020
Publication date	Apr 11, 2023
Grant date	Apr 11, 2023

Abstract

An electrochemical cell is provided herein as well as methods for preparing electrochemical cells. The electrochemical cell includes a negative electrode and a positive electrode. The negative electrode includes a prelithiated electroactive material including a lithium silicide. Lithium is present in the prelithiated electroactive material in an amount corresponding to greater than or equal to about 10% of a state of charge of the negative electrode. The electrochemical cell has a negative electrode capacity to positive electrode capacity for lithium (N/P) ratio of greater than or equal to about 1, and the electrochemical cell is capable of operating at an operating voltage of less than or equal to about 5 volts.

First claim

What is claimed is:

1. An electrochemical cell comprising:
a negative electrode comprising a first electroactive material comprising a lithium silicide, wherein lithium is present in the first electroactive material in an amount corresponding to greater than or equal to about 10% of a state of charge of the negative electrode with the amount of lithium determined by equation (i):
C pre-Li =C p ( R n/p ×E fc +X %× R n/p −1)  (i)

wherein:
C pre-Li is a capacity corresponding to the amount of lithium;
C p is the positive electrode areal capacity;
R n/p is the N/P ratio;
E fc is the first cycle capacity loss; and
X % is the state of charge of the negative electrode; and

a positive electrode comprising a second electroactive material,
wherein the electrochemical cell has a negative electrode capacity to positive electrode capacity for lithium (N/P) ratio of greater than or equal to about 1, and
wherein the electrochemical cell is capable of operating at an operating voltage of less than or equal to about 5 volts.

2. The electrochemical cell of claim 1 , 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 Fe x PO 4 , where 0<x<0.3; LiNiCoAlO 2 ; LiMPO 4 , where M is at least one of Fe, Ni, Co, and Mn; Li(Ni x Mn y Co z 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), sulfur, selenium, and a combination thereof.

3. The electrochemical cell of claim 1 , wherein the operating voltage is as low as about 2 volts, and the operating voltage is about 2 volts to about 4.5 volts.

4. The electrochemical cell of claim 1 , wherein the N/P ratio is about 1.3 to about 3.

5. The electrochemical cell of claim 1 , wherein the lithium silicide is lithium silicide particles and the lithium is present in the prelithiated electroactive material in an amount corresponding to greater than or equal to about 10% to about 70% of the state of charge of the negative electrode.

6. The electrochemical cell of claim 1 , wherein the electrochemical cell is capable of operating at the operating voltage: (i) during at least a first cycle; (ii) when discharge capacity of the electrochemical cell is less than or equal to 90%; or a combination of (i) and (ii).

7. The electrochemical cell of claim 1 , wherein the electrochemical cell is in a state prior to operation.

8. A method of preparing an electrochemical cell, the method comprising:
forming a silicon-containing negative electrode comprising:
prelithiating a silicon-containing electroactive material with an amount of lithium to form a prelithiated electroactive material comprising a lithium silicide;
wherein the amount of lithium is determined based on the following determined parameters of the electrochemical cell: (i) a positive electrode areal capacity; (ii) a negative electrode capacity to a positive electrode capacity for lithium (N/P) ratio of the electrochemical cell; (iii) a first cycle capacity loss of the electrochemical cell; and (iv) a state of charge of the silicon-containing negative electrode.

9. The method of claim 8 , wherein:
(i) the positive electrode capacity is greater than or equal to about 1 mAh/cm 2 ;
(ii) the N/P ratio is greater than or equal to about 1;
(iii) the first cycle capacity loss is greater than or equal to about 10%; and
(iv) the state of charge of silicon-containing negative is greater than or equal to 10%.

10. The method of claim 9 , wherein
(i) the positive electrode capacity is about 1 mAh/cm 2 to about 8 mAh/cm 2 ;
(ii) the N/P ratio is about 1 to 3;
(iii) the first cycle capacity loss is about 10% to about 50%; and
(iv) the state of charge of the silicon-containing negative electrode is about 10% to about 70%.

11. The method of claim 8 , wherein the amount of lithium is determined according to equation (i):
C pre-Li =C p ( R n/p ×E fc +X %× R n/p −1)  (i)

wherein:
C pre-Li is a capacity corresponding to the amount of lithium;
C p is the positive electrode areal capacity;
R n/p is the N/P ratio;
E fc is the first cycle capacity loss; and
X % is the state of charge of the silicon-containing negative electrode.

12. The method of claim 8 , further comprising admixing an electrically conductive material with the prelithiated electroactive material, wherein the electrically conductive material is selected from the group consisting of carbon black, graphene, graphene nanoplatelet, graphite, carbon nanotubes, carbon fibers, nitrogen-doped carbon, and combinations thereof.

13. The method of claim 8 , further comprising:
admixing a solvent with a polymeric binder and the prelithiated electroactive material to form a mixture, wherein the solvent is selected from the group consisting of: N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide, propylene carbonate, acetonitrile, tetrahydrofuran, and combinations thereof; and
applying the mixture to a current collector and volatilizing solvent to form the silicon-containing negative electrode.

14. The method of claim 8 , further comprising forming a positive electrode comprising a second electroactive material, 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 Fe x PO 4 , where 0<x<0.3; LiNiCoAlO 2 ; LiMPO 4 , where M is at least one of Fe, Ni, Co, and Mn; Li(Ni x Mn y Co z 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), sulfur, selenium, and a combination thereof.

15. The method of claim 8 , wherein the electrochemical cell is capable of operating at an operating voltage of about 2 volts to about 4.5 volts: (i) during at least a first cycle; (ii) when discharge capacity of the electrochemical cell is less than or equal to 90%; or a combination of (i) and (ii).

16. A method of preparing an electrochemical cell capable of operating in a designated operating voltage, the method comprising:
(a) determining an amount of lithium to prelithiate a silicon-containing electroactive material for forming a silicon-containing negative electrode and determining a negative electrode capacity to a positive electrode capacity for lithium (N/P) ratio of the electrochemical cell,
wherein determining the amount of lithium and determining the N/P ratio are based on the following parameters: (i) a determined minimum fractional lithium occupancy, (ii) a determined maximum fractional lithium occupancy, (iii) a determined first cycle efficiency of the silicon-containing negative electrode, and (iv) a determined first cycle efficiency of the positive electrode; and

(b) prelithiating the silicon-containing electroactive material with the amount of lithium determined in step (a) to form a prelithiated electroactive material comprising a lithium silicide.

17. The method of claim 16 , wherein:
the N/P ratio is determined according to equation (vii):

Assignees

• Gm Global Tech Operations Llc

Inventors

• Xiao Xingcheng
• Verbrugge Mark W
• Yang Xingyi
• Wang Lei
• K Raghunathan

Classifications

• H01M4/133

  Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• C01B33/06

  Metal silicides (alloys C22) · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/5825 Primary

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