Processes for preparing functional particles for use in electrochemical cells and electrochemical cells including said functional particles

Patent metadata

Field	Value
Publication number	US-12214331-B2
Application number	US-202117390757-A
Country	US
Kind code	B2
Filing date	Jul 30, 2021
Priority date	Jul 30, 2021
Publication date	Feb 4, 2025
Grant date	Feb 4, 2025

Abstract

Methods of making functional particles, such as functional lithium ion-exchanged zeolite particles and functional electrode particles for electrochemical cells are provided as well as electrochemical cells including such particles. A method includes combining a solution including (NH4)3PO4 with lithium ion-exchanged zeolite particles to form a first mixture. The method further includes adding a polymeric binder and a lithium salt to the first mixture to form a first slurry including the functional lithium ion-exchanged zeolite particles comprising Li3PO4.

First claim

What is claimed is:

1. A method of preparing functional lithium exchanged zeolite particles for an electrochemical cell, the method comprising:
(a) combining a solution comprising (NH 4 ) 3 PO 4 with lithium ion-exchanged zeolite particles to form a first mixture; and
(b) adding a polymeric binder and a lithium salt to the first mixture to form a first slurry comprising the functional lithium ion-exchanged zeolite particles comprising Li 3 PO 4 .

2. The method of claim 1 , wherein the functional lithium ion-exchanged zeolite particles comprise cages defined by 8-membered rings, 9-membered rings, 10-membered rings, 12-membered rings or a combination thereof and wherein the cages contain the Li 3 PO 4 .

3. The method of claim 1 , wherein the functional lithium ion-exchanged zeolite particles comprise a zeolite material having a framework type selected from the group consisting of NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA, and a combination thereof.

4. The method of claim 1 , wherein the functional lithium ion-exchanged zeolite particles comprise a zeolite material selected from the group consisting of zeolite A, zeolite Y, zeolite L, ZSM-5, and a combination thereof.

5. The method of claim 1 , wherein the lithium salt is selected from the group consisting of lithium hydroxide, lithium carbonate, lithium chloride, lithium nitrate, lithium sulfate, and a combination thereof.

6. The method of claim 1 , wherein the concentration of each of the (NH 4 ) 3 PO 4 and the lithium salt is about 0.01 M to about 1 M.

7. The method of claim 1 , further comprising one or more of:
(c1) applying the first slurry onto a first side of a porous separator, a second side of the porous separator, or both the first and second sides of the porous separator and solidifying the first slurry to form a coating layer comprising the functional lithium ion-exchanged zeolite particles, wherein the coating layer is present on the first side of the porous separator, the second side of the porous separator, or both the first and second sides of the porous separator; and
(c2) incorporating the first slurry with the porous separator and solidifying the first slurry to form a filler comprising the functional lithium ion-exchanged zeolite particles within the porous separator.

8. A method of preparing functional electrode particles for an electrochemical cell, the method comprising:
(a) combining a solution comprising (NH 4 ) 3 PO 4 with a polymeric binder to form a second mixture;
(b) adding electroactive particles to the second mixture; and
(c) adding a lithium salt to the second mixture to form a second slurry comprising functional electrode particles, wherein the functional electrode particles comprise the electroactive particles and Li 3 PO 4 .

9. The method of claim 8 , wherein the lithium salt is selected from the group consisting of lithium hydroxide, lithium carbonate, lithium chloride, lithium nitrate, lithium sulfate, and a combination thereof.

10. The method of claim 8 , wherein the concentration of each of the (NH 4 ) 3 PO 4 and the lithium salt is about 0.01 M to about 1 M.

11. The method of claim 8 , wherein the electroactive particles comprise 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 Fe x M 1−x PO 4 , where M is Mn and/or Ni, 0≤x≤1; LiMn 2 O 4 ; LiFeSiO 4 ; LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), LiMnO 2 (LMO) activated carbon, sulfur, lithium, a lithium silicon alloy, a lithium aluminum alloy, a lithium indium alloy, a lithium tin alloy, graphite, activated carbon, carbon black, hard carbon, soft carbon, graphene, silicon, tin oxide, aluminum, indium, zinc, germanium, silicon oxide, titanium oxide, lithium titanate, or a combination thereof.

12. The method of claim 8 , further comprising:
(d) applying the second slurry onto a third surface of a current collector; and
(e) solidifying the second slurry to form an electrode layer comprising the functional electrode particles.

13. An electrochemical cell comprising:
a positive electrode layer comprising a first electroactive material;
a negative electrode layer spaced apart from the positive electrode layer, wherein the negative electrode layer comprises a second electroactive material;
a porous separator disposed between confronting surfaces of the negative electrode layer and the positive electrode layer;
a liquid electrolyte infiltrating one or more of the negative electrode layer, the positive electrode layer, and the porous separator layer;
functional lithium ion-exchanged zeolite particles comprising Li 3 PO 4 , wherein the functional lithium ion-exchanged zeolite particles comprise cages defined by 8-membered rings, 9-membered rings, 10-membered rings, 12-membered rings or a combination thereof and wherein the cages contain the Li 3 PO 4 ; and
optionally, functional electrode particles comprising: (a) Li 3 PO 4 and the first electroactive material; and/or (b) Li 3 PO 4 and the second electroactive material.

14. The electrochemical cell of claim 13 , wherein the functional lithium ion-exchanged zeolite particles are present as one or more of the following:
(i) a coating layer present on a first side, a second side or both the first and second sides of the porous separator; and
(ii) a filler in the porous separator.

15. The electrochemical cell of claim 13 , wherein the functional lithium ion-exchanged zeolite particles comprise a zeolite material having a framework type selected from the group consisting of NAT, EDI, THO, ANA, YUG, GOO, MON, HEU, STI, BRE, FAU, MFI, LTL, LTA, and a combination thereof.

16. The electrochemical cell of claim 13 , wherein the functional lithium ion-exchanged zeolite particles comprise a zeolite material selected from the group consisting of zeolite A, zeolite Y, zeolite L, ZSM-5, and a combination thereof.

17. The electrochemical cell of claim 13 , wherein, when present the functional electrode particles are present in one or more of the following:
(i) the positive electrode layer; and
(ii) the negative electrode layer.

18. The electrochemical cell of claim 13 , wherein the first 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 Fe x M 1−x PO 4 , where M is Mn and/or Ni, 0≤x≤1; 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.

19. The electrochemical cell of claim 13 , wherein the second electroactive material comprises lithium, a lithium silicon alloy, a lithium aluminum alloy, a lithium indium alloy, a lithium tin alloy, graphite, activated carbon, carbon black, hard carbon, soft carbon, graphene, silicon, tin oxide, aluminum, indium, zinc, germanium, silicon oxide, titanium oxide, lithium titanate, or a combinati

Assignees

• Gm Global Tech Operations Llc

Inventors

• Xiao Xingcheng
• Cai Mei

Classifications

• H01M50/449

  having a layered structure · CPC title

• H01M50/443

  Particulate material · CPC title

• H01M50/403

  Manufacturing processes of separators, membranes or diaphragms · CPC title

• H01M10/056

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title

• H01M10/0525

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