Lithium ion-exchanged zeolite particles including lithium phosphate within cage, electrochemical cell, and method of making the same

Patent metadata

Field	Value
Publication number	US-11936066-B2
Application number	US-202117375414-A
Country	US
Kind code	B2
Filing date	Jul 14, 2021
Priority date	Jul 14, 2021
Publication date	Mar 19, 2024
Grant date	Mar 19, 2024

Abstract

Lithium ion-exchanged zeolite particles and methods of making such lithium ion-exchanged zeolite particles are provided herein. The method includes combining precursor zeolite particles with (NH 4 ) 3 PO 4 to form a first mixture including intermediate zeolite particles including NH 4 + cations. The method further includes adding a lithium salt to the first mixture to form the lithium ion-exchanged zeolite particles, or separating the intermediate zeolite particle from the first mixture and combining the intermediate zeolite particles with the lithium salt to form the lithium ion-exchanged zeolite particles.

First claim

What is claimed is:

1. A lithium ion-exchanged zeolite particle comprising:
cages defined by 8-membered rings, 9-membered rings, 10-membered rings, 12-membered rings or a combination thereof, wherein Li 3 PO 4 is present within the cages; and
Li + and NH 4 + cations; and
wherein the lithium ion-exchanged zeolite particle comprises (i) less than or equal to about 0.1 at % of one or more of Na + , K + , Mg 2 + , or Ca + ; and (ii) NH 4 + in an amount greater than an amount of the one or more of Na + , K + , Mg 2 + , or Ca + .

2. The lithium ion-exchanged zeolite particle of claim 1 , wherein the lithium ion-exchanged zeolite particle comprises 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.

3. The lithium ion-exchanged zeolite particle of claim 1 , wherein the 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.

4. An electrochemical cell comprising:
a positive electrode comprising a first electroactive material;
a negative electrode spaced apart from the positive electrode, wherein the negative electrode comprises a second electroactive material;
a porous separator disposed between confronting surfaces of the negative electrode and the positive electrode;
a liquid electrolyte infiltrating one or more of the negative electrode, the positive electrode, and the porous separator; and
lithium ion-exchanged zeolite particles comprising:
cages defined by 8-membered rings, 9-membered rings, 10-membered rings, 12-membered rings or a combination thereof, wherein Li 3 PO 4 is present within the cages; and
Li + and NH 4 + cations; and
wherein the lithium ion-exchanged zeolite particles comprise (i) less than or equal to about 0.1 at % of one or more of Na + , K + , Mg 2 + , or Ca + ; and (ii) NH 4 + in an amount greater than an amount of the one or more of Na + , K + , Mg 2 + , or Ca + .

5. The electrochemical cell of claim 4 , wherein the lithium ion-exchanged zeolite particles are present as one or more of the following:
(i) a first coating layer present on a first side, a second side or both the first and second sides of the porous separator;
(ii) a filler in the porous separator;
(iii) an additive in the positive electrode, the negative electrode, or both; and
(iv) a second coating layer present on a third side of the negative electrode, on a fourth side of the positive electrode or both the third side of the negative electrode and the fourth side of the positive electrode.

6. The electrochemical cell of claim 1 , wherein the 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.

7. The electrochemical cell of claim 4 , wherein the 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.

8. The electrochemical cell of claim 4 , 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.

9. The electrochemical cell of claim 4 , 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 combination thereof.

10. The electrochemical cell of claim 4 , wherein the porous separator comprises a composite material, a polymeric material, a nonwoven material, or a combination thereof.

11. A method of preparing lithium ion-exchanged zeolite particles, the method comprising:
(a) combining precursor zeolite particles with (NH 4 ) 3 PO 4 to form a first mixture comprising intermediate zeolite particles, wherein the precursor zeolite particles comprise a cation selected from the group consisting of H + , NH 4 + , Na + , K + , Mg 2 + , Ca + , and a combination thereof; and
(b) performing one of the following:
(i) adding a lithium salt to the first mixture to form the lithium ion-exchanged zeolite particles, or
(ii) separating the intermediate zeolite particle from the first mixture and combining the intermediate zeolite particles with the lithium salt to form the lithium ion-exchanged zeolite particles; and

wherein the 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, wherein Li 3 PO 4 is present within the cages; and Li + and NH 4 + cations; and wherein the lithium ion-exchanged zeolite particle comprises (i) less than or equal to about 0.1 at % of one or more of Na + , K + , Mg 4 + , or Ca + ; and (ii) NH 4 + in an amount greater than an amount of the one or more of Na + , K + , Mg 4 + , or Ca + .

12. The method of claim 11 ,
wherein the lithium ion-exchanged zeolite particles further comprise Li 3 PO 4 present on an exterior surface of the lithium ion-exchanged zeolite particles.

13. The method of claim 11 , wherein the 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.

14. The method of claim 11 , wherein the 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.

15. The method of claim 11 , wherein the precursor zeolite particles comprise Na + , H + , and/or K + cations and/or the intermediate zeolite particle comprise NH 4 + cations.

16. The method of claim 11 , 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.

17. The method of claim 11 ,
wherein the combining the precursor zeolite particles with (NH 4 ) 3 PO 4 , the adding the lithium salt to the first mixture to form the lithium ion-exchanged zeolite particles, and the combining the intermediate zeolite particles with the lithium salt to form the lithium ion-exchanged zeolite particles are each performed at a temperature of about 18° C. to about 120° C.

18. The method of claim 11 , further comprising performing one or more:
(c) separating the lithium ion-exchanged zeolite particles; and
(d) heating the lithium ion-exchanged zeolite particles.

19. The method of claim 18 , wherein the heating is perform

Assignees

• Gm Global Tech Operations Llc

Inventors

• Xiao Xingcheng
• Cai Mei

Classifications

• H01M50/431 Primary

  Inorganic material · CPC title

• C01B39/14

  Type A · CPC title

• C01B39/24

  Type Y {(C01B39/205 takes precedence)} · CPC title

• C01B39/32 Primary

  Type L · CPC title

• C01B39/38

  Type ZSM-5 · CPC title