# US 12,214,331 B2 · Processes for preparing functional particles for use in electrochemical cells and electrochemical cells including said functional particles

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- Number: US 12,214,331 B2
- Document ID: US12214331B2
- Status: Granted
- Kind: B2
- Application number: 17/390,757
- Filed: 2021-07-30
- Published: 2023-02-02
- Granted: 2025-02-04
- Earliest claimed: 2021-07-30
- Assignees: GM Global Technology Operations LLC
- Applicants: GM Global Technology Operations LLC
- Inventors: Xingcheng Xiao; Mei Cai
- Web page: https://patentgrep.com/patent/US12214331B2

## CPC

- B01J 20/3042: {Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent}
- B01J 20/186: {Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity}
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/1397: of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/364: {as mixtures}
- H01M 4/366: {as layered products}
- H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 4/621: {Binders}
- H01M 4/622: {being polymers}
- H01M 4/625: {Carbon or graphite}
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 50/403: Manufacturing processes of separators, membranes or diaphragms
- H01M 50/443: Particulate material
- H01M 50/449: having a layered structure
- H01M 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- Y02E 60/10: Energy storage using batteries
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## 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.

## Claims

### Claim 1

A method of preparing functional lithium exchanged zeolite particles for an electrochemical cell, the method comprising:
(a) combining a solution comprising (NH4)3PO4 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 Li3PO4.

### Claim 2 (depends on 1)

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 Li3PO4.

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 1)

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.

### Claim 6 (depends on 1)

The method of claim 1, wherein the concentration of each of the (NH4)3PO4 and the lithium salt is about 0.01 M to about 1 M.

### Claim 7 (depends on 1)

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.

### Claim 8

A method of preparing functional electrode particles for an electrochemical cell, the method comprising:
(a) combining a solution comprising (NH4)3PO4 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 Li3PO4.

### Claim 9 (depends on 8)

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.

### Claim 10 (depends on 8)

The method of claim 8, wherein the concentration of each of the (NH4)3PO4 and the lithium salt is about 0.01 M to about 1 M.

### Claim 11 (depends on 8)

The method of claim 8, wherein the electroactive particles comprise Li(1+x)Mn2O4, where 0.1≤x≤1; LiMn(2−x)NixO4, where 0≤x≤0.5; LiCoO2; Li(NixMnyCoz)O2, where 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1; LiNi(1−x−y)CoxMyO2, where 0<x<0.2, y<0.2, and M is Al, Mg, or Ti; LiFePO4, LiMn2−xFexPO4, where 0<x<0.3; LiNiCoAlO2; LiMPO4, where M is at least one of Fe, Ni, Co, and Mn; Li(NixMnyCozAlp)O2, where 0≤x≤1, 0≤y≤1, 0≤z≤1, 0≤P≤1, x+y+z+p=1 (NCMA); LiNiMnCoO2; Li2FexM1−xPO4, where M is Mn and/or Ni, 0≤x≤1; LiMn2O4; LiFeSiO4; LiNi0.6Mn0.2Co0.2O2 (NMC622), LiMnO2 (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.

### Claim 12 (depends on 8)

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.

### Claim 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 Li3PO4, 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 Li3PO4; and
optionally, functional electrode particles comprising: (a) Li3PO4 and the first electroactive material; and/or (b) Li3PO4 and the second electroactive material.

### Claim 14 (depends on 13)

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.

### Claim 15 (depends on 13)

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.

### Claim 16 (depends on 13)

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.

### Claim 17 (depends on 13)

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.

### Claim 18 (depends on 13)

The electrochemical cell of claim 13, wherein the first electroactive material is selected from the group consisting of Li(1+x)Mn2O4, where 0.1≤x≤1; LiMn(2−x)NixO4, where 0≤x≤0.5; LiCoO2; Li(NixMnyCoz)O2, where 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1; LiNi(1−x−y)CoxMyO2, where 0<x<0.2, y<0.2, and M is Al, Mg, or Ti; LiFePO4, LiMn2−xFexPO4, where 0<x<0.3; LiNiCoAlO2; LiMPO4, where M is at least one of Fe, Ni, Co, and Mn; Li(NixMnyCozAlp)O2, where 0≤x≤1, 0≤y≤1, 0≤z≤1, 0≤P<1, x+y+z+p=1 (NCMA); LiNiMnCoO2; Li2FexM1−xPO4, where M is Mn and/or Ni, 0≤x≤1; LiMn2O4; LiFeSiO4; LiNi0.6Mn0.2Co0.2O2 (NMC622), LiMnO2 (LMO), activated carbon, sulfur, and a combination thereof.

### Claim 19 (depends on 13)

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 combination thereof.