# US 2020/0403204 A1 · Ceramic-coated separators for lithium-containing electrochemical cells and methods of making the same

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- Number: US 2020/0403204 A1
- Document ID: US20200403204A1
- Status: Published application
- Kind: A1
- Application number: 16/445,610
- Filed: 2019-06-19
- Published: 2020-12-24
- Earliest claimed: 2019-06-19
- Assignees: GM Global Technology Operations LLC
- Applicants: GM Global Technology Operations LLC
- Inventors: Xingcheng XIAO; Jiagang XU; Mei CAI
- Web page: https://patentgrep.com/patent/US20200403204A1

## CPC

- H01M 50/403: Manufacturing processes of separators, membranes or diaphragms
- B05D 1/12: Applying particulate materials (B05D1/06, B05D1/10 take precedence)
- C04B 35/50: based on rare-earth compounds {(non-oxide rare earth compounds C04B35/5156)}
- H01M 50/414: Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M 50/42: Acrylic resins
- H01M 50/434: Ceramics
- H01M 50/446: Composite material consisting of a mixture of organic and inorganic materials
- H01M 50/451: comprising layers of only organic material and layers containing inorganic material
- H01M 50/457: comprising three or more layers
- H01M 50/489: Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 2220/20: Batteries in motive systems, e.g. vehicle, ship, plane
- H01M 2300/0025: Organic electrolyte
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A ceramic-coated separator for a lithium-containing electrochemical cell and methods of preparing the ceramic-coated separator are provided. The ceramic-coated separator may be manufactured by preparing a slurry that includes one or more lithiated oxides and a binder and disposing the slurry onto one or more surfaces of a porous substrate. The slurry may be dried to from a ceramic coating on the one or more surfaces of the porous substrate so as to create the ceramic-coated separator. The ceramic coating may include one or more lithiated oxides selected from Li2SiO3, LiAlO2, Li2TiO3, LiNbO3, Li3PO4, Li2CrO4, and Li2Cr2O7.

## Claims

### Claim 1

A method of manufacturing a ceramic-coated separator for a lithium-containing electrochemical cell, the method comprising:
admixing a powder comprising one or more lithiated oxides selected from the group consisting of Li2SiO3, LiAlO2, Li2TiO3, LiNbO3, Li3PO4, Li2CrO4, Li2Cr2O7, and combinations thereof with a binder so as to form a slurry having a viscosity ranging from greater than or equal to about 300 cps to less than or equal to about 1400 cps at a temperature of about 25° C.;
disposing the slurry onto one or more surfaces of a porous substrate to form an inorganic surface layer; and
removing liquid from the inorganic surface layer by exposing the inorganic surface layer to a temperature greater than or equal to about 50° C. to less than or equal to about 100° C. for a time greater than or equal to about 6 hours to less than or equal to about 24 hours to form a ceramic coating on the one or more surfaces of the porous substrate so as to create the ceramic-coated separator.

### Claim 2 (depends on 1)

The method of claim 1, wherein the slurry is a first slurry and the method further comprises:
admixing a precursor zeolite powder with an aqueous solution comprising lithium hydroxide (LiOH) to form a second slurry; and
promoting lithium-ion exchange between the precursor zeolite powder and the lithium hydroxide (LiOH) by subjecting the second slurry to a temperature greater than or equal to about 30° C. to less than or equal to about 100° C. for a time greater than or equal to about 6 hours to less than or equal to about 24 hours.

### Claim 3 (depends on 2)

The method of claim 2, wherein the precursor zeolite powder includes one or more zeolite materials selected from the group consisting of zeolite A, zeolite X, zeolite Y, zeolite L, ZSM-5, zeolite beta, mordenite, ferrierite, and combinations thereof, and wherein the precursor zeolite powder has a cumulative total concentration of sodium and hydrogen that is less than a lithium hydroxide concentration of the aqueous solution.

### Claim 4 (depends on 2)

The method of claim 2, wherein the precursor zeolite powder further comprises greater than about 1 wt. % to less than or equal to about 20 wt. % of sodium oxide (NaO2).

### Claim 5 (depends on 2)

The method of claim 2, wherein the method further includes, prior to the admixing of the powder with the binder, calcining the powder at a temperature greater than or equal to about 200° C. to less than or equal to about 400° C. for a time greater than or equal to about 2 hours to less than or equal to about 6 hours.

### Claim 6 (depends on 1)

The method of claim 1, wherein the powder comprising one or more lithiated oxides comprises a plurality of particles and the method further includes comminuting the slurry with a grinding media so that the particles have an average diameter of less than or equal to about 1 μm.

### Claim 7 (depends on 6)

The method of claim 6, wherein the grinding media comprises one or more materials selected from the group consisting of: zirconia, alumina, stainless steel, and combinations thereof.

### Claim 8 (depends on 1)

The method of claim 1, wherein the slurry is disposed on the one or more surfaces of the porous substrate using a process selected from the group consisting of: spraying, brushing, dip coating, doctor-blade coating, spin coating, casting, printing, and combinations thereof.

### Claim 9 (depends on 1)

The method of claim 1, wherein the slurry is disposed on the one or more surfaces of the porous substrate using a doctor-blade coating method having a blade gap of less than 30 μm.

### Claim 10 (depends on 1)

The method of claim 1, wherein a weight ratio of the binder to the powder is greater than or equal to about 5% to less than or equal to about 30%, and wherein the binder is selected from the group consisting of: carboxymethyl cellulose (CMC), sodium alginate, polyacrylic acid (PAA), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVdF), and combinations thereof.

### Claim 11 (depends on 1)

The method of claim 1, wherein the ceramic coating has a thickness of less than about 10 μm.

### Claim 12 (depends on 1)

The method of claim 1, wherein the lithium-containing electrochemical cell comprising the ceramic-coated separator cycles at temperatures greater than or equal to about 50° C. and has a charge capacity loss of less than or equal to about 25% after 25 cycles of lithiation and delithiation.

### Claim 13

A method of manufacturing a ceramic-coated substrate for a lithium-containing electrochemical cell, the method comprising:
admixing a precursor zeolite powder with an aqueous solution comprising lithium hydroxide (LiOH) to form a zeolite slurry;
exposing the zeolite slurry to a temperature greater than or equal to about 50° C. to less than or equal to about 100° C. for a time greater than or equal to about 6 hours to less than or equal to about 24 hours to form a lithiated-oxide powder, wherein the lithiated-oxide powder comprises one or more lithiated oxides selected from the group consisting of Li2SiO3, LiAlO2, Li2TiO3, LiNbO3, Li3PO4, Li2CrO4, Li2Cr2O7, and combinations thereof;
admixing the lithiated-oxide powder with a binder selected from the group consisting of: carboxymethyl cellulose (CMC), sodium alginate, polyacrylic acid (PAA), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVdF), and combinations thereof to form a lithiated-oxide slurry;
disposing the lithiated-oxide slurry onto one or more surfaces of a substrate; and
exposing the lithiated-oxide slurry to a temperature greater than or equal to about 50° C. to less than or equal to about 120° C. for a time greater than or equal to about 6 hours to less than or equal to about 24 hours to form a ceramic coating on the one or more surfaces of the substrate so as to create the ceramic-coated substrate, wherein the lithium-containing electrochemical cell comprising the ceramic-coated separator cycles at temperatures greater than or equal to about 50° C. and has a charge capacity loss of less than or equal to about 25% after 25 cycles of lithiation and delithiation.

### Claim 14 (depends on 13)

The method of claim 13, wherein preparing the lithiated-oxide powder further includes contacting the lithiated-oxide powder with an aqueous liquid and calcining the lithiated-oxide powder at a temperature greater than or equal to about 50° C. to less than or equal to about 100° C. for a time greater than or equal to about 2 hours to less than or equal to about 6 hours.

### Claim 15 (depends on 13)

The method of claim 13, wherein the precursor zeolite powder includes one or more zeolite materials selected from the group consisting of zeolite A, zeolite X, zeolite Y, zeolite L, ZSM-5, zeolite beta, mordenite, ferrierite, and combinations thereof, and wherein the precursor zeolite powder has a cumulative total concentration of sodium and hydrogen that is less than a lithium hydroxide concentration of the aqueous solution.

### Claim 16 (depends on 13)

The method of claim 13, wherein the lithiated-oxide powder comprises a plurality of particles and the method further includes comminuting the slurry with a grinding media so that the particles have an average diameter of less than or equal to about 1 μm.

### Claim 17 (depends on 13)

The method of claim 13, wherein the lithiated-oxide slurry has a viscosity ranging from greater than or equal to about 300 cps to less than or equal to about 1400 cps at a temperature of about 25° C.

### Claim 18 (depends on 13)

The method of claim 13, wherein the lithiated-oxide slurry is disposed on the one or more surfaces of the porous substrate using a doctor-blade coating method having a blade gap of less than 30 μm.

### Claim 19 (depends on 13)

The method of claim 13, wherein a weight ratio of the binder to the lithiated-oxide powder is greater than or equal to about 5% to less than or equal to about 30%.

### Claim 20

A ceramic-coated separator for a lithium-containing electrochemical cell, the ceramic-coated separator comprising:
a porous substrate; and
a ceramic coating disposed on one or more surfaces of the porous substrate, wherein the ceramic coating comprises one or more lithiated oxides selected from the group consisting of Li2SiO3, LiAlO2, Li2TiO3, LiNbO3, Li3PO4, Li2CrO4, Li2Cr2O7, and combinations thereof and a thickness of greater than or equal to about 5 μm to less than about 10 μm,
wherein the lithium-containing electrochemical cell comprising the ceramic-coated separator cycles at temperatures greater than or equal to about 50° C. and has a charge capacity loss of less than or equal to about 25% after 25 cycles of lithiation and delithiation.