# US 2021/0242495 A1 · Solid electrolyte, method of preparing the same, and secondary battery including the same

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- Number: US 2021/0242495 A1
- Document ID: US20210242495A1
- Status: Published application
- Kind: A1
- Application number: 17/238,488
- Filed: 2021-04-23
- Published: 2021-08-05
- Earliest claimed: 2018-09-06
- Assignees: Samsung Electronics Co., Ltd.; Corning Incorporated
- Applicants: Samsung Electronics Co., Ltd.; Corning Incorporated
- Inventors: Jusik KIM; Sewon KIM; Hyunseok KIM; Michael Edward BADDING; Zhen SONG; Karen E. THOMAS-ALYEA; Lincoln James MIARA; Dongmin IM
- Web page: https://patentgrep.com/patent/US20210242495A1

## CPC

- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 10/0562: Solid materials
- 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 50/431: Inorganic material
- H01M 50/449: having a layered structure
- H01M 50/491: Porosity
- H01M 2300/0068: inorganic
- H01M 2300/0094: in the form of layered products, e.g. coatings
- Y02E 60/10: Energy storage using batteries
- 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

A solid electrolyte including an inorganic lithium ion conductive film and a porous layer on a surface of the inorganic lithium ion conductive film, wherein the porous layer includes a first porous layer and a second porous layer, and the second porous layer is disposed between the inorganic lithium ion conductive film and the first porous layer, and wherein the first porous layer has a size greater which is than a pore size of the second porous layer.

## Claims

### Claim 1

A solid electrolyte comprising:
an inorganic lithium ion conductive film; and
a porous layer on a surface of the inorganic lithium ion conductive film,
wherein the porous layer comprises a first porous layer and a second porous layer, and the second porous layer is disposed between the inorganic lithium ion conductive film and the first porous layer, and
wherein the first porous layer has a pore size which is greater than a pore size of the second porous layer,
wherein the first porous layer comprises a first inorganic lithium ion conductor substituted with about 2% to about 100% protons, and the second porous layer solid electrolyte comprises a second inorganic lithium ion conductor substituted with about 0.01% to about 20% protons, based on the total number of protons and lithium ions.

### Claim 2 (depends on 1)

The solid electrolyte of claim 1, wherein the porous layer has a total thickness and density to be impermeable to a liquid.

### Claim 3 (depends on 1)

The solid electrolyte of claim 1, wherein the porous layer of the solid electrolyte has a thickness of about 5% to about 95% of the total thickness of the solid electrolyte.

### Claim 4 (depends on 1)

The solid electrolyte of claim 1, wherein an average pore size of a pore in the porous layer is from about 0.1 micrometer to about 1,000 micrometers.

### Claim 5 (depends on 1)

The solid electrolyte of claim 1, wherein a pore in the first porous layer has an average pore size of about 10 micrometers to about 500 micrometers, and a pore in the second porous layer has an average pore size of about 0.1 micrometer to about 10 micrometers.

### Claim 6 (depends on 1)

The solid electrolyte of claim 1, wherein at least a portion of the solid electrolyte comprises an inorganic lithium ion conductor comprising lithium, and a portion of the lithium is substituted by a proton.

### Claim 7 (depends on 6)

The solid electrolyte of claim 6, wherein an amount of protons in the porous layer is from about 0.01 mole percent to about 50 mole percent based on a total number of protons and lithium ions in the porous layer.

### Claim 8 (depends on 1)

The solid electrolyte of claim 1, wherein the porous layer is a product obtained by:
acid-treating the inorganic lithium ion conductive film with an acid having a concentration of greater than or equal to about 0.1 molar and less than or equal to about 5 molar.

### Claim 9 (depends on 8)

The solid electrolyte of claim 8, wherein the concentration of the acid is from about 0.5 molar to about 4.5 molar.

### Claim 10 (depends on 1)

The solid electrolyte of claim 1, wherein the porous layer is a product obtained by:
forming a multilayer film comprising two or more layers on an inorganic lithium ion conductive film; and
heat-treating the multilayer film,
wherein the forming of the multilayer film comprises coating a first composition comprising a pore former on a surface of the inorganic lithium ion conductive film and coating a second composition comprising a pore former on the first composition, wherein the amount of the pore former in the first composition is different from the amount of the pore former in the second composition.

### Claim 11 (depends on 1)

The solid electrolyte of claim 1, wherein a lattice constant of the porous layer as measured by X-ray diffraction is greater than a lattice constant of the remaining area of the solid electrolyte excluding the porous layer by about 0.005 angstrom to about 0.1 angstrom, and
an average grain size of the porous layer is greater than an average grain size of the remaining area of the solid electrolyte excluding the porous layer by twice or more.

### Claim 12 (depends on 1)

The solid electrolyte of claim 1, wherein the inorganic lithium ion conductive film comprises at least one of a garnet compound, an argyrodite compound, a lithium super-ion-conductor compound, a Li nitride, a Li hydride, a perovskite, or a Li halide.

### Claim 13 (depends on 1)

The solid electrolyte of claim 1, wherein the inorganic lithium ion conductive film comprises at least one of Li3+xLa3M2O12 wherein 0≤x≤5 and M is W, Ta, Te, Nb, Zr or a combination thereof, Li3+xLa3M2O12 wherein 0≤x≤5 and M is W, Ta, Te, Nb, Zr or a combination thereof, Li1+x+yAlxTi2−xSiyP3−yO12 wherein 0<x<2 and 0≤y<3, BaTiO3, Pb(ZraTi1−a)O3 wherein 0≤a≤1, Pb1−xLaxZr1−yTiyO3 wherein 0≤x<1 and 0≤y<1, Pb(Mg1/3Nb2/3)O3—PbTiO3, Li3PO4, LixTiy(PO4)3 wherein 0<x<2 and 0<y<3, LixAlyTiz(PO4)3 wherein 0<x<2, 0<y<1, and 0<z<3, Li1+x+y(Al,Ga)x(Ti,Ge)2−xSiyP3−yO12 wherein 0≤x≤1 and 0≤y≤1, LixLayTiO3, wherein 0<x<2, and 0<y<3, LixGeyPzSw wherein 0<x<4, 0<y<1, 0<z<1, and 0<w<5, LixNy wherein 0<x<4, and 0<y<2, LixSiySz wherein 0≤x<3, 0<y<2, and 0<z<4, LixPySz wherein 0≤x<3, 0<y<3, and 0<z<7, Li3xLa2/3−xTiO3 wherein 0≤x≤⅙, Li1+yAlyTi2−y(PO4)3 wherein 0≤y≤1, Li1+zAlzGe2−z(PO4)3 wherein 0≤z≤1, Li2O, LiF, LiOH, Li2CO3, LiAlO2, a Li2O—Al2O3—SiO2—P2O5—TiO2—GeO2 ceramic, Li7La3Zr2O12, Li10GeP2S12, Li3.25Ge0.25P0.75S4, Li3PS4, Li6PS5Br, Li6PS5Cl, Li7PS5, Li6PS5I, Li1.3Al0.3Ti1.7(PO4)3, LiTi2(PO4)3, LiGe2(PO4)3, LiHf2(PO4)3, LiZr2(PO4)3, Li2NH, Li3(NH2)2I, LiBH4, LiAlH4, LiNH2, Li0.34La0.51TiO2.94, LiSr2Ti2NbO9, Li0.06 La0.66Ti0.93Al0.03O3, Li0.34Nd0.55TiO3, Li2CdCl4, Li2MgCl4, Li2ZnI4, Li2CdI4, Li4.9Ga0.5+δLa3Zr1.7W0.3O12 wherein 0≤δ<1.6, Li4.9Ga0.5+δLa3Zr1.7W0.3O12 wherein 1.7≤δ≤2.5, or Li5.39Ga0.5+δLa3Zr1.7W0.3O12 wherein 0≤δ<1.11.

### Claim 14 (depends on 1)

The solid electrolyte of claim 1, wherein the inorganic lithium ion conductive film comprises at least one of a compound of Formula 1 and a compound of Formula 1a:
Li7−xM1xLa3−aM2aZr2−bM3bO12, and Formula 1
Li7−xLa3−aM2aZr2−bM3bO12 Formula 1a
wherein,
in Formula 1, M1 comprises at least one of gallium or aluminum,
in Formulas 1 and 1a, M2 comprises at least one of calcium, strontium, cesium, or barium,
M3 comprises at least one of aluminum, tungsten, niobium, or tantalum, and
0≤x<3, 0≤a≤3, and 0≤b<2.

### Claim 15 (depends on 1)

The solid electrolyte of claim 1, wherein the inorganic lithium ion conductive film comprises at least one of Li7La3Zr2O12, Li6.4La3Zr1.7W0.3O12, Li6.5La3Zr1.5Ta0.3O12, Li7La3Zr1.7W0.3O12, Li4.9La2.5Ca0.5Zr1.7Nb0.3O12, Li4.9Ga2.1La3Zr1.7W0.3O12, Li7La3Zr1.5W0.5O12, Li7La2.75Ca0.25Zr1.75Nb0.25O12, Li7La3Zr1.5Nb0.5O12, Li7La3Zr1.5Ta0.5O12, Li6.272La3Zr1.7W0.3O12, or Li5.39Ga1.61La3Zr1.7W0.3O12.

### Claim 16 (depends on 1)

The solid electrolyte of claim 1, wherein a surface of the solid electrolyte comprises Li7−xHxLa3Zr2−yMyO12 wherein 0.1≤x≤7, 0≤y≤2, and M is at least one of W, Ta, Te, or Nb, and the interior of the solid electrolyte comprises Li7−xHxLa3Zr2−yMyO12 wherein 0≤x≤6.5, 0≤y≤2, and M is at least one of W, Ta, Te, or Nb.

### Claim 17 (depends on 1)

The solid electrolyte of claim 1, wherein the first porous layer defines a surface of the solid electrolyte and has a porosity of about 5% to about 80%, and the second porous layer has a porosity of about 1% to about 50%.

### Claim 18 (depends on 1)

The solid electrolyte of claim 1, wherein the first porous layer comprises a lithium ion conductor substituted with Li7−xHxLa3Zr2O12 wherein 0.1≤x≤7 and the second porous layer comprises Li7−xHxLa3Zr2O12 wherein 0≤x≤6.5.

### Claim 19 (depends on 1)

The solid electrolyte of claim 1, wherein the first porous layer comprises a lithium ion conductor substituted with Li6.75−xHxLa2.9Ga0.1Nb0.25Zr1.75O12 wherein 0.1≤x≤6.75, and the second porous layer comprises Li7−xHxLa3Zr2O12wherein 0≤x≤6.5.

### Claim 20 (depends on 1)

The solid electrolyte of claim 1, wherein the porous layer has a porosity of about 5% to about 60%, based on a total porosity of the porous layer.

### Claim 21 (depends on 1)

The solid electrolyte of claim 1, wherein inorganic lithium ion conductive film comprises an inorganic lithium ion conductor having a particle structure or a columnar structure.

### Claim 22 (depends on 21)

The solid electrolyte of claim 21, wherein a grain of the inorganic lithium ion conductor has a polyhedral shape.

### Claim 23 (depends on 1)

A secondary battery comprising:
a positive electrode,
a negative electrode, and
the solid electrolyte of claim 1 interposed between the positive electrode and the negative electrode.

### Claim 24 (depends on 23)

The secondary battery of claim 23, further comprising at least one of a liquid electrolyte, a polymer electrolyte, a lithium salt, an ionic liquid, or a polymer ionic liquid in the solid electrolyte.

### Claim 25 (depends on 23)

The secondary battery of claim 23, further comprising a solid sulfide electrolyte between the negative electrode and the solid electrolyte.

### Claim 26 (depends on 25)

The secondary battery of claim 25, wherein the solid sulfide electrolyte comprises Li2S—P2S5—LiX wherein X is at least one of F, Cl, Br, or I.

### Claim 27 (depends on 23)

The secondary battery of claim 23, wherein the negative electrode comprises at least one of a lithium metal or a lithium metal alloy.

### Claim 28 (depends on 23)

The secondary battery of claim 23, wherein a surface of the solid electrolyte in contact with the negative electrode has a pore size which is greater than a pore size of a surface of the solid electrolyte not in contact with the negative electrode, and the pore size of the solid electrolyte decreases in a direction extending away from the negative electrode in the solid electrolyte.

### Claim 29 (depends on 23)

The secondary battery of claim 23, wherein the secondary battery is configured to operate at greater than 1000 cycles at current density of 3 milliamperes per square centimeter.