# US 2020/0403266 A1 · Solid electrolyte, and preparation method therefor and application thereof

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- Number: US 2020/0403266 A1
- Document ID: US20200403266A1
- Status: Published application
- Kind: A1
- Application number: 16/969,159
- Filed: 2019-03-20
- Published: 2020-12-24
- Earliest claimed: 2018-02-11
- Assignees: Suzhou Institute of Nano-Tech and Nano-Bionics (Sinano) , Chinese Academy of Sciences
- Applicants: Suzhou Institute of Nano-Tech & Nano-Bionics (SINANO), Chinese Academy of Sciences
- Inventors: Chenji HU; Yanbin SHEN; Wei LU; Liwei CHEN
- Web page: https://patentgrep.com/patent/US20200403266A1

## CPC

- H01M 10/052: Li-accumulators
- H01M 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- D04H 1/728: by electro-spinning {(electro-spinning methods and apparatus D01D5/0007)}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0562: Solid materials
- H01M 10/0585: of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
- H01M 50/414: Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M 50/42: Acrylic resins
- H01M 50/426: Fluorocarbon polymers
- H01M 50/497: Ionic conductivity
- H01M 50/443: Particulate material
- 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 2300/0068: inorganic
- H01M 2300/0082: Organic polymers
- H01M 2300/0091: in the form of mixtures
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- D04H: MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL (weaving D03; knitting D04B; braiding D04C; net-making D04G; sewing D05B; tufting D05C; finishing non-woven fabrics D06); FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING {; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION}(non-woven fabrics having an intermediate or external layer of a different kind, e.g. of woven fabric, B32B)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention discloses a solid-state electrolyte and a preparation method and application thereof, the solid-state electrolyte comprises membrane material(s) and electrolyte salt(s), the organic phase of the membrane material(s) comprises a three-dimensionally interconnected interface and has a specific interfacial area greater than or equal to 1×104 cm2/cm3, and the electrolyte salt(s) is dissolved in the organic phase. The preparation method of the solid-state electrolyte comprises: spraying the polymeric material solution onto the selected receiving surface using electrostatic spinning technique to form a three-dimensional structure, and optionally, at the same time, spraying the dispersion liquid of the inorganic particles onto the selected receiving surface using electrostatic spraying technique, then treating under pressure to give the membrane material(s), and then dropwise adding or spraying the electrolyte salt(s) solution into the membrane material(s) or immersing the thin film in the electrolyte salt(s) solution. The room-temperature conductivity of the solid-state electrolyte of the present disclosure is up to over 10−3 S/cm, does not depend on the addition of special polymers or fillers, and has the advantages of simple preparation, low cost, and wide source of raw materials, etc.

## Claims

### Claim 1

A solid-state electrolyte, comprising membrane material(s) and electrolyte salt(s), wherein, the membrane material(s) comprises an organic phase formed of polymeric material(s), the organic phase comprises a three-dimensionally interconnected interface and has a specific interfacial area greater than or equal to 1×104 cm2/cm3, and the electrolyte salt(s) is dissolved in the organic phase.

### Claim 2 (depends on 1)

The solid-state electrolyte according to claim 1, wherein, the ionic conductivity of the solid-state electrolyte under room temperature is greater than or equal to 1.0×10−4 S/cm, and/or the specific interfacial area of the organic phase is 1×104 cm2/cm3 to 1×108 cm2/cm3.

### Claim 3

(canceled)

### Claim 4

(canceled)

### Claim 5 (depends on 1)

The solid-state electrolyte according to claim 1, wherein the thickness of the membrane material(s) is 5 to 90 μm.

### Claim 6

(canceled)

### Claim 7 (depends on 1)

The solid-state electrolyte according to claim 1, wherein the area specific conductance of the solid-state electrolyte at room temperature is 500 to 2500 mS·cm−2, preferably 1000 to 2500 mS·cm−2, and more preferably 2000 to 2500 mS·cm−2.

### Claim 8

(canceled)

### Claim 9

(canceled)

### Claim 10 (depends on 1)

The solid-state electrolyte according to claim 1, wherein the mass ratio of the electrolyte salt(s) to the organic phase is 1:−2 to 1:10.

### Claim 11

(canceled)

### Claim 12 (depends on 1)

The solid-state electrolyte according to claim 1, wherein the membrane material(s) is consisted of the organic phase; or the membrane material(s) further comprises inorganic particles for increasing the specific interfacial area of the organic phase.

### Claim 13 (depends on 1)

The solid-state electrolyte according to claim 1, wherein the organic phase has secondary structure(s) formed by primary structural unit(s) in an aggregated and/or superimposed manner, and the secondary structure(s) provides the three-dimensionally interconnected interface; and/or the membrane material(s) further comprises inorganic particles for increasing the specific interfacial area of the organic phase, and the inorganic particles are distributed between the primary structural unit(s).

### Claim 14

(canceled)

### Claim 15 (depends on 14)

The solid-state electrolyte according to claim 14, wherein the primary structural unit(s) is selected from the group consisting of polymeric fibers, polymeric particles, and polymeric sheets and any combination thereof, and the inorganic particles are attached to and/or embedded in the surfaces of the primary structural unit(s).

### Claim 16 (depends on 1)

The solid-state electrolyte according to claim 1, wherein the organic phase is a film formed by aggregation of polymeric fibers.

### Claim 17 (depends on 12)

The solid-state electrolyte according to claim 12, wherein the particle size of the inorganic particles is 2 nm to 10 μm, preferably 10 nm to 2 μm, further preferably 20 nm to 2 μm, more preferably 50 nm to 2 μm, most preferably 50 nm to 500 nm, and/or the inorganic particles are inorganic non-ionic conductors; or, the inorganic particles are inorganic ionic conductors; or, the inorganic particles are a combination of inorganic non-ionic conductors and inorganic ionic conductors.

### Claim 18

(canceled)

### Claim 19 (depends on 10)

The solid-state electrolyte according to claim 10, wherein the inorganic non-ionic conductors are selected from the group consisting of oxides, sulfides, nitrides, fluorides, chlorides, carbides, and combinations thereof.

### Claim 20 (depends on 12)

The solid-state electrolyte according to claim 12, wherein the content of inorganic particles in the solid-state electrolyte is less than or equal to 95 wt. %, preferably less than or equal to 80 wt. %.

### Claim 21

(canceled)

### Claim 22 (depends on 1)

The solid-state electrolyte according to claim 1, wherein, the solid-state electrolyte is prepared according to the following steps:
spraying solution(s) of the polymeric material(s) onto a selected receiving surface using electrostatic spinning technique to form primary structure(s) in the form of fibers and causing the primary structure(s) in the form of fibers to aggregate and form three-dimensional secondary structure(s), then treating the secondary structure(s) under pressure to be more dense to give the organic phase as the membrane material(s); or spraying solution(s) of the polymeric material(s) onto a selected receiving surface using electrostatic spinning technique to form primary structure(s) in the form of fibers and causing the primary structure(s) in the form of fibers to aggregate and form three-dimensional secondary structure(s), and at the time of performing electrostatic spinning, spraying dispersion liquid(s) of inorganic particles onto the selected receiving surface using electrostatic spraying technique to obtain a composite material constituted by the organic phase composed of the polymeric material(s) and the inorganic particles, then treating the composite material under pressure to be more dense to serve as the membrane material(s); and
dropwise adding or spraying solution(s) of the electrolyte salt(s) into the membrane material(s); or, immersing the membrane material(s) in the solution(s) of the electrolyte salt(s).

### Claim 23 (depends on 1)

The solid-state electrolyte according to claim 1, wherein the molecular structure of the polymeric material(s) has polar group(s) capable of complexing with metal ion(s) of the electrolyte salt(s), wherein the polymeric material(s) is polymeric material(s) having molecular structure(s) with polar group(s) selected from the group consisting of ether bonds, carbonyl, ester, amino, fluorine, amide, cyano, and combinations thereof, and/or the electrolyte salt is a lithium salt, a sodium salt, a potassium salt, a magnesium salt or an aluminum salt.

### Claim 24

(canceled)

### Claim 25 (depends on 23)

The solid-state electrolyte according to claim 23, wherein the polymeric material(s) is selected from the group consisting of polyacrylonitrile, polyvinylpyrrolidone, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene oxide, polypropylene oxide, poly(ethylene succinate), polyethylene sebacate, polyethylene glycol, polyethylene glycol diamine, and combinations thereof; and/or the electrolyte salt is selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(pentafluoroethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, and combinations thereof.

### Claim 26 (depends on 1)

The solid-state electrolyte according to claim 1, wherein the solid-state electrolyte is composed of the membrane material(s) and the electrolyte salt(s).

### Claim at position 27

-34. (canceled)

### Claim 35 (depends on 1)

A preparation method of the solid-state electrolyte according to claim 1, wherein the method comprises:
(1) obtaining the membrane material(s) by the following method a) or b):
a) spraying solution(s) of the polymeric material(s) onto a selected receiving surface using electrostatic spinning technique to cause the polymeric fibers to aggregate and form three-dimensional structure(s), and then treating the three-dimensional structure(s) under pressure to be more dense to obtain an organic phase with a three-dimensionally interconnected interface as the membrane material(s);
b) spraying solution of the polymeric material(s) onto a selected receiving surface using electrostatic spinning technique to aggregate the polymeric fibers to form three-dimensional structure(s), and at the time of performing electrostatic spinning, spraying dispersion liquid(s) of inorganic particles onto the selected receiving surface using electrostatic spraying technique to obtain a composite material constituted by the organic phase and the inorganic particles, then treating the composite material under pressure to be more dense to serve as the membrane material(s), wherein electrostatic spinning liquid outlet(s) for spraying the polymeric solution(s) and electrostatic spraying liquid outlet(s) for spraying the dispersion liquid(s) of the inorganic particles are arranged side by side in parallel, and the spraying direction of the electrostatic spinning liquid outlet(s) and the spraying direction of the electrostatic spraying liquid outlet(s) form an angle greater than or equal to 0 and less than 90°; and
(2) dropwise adding or spraying solution(s) of the electrolyte salt (s) into the membrane material(s); or, immersing the membrane material(s) in solution(s) of the electrolyte salt(s).

### Claim 36 (depends on 35)

The preparation method according to claim 35, wherein the receiving surface is a surface of a receiving device, and the receiving device is selected from the group consisting of drum receiving devices, flat receiving devices, aqueous solution receiving devices, and combinations thereof.

### Claim 37 (depends on 36)

The preparation method according to claim 36, wherein the receiving device is a drum receiving device, and the drum keeps rotating during spraying.

### Claim 38

(canceled)

### Claim 39

(canceled)

### Claim 40 (depends on 1)

An electrochemical device, comprising the solid-state electrolyte according to claim 1.