CN112531203A - Solid electrolyte with high ionic conductivity and preparation method thereof - Google Patents

Solid electrolyte with high ionic conductivity and preparation method thereof Download PDF

Info

Publication number
CN112531203A
CN112531203A CN202011435129.7A CN202011435129A CN112531203A CN 112531203 A CN112531203 A CN 112531203A CN 202011435129 A CN202011435129 A CN 202011435129A CN 112531203 A CN112531203 A CN 112531203A
Authority
CN
China
Prior art keywords
solid electrolyte
equal
ionic conductivity
high ionic
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011435129.7A
Other languages
Chinese (zh)
Inventor
胡少强
贾明
潘振炎
张茂贵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Aihua Group Co Ltd
Original Assignee
Hunan Aihua Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Aihua Group Co Ltd filed Critical Hunan Aihua Group Co Ltd
Priority to CN202011435129.7A priority Critical patent/CN112531203A/en
Publication of CN112531203A publication Critical patent/CN112531203A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A solid electrolyte with high ionic conductivity comprises a cross-linking agent, an ionic conductor and a positive electrode active material; the cross-linking agent comprises a high-molecular polymer formed by cross-linking polyvinylidene fluoride and polyethylene oxide; the ion conductor comprises Li1.4Al0.4Ti1.6(PO4)3(ii) a The anode active material is LiFePO4Or LicNiaCobMn1‑a‑bO2Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, and c is more than or equal to 0.4 and less than or equal to 1.5. In the invention, the polyvinylidene fluoride and the polyethylene oxide form a cross-linked structure, which is beneficial to enhancing the mechanical property of the solid electrolyte. Meanwhile, polyvinylidene fluoride and polyethylene oxide have high dielectric constants, the former has good electrochemical stability, and the ether oxygen group in the latter can be coordinated with lithium ions to produce ethylene oxide lithium; this allows more lithium ions to be accommodated in the organic polymer.

Description

Solid electrolyte with high ionic conductivity and preparation method thereof
Technical Field
The invention relates to a solid electrolyte, in particular to a solid electrolyte with high ionic conductivity and a preparation method thereof.
Background
Lithium ion batteries have high energy density, long cycle life, no memory effect and excellent environmental friendliness, and thus, lithium ion batteries are ubiquitous energy sources in many fields. While lithium ion batteries have met with great success in portable devices, conventional liquid lithium ion batteries have problems of volatility, easy decomposition, leakage, and flammability, which have limited the development of liquid lithium ion batteries.
In order to overcome the defects of the liquid lithium ion battery, the all-solid lithium ion battery utilizes the solid electrolyte with better safety to overcome the defects of the liquid lithium ion battery. Solid electrolytes are generally classified into three categories: inorganic solid electrolytes, organic polymer solid electrolytes, and organic-inorganic composite solid electrolytes; inorganic solid electrolytes are generally classified into oxides and sulfides.
In contrast, the organic-inorganic composite solid electrolyte can maintain excellent ionic conductivity at room temperature due to mechanical stability of inorganic materials and interfacial compatibility between organic polymers and electrodes; however, in the organic-inorganic composite solid electrolyte, more lithium ions cannot be accommodated in the organic material, and the mechanical properties of the solid electrolyte cannot be satisfied by a single organic material in lithium ion batteries with higher and higher requirements.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a solid electrolyte with high ionic conductivity and good cycle performance and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a solid electrolyte with high ionic conductivity comprises a cross-linking agent, an ionic conductor and a positive electrode active material; the cross-linking agent comprises a high-molecular polymer formed by cross-linking polyvinylidene fluoride and polyethylene oxide; the ion conductor comprises Li1.4Al0.4Ti1.6(PO4)3(ii) a The positive active material is LiPF6Or LicNiaCobMn1-a-bO2Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, and c is more than or equal to 0.4 and less than or equal to 1.5.
In the solid electrolyte having high ionic conductivity, the weight ratio of the polyvinylidene fluoride to the polyethylene oxide is preferably 20:1 to 5: 1.
In the above solid electrolyte having high ionic conductivity, preferably, the Li1.4Al0.4Ti1.6(PO4)3The weight ratio of the poly (vinylidene fluoride) to the poly (vinylidene fluoride) is 1:100-1: 20.
In the solid electrolyte with high ionic conductivity, the weight ratio of the positive electrode active material to the polyvinylidene fluoride is preferably 1:100 to 1: 10.
A method for preparing a solid electrolyte with high ionic conductivity comprises the following steps,
1) adding polyvinylidene fluoride and polyethylene oxide powder into a solvent, and uniformly dispersing; the solvent is NMP;
2) adding an ion conductor and a positive electrode active material into the solution obtained in the step 1), and stirring at the temperature of between room temperature and 50 ℃ for more than 10 hours to form slurry;
3) drying the slurry obtained in the step 2) at the temperature of 40-80 ℃ for 1-3 hours under the protection of vacuum or inert gas to form the solid electrolyte with high ionic conductivity.
In the above method for producing a solid electrolyte having high ionic conductivity, the method for producing an ionic conductor preferably comprises the steps of:
1) dissolving 28 parts by weight of lithium nitrate and 39 parts by weight of aluminum nitrate in 32 parts by weight of absolute ethanol, respectively;
2) dropwise adding the lithium nitrate solution obtained in the step 1) into an aluminum nitrate solution to form a mixed solution;
3) dissolving 123.5 parts by weight of titanium isopropoxide and 100 parts by weight of phosphoric acid in 24 parts by weight of absolute ethanol, respectively;
4) adding the mixed solution in the step 2) into the titanium isopropoxide solution in the step 3) under stirring, and then adding the phosphoric acid solution in the step 3); forming a transparent mixed solution;
5) putting the mixed solution in the step 4) in a water bath at 60-80 ℃ to form gel, and generating light yellow gel at 80 ℃;
6) grinding the gel in the step 5) and calcining the gel for more than 5 hours at the temperature of 400-600 ℃, wherein the heating rate is 1 ℃ per minute during calcining;
7) after natural cooling, grinding the powder again, and calcining for more than 5 hours at the temperature of 850 ℃ to form an ion conductor; the heating rate during calcination is 1 degree centigrade/min.
Compared with the prior art, the invention has the advantages that: in the invention, the polyvinylidene fluoride and the polyethylene oxide form a cross-linked structure, which is beneficial to enhancing the mechanical property of the solid electrolyte. Meanwhile, polyvinylidene fluoride and polyethylene oxide have high dielectric constants, the former has good electrochemical stability, and the ether oxygen group in the latter can be coordinated with lithium ions to produce ethylene oxide lithium; this allows more lithium ions to be accommodated in the organic polymer.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Example 1
A solid electrolyte with high ionic conductivity comprises a cross-linking agent, an ionic conductor and a positive electrode active material; the cross-linking agent comprises a high-molecular polymer formed by cross-linking polyvinylidene fluoride (PVDF) and polyethylene oxide (PEO); the ion conductor comprises Li1.4Al0.4Ti1.6(PO4)3(LATP); the positive active material is LiPF6。
In this example, the weight ratio of polyvinylidene fluoride to polyethylene oxide is 20:1 to 5: 1. Li1.4Al0.4Ti1.6(PO4)3The weight ratio of the poly (vinylidene fluoride) to the poly (vinylidene fluoride) is 1:100-1: 20. The weight ratio of the positive electrode active material to the polyvinylidene fluoride is 1:100-1: 10.
In this embodiment, polyvinylidene fluoride and polyethylene oxide form a crosslinked structure useful for enhancing solid state electrolysisMechanical properties of the material. Meanwhile, polyvinylidene fluoride and polyethylene oxide have high dielectric constants, the former has good electrochemical stability, and the ether oxygen group in the latter can be coordinated with lithium ions to produce ethylene oxide lithium; this allows more lithium ions to be accommodated in the organic polymer. In this example, LATP is highly inert to water and oxygen and has a high ionic conductivity up to 10 at room temperature-3S/cm. LATP can supplement the low ionic conductivity defect in polyvinylidene fluoride and polyethylene oxide crosslinked organic polymers in this example.
In this example, submicron ion conductor LATP particles and LiPF were added to a polyvinylidene fluoride and polyethylene oxide crosslinked polymer solution6And is uniformly dispersed to improve mechanical and electrochemical properties of the solid electrolyte (SSE).
In this example, a large number of hydroxyl groups are present in the PEO molecule, and the PVDF molecule has a backbone and sufficient fluoride so that the fluoride forms a large number of hydrogen bonds with hydrogen atoms on the PEO, and under the action of the large number of hydrogen bonds, the PVDF and the PEO can be constructed to form a 3D dual matrix cross-linked structure, while the PEO with a low crystallinity can enhance the mechanical properties of the solid electrolyte in the cross-linked structure and form an amorphous region, which is beneficial to the transport of lithium ions, thereby improving the ionic conductivity.
The composite polymer of this example allows the creation of a composite interface between the LATP particles and the organic matrix, further altering the environment of the organic molecule. Li+Readily migrating to the amorphous regions of the composite electrolyte. When the submicron ionic conductor LATP is uniformly dispersed in the PVDF @ PEO polymer matrix, the crystallinity is further reduced, and the submicron ionic conductor LATP is helpful for Li in the composite electrolyte+Conductivity and electrochemical properties. Finally, added LiPF6A composite electrolyte having more free lithium ions is provided.
The ionic conductivity of the solid electrolyte in the embodiment can reach 5.3 × 10-4S/cm, and the capacity retention rate is 92.3% after the solid electrolyte is cycled for 1000 times under the condition of the current density of 0.1C.
The embodiment also provides a preparation method of the solid electrolyte with high ionic conductivity, which comprises the following steps,
1) adding polyvinylidene fluoride and polyethylene oxide powder into a solvent, and uniformly dispersing; the solvent is NMP;
2) adding an ion conductor and a positive electrode active material into the solution obtained in the step 1), and stirring at the temperature of between room temperature and 50 ℃ for more than 10 hours to form slurry;
3) drying the slurry obtained in the step 2) at the temperature of 40-80 ℃ for 1-3 hours under the protection of vacuum or inert gas to form the solid electrolyte with high ionic conductivity. When the solid lithium ion battery is prepared, the slurry obtained in the step 2) is coated on a positive current collector (aluminum foil), and then the positive current collector is dried and cut under the condition of the step 3) to obtain a positive plate.
In this embodiment, the method for preparing the ion conductor includes the following steps:
1) dissolving 28 parts by weight of lithium nitrate and 39 parts by weight of aluminum nitrate in 32 parts by weight of absolute ethanol, respectively;
2) dropwise adding the lithium nitrate solution obtained in the step 1) into an aluminum nitrate solution to form a mixed solution;
3) dissolving 123.5 parts by weight of titanium isopropoxide and 100 parts by weight of phosphoric acid in 24 parts by weight of absolute ethanol, respectively;
4) adding the mixed solution in the step 2) into the titanium isopropoxide solution in the step 3) under stirring, and then adding the phosphoric acid solution in the step 3); forming a transparent mixed solution;
5) putting the mixed solution in the step 4) in a water bath at 60-80 ℃ to form gel, and generating light yellow gel at 80 ℃;
6) grinding the gel in the step 5) and calcining the gel for more than 5 hours at the temperature of 400-600 ℃, wherein the heating rate is 1 ℃ per minute during calcining;
7) after natural cooling, grinding the powder again, and calcining for more than 5 hours at the temperature of 850 ℃ to form an ion conductor; the heating rate during calcination is 1 degree centigrade/min.
In this embodiment, lithium ions are assembledIn the case of a battery, the negative current collector can be aluminum foil, and the negative material can be 80% of LiFePO4After 10% of conductive carbon black and 10% of PVDF are dissolved in NMP solvent, fully and uniformly stirring to form negative electrode slurry, wherein the weight percentages are above. And after coating the negative electrode slurry on a negative electrode current collector, drying at the temperature of 110 ℃ for 12 hours under the protection of vacuum or inert gas, slicing, then winding the positive plates together into a battery cell, and assembling into the solid-state lithium ion battery.

Claims (6)

1. A solid electrolyte having high ionic conductivity, characterized in that: comprises a cross-linking agent, an ion conductor and a positive active material; the cross-linking agent comprises a high-molecular polymer formed by cross-linking polyvinylidene fluoride and polyethylene oxide; the ion conductor comprises Li1.4Al0.4Ti1.6(PO4)3(ii) a The positive active material is LiPF6Or LicNiaCobMn1-a-bO2Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, and c is more than or equal to 0.4 and less than or equal to 1.5.
2. The solid electrolyte of high ionic conductivity according to claim 1, wherein: the weight ratio of the polyvinylidene fluoride to the polyethylene oxide is 20:1-5: 1.
3. The solid electrolyte of high ionic conductivity according to claim 1, wherein: the Li1.4Al0.4Ti1.6(PO4)3The weight ratio of the poly (vinylidene fluoride) to the poly (vinylidene fluoride) is 1:100-1: 20.
4. The solid electrolyte of high ionic conductivity according to claim 1, wherein: the weight ratio of the positive electrode active material to the polyvinylidene fluoride is 1:100-1: 10.
5. The method for producing a solid electrolyte having high ionic conductivity according to any one of claims 1 to 4, wherein: comprises the following steps of (a) carrying out,
1) adding polyvinylidene fluoride and polyethylene oxide powder into a solvent, and uniformly dispersing; the solvent is NMP;
2) adding an ion conductor and a positive electrode active material into the solution obtained in the step 1), and stirring at the temperature of between room temperature and 50 ℃ for more than 10 hours to form slurry;
3) drying the slurry obtained in the step 2) at the temperature of 40-80 ℃ for 1-3 hours under the protection of vacuum or inert gas to form the solid electrolyte with high ionic conductivity.
6. The method for producing a solid electrolyte having high ionic conductivity according to claim 5, wherein: the preparation method of the ion conductor comprises the following steps:
1) dissolving 28 parts by weight of lithium nitrate and 39 parts by weight of aluminum nitrate in 32 parts by weight of absolute ethanol, respectively;
2) dropwise adding the lithium nitrate solution obtained in the step 1) into an aluminum nitrate solution to form a mixed solution;
3) dissolving 123.5 parts by weight of titanium isopropoxide and 100 parts by weight of phosphoric acid in 24 parts by weight of absolute ethanol, respectively;
4) adding the mixed solution in the step 2) into the titanium isopropoxide solution in the step 3) under stirring, and then adding the phosphoric acid solution in the step 3); forming a transparent mixed solution;
5) putting the mixed solution in the step 4) in a water bath at 60-80 ℃ to form gel, and generating light yellow gel at 80 ℃;
6) grinding the gel in the step 5) and calcining the gel for more than 5 hours at the temperature of 400-600 ℃, wherein the heating rate is 1 ℃ per minute during calcining;
7) after natural cooling, grinding the powder again, and calcining for more than 5 hours at the temperature of 850 ℃ to form an ion conductor; the heating rate during calcination is 1 degree centigrade/min.
CN202011435129.7A 2020-12-10 2020-12-10 Solid electrolyte with high ionic conductivity and preparation method thereof Pending CN112531203A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011435129.7A CN112531203A (en) 2020-12-10 2020-12-10 Solid electrolyte with high ionic conductivity and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011435129.7A CN112531203A (en) 2020-12-10 2020-12-10 Solid electrolyte with high ionic conductivity and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112531203A true CN112531203A (en) 2021-03-19

Family

ID=74998944

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011435129.7A Pending CN112531203A (en) 2020-12-10 2020-12-10 Solid electrolyte with high ionic conductivity and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112531203A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113793936A (en) * 2021-08-24 2021-12-14 广州市乐基智能科技有限公司 Composite binder for solid lithium battery and preparation method and application thereof
CN114628775A (en) * 2021-07-08 2022-06-14 万向一二三股份公司 LATP composite positive plate with low interface internal resistance, preparation method and all-solid-state lithium ion battery

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100092870A1 (en) * 2008-09-12 2010-04-15 Enerize Corporation Solid polymer electrolyte for solar cells and lithium batteries
CN107834104A (en) * 2017-12-12 2018-03-23 清陶（昆山）能源发展有限公司 A kind of composite solid electrolyte and preparation method thereof and the application in solid lithium battery
CN108039463A (en) * 2017-11-27 2018-05-15 北京化工大学 A kind of solid state battery of the preparation and application of solid electrolyte/electrode composite material material
CN108539260A (en) * 2018-04-13 2018-09-14 中国航发北京航空材料研究院 With multiple Li+Compound organic solid electrolyte of conduction path and preparation method thereof
CN109742442A (en) * 2018-12-24 2019-05-10 北京化工大学 The secondary cell of the preparation and application of the Garnet-type solid electrolyte solid electrolyte
CN109968622A (en) * 2019-03-25 2019-07-05 成都新柯力化工科技有限公司 A kind of method that clean type Screw Extrusion prepares lithium battery polymer dielectric film
US20190393543A1 (en) * 2018-06-21 2019-12-26 Nanotek Instruments, Inc. Lithium metal secondary battery featuring an anode-protecting layer
CN111584929A (en) * 2020-04-29 2020-08-25 中国科学院福建物质结构研究所 Solid electrolyte, preparation method and lithium battery
CN111799503A (en) * 2020-07-21 2020-10-20 哈尔滨工业大学 NASICON type electrolyte-based composite solid electrolyte film and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100092870A1 (en) * 2008-09-12 2010-04-15 Enerize Corporation Solid polymer electrolyte for solar cells and lithium batteries
CN108039463A (en) * 2017-11-27 2018-05-15 北京化工大学 A kind of solid state battery of the preparation and application of solid electrolyte/electrode composite material material
CN107834104A (en) * 2017-12-12 2018-03-23 清陶（昆山）能源发展有限公司 A kind of composite solid electrolyte and preparation method thereof and the application in solid lithium battery
CN108539260A (en) * 2018-04-13 2018-09-14 中国航发北京航空材料研究院 With multiple Li+Compound organic solid electrolyte of conduction path and preparation method thereof
US20190393543A1 (en) * 2018-06-21 2019-12-26 Nanotek Instruments, Inc. Lithium metal secondary battery featuring an anode-protecting layer
CN109742442A (en) * 2018-12-24 2019-05-10 北京化工大学 The secondary cell of the preparation and application of the Garnet-type solid electrolyte solid electrolyte
CN109968622A (en) * 2019-03-25 2019-07-05 成都新柯力化工科技有限公司 A kind of method that clean type Screw Extrusion prepares lithium battery polymer dielectric film
CN111584929A (en) * 2020-04-29 2020-08-25 中国科学院福建物质结构研究所 Solid electrolyte, preparation method and lithium battery
CN111799503A (en) * 2020-07-21 2020-10-20 哈尔滨工业大学 NASICON type electrolyte-based composite solid electrolyte film and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHUHONG YI ET AL.: "《Fast ion conductor modified double-polymer (PVDF and PEO) matrix electrolyte for solid lithium-ion batteries》", 《SOLID STATE IONICS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114628775A (en) * 2021-07-08 2022-06-14 万向一二三股份公司 LATP composite positive plate with low interface internal resistance, preparation method and all-solid-state lithium ion battery
CN113793936A (en) * 2021-08-24 2021-12-14 广州市乐基智能科技有限公司 Composite binder for solid lithium battery and preparation method and application thereof
CN113793936B (en) * 2021-08-24 2023-04-11 广州市乐基智能科技有限公司 Composite binder for solid lithium battery and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN111244537A (en) Composite solid electrolyte, solid battery and preparation method thereof
KR101954601B1 (en) Organic-inorganic composite solid electrolyte, lithium secondary cell comprising the same, and manufacturing method for the lithium secondary cell
CN108417777A (en) A kind of porous triple anode composite piece and preparation method thereof and its application
CN111934020B (en) High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof
CN107994257A (en) A kind of high-performance solid electrolyte and preparation method thereof
CN108428935A (en) A kind of solid electrolyte membrane preparation method and lithium battery
CN112531203A (en) Solid electrolyte with high ionic conductivity and preparation method thereof
CN110911741B (en) Carbon oxide sphere doped solid polymer electrolyte membrane and preparation method and application thereof
EP3316380B1 (en) Battery cell in which gelation electrolyte solution component is included in pore of separator configuring electrode assembly
KR20170050278A (en) Polymer Electrolyte comprising Lithium Nitrate and All-Solid-State Battery comprising The Same
EP4312297A1 (en) Solid-state electrolyte (sse) with sandwich structure and preparation method and use thereof, and solid-state lithium ion battery
CN115832412A (en) Composite solid electrolyte and preparation method and application thereof
CN111799508B (en) All-solid-state polymer electrolyte diaphragm, preparation method and all-solid-state lithium ion battery
CN115149206A (en) Fluorine modified quasi-solid mixed matrix lithium battery diaphragm and lithium battery preparation method
CN111040061B (en) Solid sodium ion electrolyte, preparation method thereof and all-solid-state sodium battery
CN115188945A (en) Coated positive electrode material and preparation method and application thereof
CN114864916A (en) Niobium pentoxide coated graphite composite negative electrode material and preparation method thereof
CN114566702A (en) Sandwich integrated all-solid-state polymer electrolyte membrane, and preparation method and application thereof
CN111969246A (en) Preparation method and application of nano bacterial cellulose/polyoxyethylene composite solid electrolyte
CN111293297A (en) Carbon-coated MoSe2Black phosphorus composite material and preparation method thereof
CN114927645B (en) Preparation method of positive electrode of lithium-sulfur battery
CN113793936B (en) Composite binder for solid lithium battery and preparation method and application thereof
CN113964378B (en) Composite solid electrolyte and manufacturing method thereof
CN116130882A (en) Sodium battery diaphragm and sodium battery
CN117832604A (en) Solid polymer electrolyte membrane and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20210319

RJ01 Rejection of invention patent application after publication