CN109599593B - Method for preparing solid-state battery with multilayer composite electrolyte - Google Patents
Method for preparing solid-state battery with multilayer composite electrolyte Download PDFInfo
- Publication number
- CN109599593B CN109599593B CN201811387353.6A CN201811387353A CN109599593B CN 109599593 B CN109599593 B CN 109599593B CN 201811387353 A CN201811387353 A CN 201811387353A CN 109599593 B CN109599593 B CN 109599593B
- Authority
- CN
- China
- Prior art keywords
- solid
- organic
- electrolyte
- lithium
- state battery
- 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.)
- Active
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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a preparation method of a solid-state battery with multilayer composite electrolyte. The method comprises the following specific steps: a. coating an organic-inorganic composite conductive material prepolymer A on the surface of an electrode and curing; b. continuously coating an organic electrolyte layer B with a lithium stabilizing effect on the surface of the electrolyte layer of the electrode obtained in the step a and solidifying; c. and c, assembling the lithium metal or the material containing the lithium metal as a negative electrode and the electrode obtained in the step b into a solid-state battery. Due to multi-component compounding, the crystallinity of the electrolyte is reduced, and the room-temperature conductivity of the electrolyte is improved; the anode and the cathode respectively consist of high-voltage resistant/lithium-pair stable components, so that the electrochemical window of the electrolyte is expanded; the addition of inorganic matter improves the mechanical strength of the electrolyte. Therefore, the room temperature solid lithium ion battery using the solid electrolyte has better cycle stability and safety, and has wide application prospect in the fields of portable electronic devices, power energy storage and the like.
Description
Technical Field
The invention relates to a preparation method of a solid-state battery with multilayer composite electrolyte.
Background
Compared with the traditional lithium ion battery, the solid-state lithium ion battery has higher energy density, longer cycle life and better safety. However, the existing solid electrolyte has low ionic conductivity and high interface resistance, which is a bottleneck restricting the development of solid batteries. The contact between the anode material and the electrolyte can be improved through in-situ polymerization on the surface of the anode material, so that the interface impedance is reduced; the ion conduction of the solid electrolyte can be effectively improved by compounding the organic-inorganic solid electrolyte. The in-situ preparation method of the multilayer electrolyte can obviously improve the circulation capacity of the solid-state battery and reduce the internal resistance, thereby improving the comprehensive performance of the solid-state battery.
Disclosure of Invention
The invention relates to a preparation method of a solid-state battery with multilayer composite electrolyte.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a solid-state battery with multilayer composite electrolyte is characterized by comprising the following specific steps:
a. coating an organic-inorganic composite conductive material prepolymer A on the surface of an electrode and curing;
b. continuously coating an organic electrolyte layer B with a lithium stabilizing effect on the surface of the electrolyte layer of the electrode obtained in the step a and solidifying;
c. And c, assembling the lithium metal or the material containing the lithium metal as a negative electrode and the electrode obtained in the step b into a solid-state battery.
The organic part of the organic-inorganic composite conductive material prepolymer consists of an organic in-situ polymerization prepolymer and a polymer, wherein the organic in-situ polymerization prepolymer is a monomer containing one or more of ester or alkenyl functional groups and an oligomer formed by the monomer, and the polymer is one or more of polyethylene, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethacrylate and a polymer modification product.
The in-situ polymerized monomers mentioned above can be described as
Wherein R1, R2 and R3 are respectively and independently straight-chain or branched-chain alkyl of C1-C30.
The inorganic part in the organic-inorganic composite conductive material prepolymer is as follows: li7La3Zr2O12、LiTi2(PO4)3、Li1.5Al0.5Ge1.5(PO4)3、Li1.3Al0.3Ti1.7(PO4)3、Li3ClO、LiPON、Li0.29S0.28O0.35N0.09、Li2S-GeS2、Li2S-P2S5、Li2S-B2S3、Li2S-SiS2And one or more of the modified products of the inorganic solid conductive material, and in addition, the inorganic component of the mixture also comprises lithium salt, and the content of the lithium salt is 1-50 wt% of the organic-inorganic composite conductive material mixture.
The organic electrolyte layer with the stabilizing effect on lithium has a C-O-C and/or C-F structure in a molecule, and the coating mixture contains 10-50 wt% of lithium salt.
The lithium salt is LiPF6、LiBF4、LiCF3SO3、LiODFB、LiN(SO2CF3)2One or a combination of several of them.
The coating mixture is one or a combination of a plurality of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyperfluoroethylene, polymethacrylate and other polymers containing C-O-C and/or C-F structures.
The solvent used in the above coating is a solvent containing a nitrile or carbonate compound.
The solvent is as follows: dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, acetonitrile, acetone, dimethyl formamide, ethylene glycol dimethyl ether and one or more of other compounds with carbon content less than 10 and boiling point lower than 160 ℃.
The curing process is carried out under the conditions of ultraviolet irradiation and/or heating to polymerize into a film, wherein the wavelength range of ultraviolet light is 200-400nm, and the initiator corresponding to the in-situ polymerization prepolymer is used.
Due to multi-component compounding, the crystallinity of the electrolyte is reduced, and the room-temperature conductivity of the electrolyte is improved; the anode and the cathode respectively consist of high-voltage resistant/lithium-pair stable components, so that the electrochemical window of the electrolyte is expanded; the addition of inorganic matter improves the mechanical strength of the electrolyte. Therefore, the room temperature solid lithium ion battery using the solid electrolyte has better cycle stability and safety, and has wide application prospect in the fields of portable electronic devices, power energy storage and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Wherein Arm2 is
MMA is methyl methacrylate and LLZO is Li7La3Zr2O12The LATP is Li1.3Al0.3Ti1.7(PO4)3LTP is LiTi2(PO4)3LLZTO is Li6.75La3Zr1.75Ta0.25O12,
2-hydroxy-2-methyl-1-phenyl-1-acetone is adopted as an initiator, lithium cobaltate is adopted as an anode active material, a lithium sheet is adopted as a cathode, acetonitrile is adopted as a solvent,
the first embodiment is as follows: coating the mixture A1 on the surface of a pole piece, carrying out ultraviolet irradiation at 70 ℃ for 45min, then coating the mixture B1 on the surface of the electrolyte layer, heating at 70 ℃ for 3h, and finally superposing metal lithium to prepare the solid-state battery.
Example two: coating the mixture A2 on the surface of a pole piece, carrying out ultraviolet irradiation at 70 ℃ for 45min, then coating the mixture B2 on the surface of the electrolyte layer, heating at 70 ℃ for 3h, and finally superposing metallic lithium to prepare the solid-state battery.
Example three: and coating the mixture A3 on the surface of a pole piece, heating at 85 ℃ for 3h, coating the mixture B1 on the surface of the electrolyte layer, heating at 70 ℃ for 3h, and finally superposing metallic lithium to prepare the solid-state battery.
Example four: coating the mixture A1 on the surface of a pole piece, carrying out ultraviolet irradiation at 70 ℃ for 45min, then coating the mixture B1 on the surface of the electrolyte layer, heating at 70 ℃ for 3h, and finally superposing metallic lithium to prepare the solid-state battery.
Li at room temperature and 2.5-4.25V vs+0.1C cycle test in the Li range, the results are as follows (mAh/g):
Claims (5)
1. a preparation method of a solid-state battery with multilayer composite electrolyte is characterized by comprising the following specific steps:
a. coating an organic-inorganic composite conductive material prepolymer A on the surface of an electrode and curing;
b. continuously coating an organic electrolyte layer B with a lithium stabilizing effect on the surface of the electrolyte layer of the electrode obtained in the step a and solidifying;
c. b, assembling the lithium metal or the material containing the lithium metal as a negative electrode and the electrode obtained in the step b into a solid battery;
the organic part of the organic-inorganic composite conductive material prepolymer A consists of an organic in-situ polymerization prepolymer and a polymer, wherein the polymer is one or a mixture of polyethylene, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethacrylate and a modified product of the polymer;
The organic in-situ polymerization prepolymer has the chemical formula:
wherein R is1,R2,R3Each independently is C1~C30Linear or branched alkyl.
2. The method for producing a solid-state battery comprising a multilayer composite electrolyte according to claim 1, wherein the organic-inorganic composite electrolyte is used as a conductive materialThe inorganic portion of the electrical material prepolymer a is: li7La3Zr2O12、LiTi2(PO4)3、Li1.5Al0.5Ge1.5(PO4)3、Li1.3Al0.3Ti1.7(PO4)3、Li3ClO、LiPON、Li0.29S0.28O0.35N0.09、Li2S-GeS2、Li2S-P2S5、Li2S-B2S3、Li2S-SiS2And one or more of the modified products of the inorganic solid conductive material, wherein the inorganic component also comprises lithium salt, and the content of the lithium salt is 1-50 wt% of the organic-inorganic composite conductive material prepolymer A;
the organic electrolyte layer B with the stabilizing effect on lithium contains 10-50 wt% of lithium salt;
the organic electrolyte layer B also contains one or a combination of more of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyperfluoroethylene, polymethacrylate and other polymers containing C-O-C and/or C-F structures;
and the curing process is carried out under the conditions of ultraviolet irradiation and/or heating to polymerize into a film, wherein the wavelength range of ultraviolet light is 200-400nm, and an initiator corresponding to the in-situ polymerization prepolymer is used.
3. The method for producing a solid-state battery comprising a multilayer composite electrolyte according to claim 2, wherein the lithium salt is LiPF 6、LiBF4、LiCF3SO3、LiODFB、LiN(SO2CF3)2One or a combination of several of them.
4. The method for producing a solid-state battery with a multilayer composite electrolyte according to claim 2, characterized in that the solvent used in the coating is a solvent containing a nitrile or carbonate compound.
5. The method for producing a solid-state battery with a multilayer composite electrolyte according to claim 4, wherein the solvent is: one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and acetonitrile.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811387353.6A CN109599593B (en) | 2018-11-21 | 2018-11-21 | Method for preparing solid-state battery with multilayer composite electrolyte |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811387353.6A CN109599593B (en) | 2018-11-21 | 2018-11-21 | Method for preparing solid-state battery with multilayer composite electrolyte |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109599593A CN109599593A (en) | 2019-04-09 |
CN109599593B true CN109599593B (en) | 2022-06-10 |
Family
ID=65958772
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811387353.6A Active CN109599593B (en) | 2018-11-21 | 2018-11-21 | Method for preparing solid-state battery with multilayer composite electrolyte |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109599593B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021003712A1 (en) * | 2019-07-10 | 2021-01-14 | 瑞声声学科技(深圳)有限公司 | Preparation method for solid-state battery, and solid-state battery |
CN110828890B (en) * | 2019-09-26 | 2022-12-27 | 湖南工业大学 | Preparation method of polymer-based solid electrolyte with high room-temperature ionic conductivity |
CN112635815A (en) * | 2019-10-09 | 2021-04-09 | 中国科学院宁波材料技术与工程研究所 | Composite electrolyte material with electrochemical buffer layer, preparation method thereof and lithium metal battery |
CN111129602A (en) * | 2019-12-20 | 2020-05-08 | 中国电子科技集团公司第十八研究所 | Preparation method of integrally-formed solid-state battery |
CN111313089B (en) * | 2020-01-03 | 2021-11-30 | 武汉理工大学 | Preparation method of ion conductor/polyethylene oxide composite solid electrolyte based on ultraviolet crosslinking |
CN111463478B (en) * | 2020-03-31 | 2021-08-17 | 珠海冠宇电池股份有限公司 | Solid-state battery comprising interface buffer layer and preparation method thereof |
CN112366292A (en) * | 2020-11-10 | 2021-02-12 | 广东天劲新能源科技股份有限公司 | All-solid-state lithium battery and preparation method thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105098233A (en) * | 2014-05-22 | 2015-11-25 | 上海交通大学 | Preparation method of semi-interpenetrating network polymer gel electrolyte membrane |
CN106159312A (en) * | 2015-05-15 | 2016-11-23 | 精工爱普生株式会社 | Solid electrolyte battery and manufacture method, electrode complex, composite solid electrolyte |
CN106537679A (en) * | 2014-07-31 | 2017-03-22 | 富士胶片株式会社 | All-solid secondary battery, and method for manufacturing inorganic solid electrolyte particles, solid electrolyte composition, electrode sheet for batteries, and all-solid secondary battery |
CN107039680A (en) * | 2016-02-03 | 2017-08-11 | 三星电子株式会社 | Solid electrolyte and the lithium battery for including the solid electrolyte |
CN107394261A (en) * | 2017-07-03 | 2017-11-24 | 清华大学深圳研究生院 | Lithium metal battery inorganic/organic hybrid films solid electrolyte and preparation method thereof |
CN107591554A (en) * | 2017-09-15 | 2018-01-16 | 中国科学院化学研究所 | A kind of preparation method of three-dimensional collector solid state battery |
CN108365258A (en) * | 2018-01-19 | 2018-08-03 | 上海大学 | The solid electrolyte of polymer substrate and preparation method thereof with room-temperature conductivity |
CN108598560A (en) * | 2018-02-27 | 2018-09-28 | 北京匠芯电池科技有限公司 | Composite solid electrolyte and its preparation method and application |
CN108695547A (en) * | 2018-04-28 | 2018-10-23 | 浙江锋锂新能源科技有限公司 | A kind of Organic-inorganic composite dielectric film and the battery with the dielectric film |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10079404B1 (en) * | 2017-03-03 | 2018-09-18 | Blue Current, Inc. | Polymerized in-situ hybrid solid ion-conductive compositions |
-
2018
- 2018-11-21 CN CN201811387353.6A patent/CN109599593B/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105098233A (en) * | 2014-05-22 | 2015-11-25 | 上海交通大学 | Preparation method of semi-interpenetrating network polymer gel electrolyte membrane |
CN105098233B (en) * | 2014-05-22 | 2017-10-24 | 上海交通大学 | The preparation method of semi-interpenetrating network polymer gel electrolyte membrane |
CN106537679A (en) * | 2014-07-31 | 2017-03-22 | 富士胶片株式会社 | All-solid secondary battery, and method for manufacturing inorganic solid electrolyte particles, solid electrolyte composition, electrode sheet for batteries, and all-solid secondary battery |
CN106159312A (en) * | 2015-05-15 | 2016-11-23 | 精工爱普生株式会社 | Solid electrolyte battery and manufacture method, electrode complex, composite solid electrolyte |
CN107039680A (en) * | 2016-02-03 | 2017-08-11 | 三星电子株式会社 | Solid electrolyte and the lithium battery for including the solid electrolyte |
CN107394261A (en) * | 2017-07-03 | 2017-11-24 | 清华大学深圳研究生院 | Lithium metal battery inorganic/organic hybrid films solid electrolyte and preparation method thereof |
CN107591554A (en) * | 2017-09-15 | 2018-01-16 | 中国科学院化学研究所 | A kind of preparation method of three-dimensional collector solid state battery |
CN108365258A (en) * | 2018-01-19 | 2018-08-03 | 上海大学 | The solid electrolyte of polymer substrate and preparation method thereof with room-temperature conductivity |
CN108598560A (en) * | 2018-02-27 | 2018-09-28 | 北京匠芯电池科技有限公司 | Composite solid electrolyte and its preparation method and application |
CN108695547A (en) * | 2018-04-28 | 2018-10-23 | 浙江锋锂新能源科技有限公司 | A kind of Organic-inorganic composite dielectric film and the battery with the dielectric film |
Also Published As
Publication number | Publication date |
---|---|
CN109599593A (en) | 2019-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109599593B (en) | Method for preparing solid-state battery with multilayer composite electrolyte | |
CA2717503C (en) | Method for preparing an electrochemical cell having a gel electrolyte | |
EP3261164B1 (en) | Gel polymer electrolyte, method for preparing same, and electrochemical device comprising same | |
KR101322694B1 (en) | Electrolyte for electrochemical device, the preparation method thereof and electrochemical device comprising the same | |
CN1324728C (en) | Lithium secondary cell of electrolyte decomposition being inhibited and preparing process thereof | |
JP4370079B2 (en) | Lithium polymer battery | |
US7135254B2 (en) | Multi-layered, UV-cured polymer electrolyte and lithium secondary battery comprising the same | |
Qin et al. | A single-ion gel polymer electrolyte system for improving cycle performance of LiMn2O4 battery at elevated temperatures | |
US8216723B2 (en) | Polymer electrolyte and electrochemical device | |
CN110808409A (en) | Polymer lithium secondary battery and in-situ preparation method thereof | |
EP2184799A1 (en) | Polymer electrolyte, lithium battery comprising the polymer electrolyte, method of preparing the polymer electrolyte, and method of preparing the lithium battery | |
CN111786018B (en) | High-voltage polymer electrolyte, high-voltage polymer lithium metal battery and preparation method of battery | |
CN111934020B (en) | High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof | |
CN114292484A (en) | Interpenetrating network structure layer, in-situ preparation method and application thereof | |
KR101807693B1 (en) | Gel polymer electrolyte and Lithium battery comprising gel polymer electrolyte and method for preparing gel polymer electrolyte | |
KR20100052407A (en) | Gel polymer electrolyte, lithium battery comprising gel polymer electrolyte, method for preparing gel polymer electrolyte, and method for preparing lithium battery | |
JP2022536290A (en) | In-situ polymerized polymer electrolyte for lithium-ion batteries | |
JP6116029B2 (en) | Gel electrolyte and polymer secondary battery using the same | |
CN113161608A (en) | Polymer solid electrolyte with excellent performance at room temperature and application thereof in lithium ion battery | |
CN110970654A (en) | Composite gel polymer electrolyte for lithium ion battery and preparation and application thereof | |
CN109599590B (en) | Preparation method of non-woven fabric-based composite solid electrolyte battery | |
KR100533647B1 (en) | A uv-cured multi-component polymer blend electrolyte, lithium secondary battery and their fabrication method | |
Shao | Highly electrochemical stable quaternary solid polymer electrolyte for all-solid-state lithium metal batteries | |
CN117673457A (en) | Solid-state battery and secondary polymerization preparation method thereof | |
CN113851702A (en) | All-solid-state electrolyte battery 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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |