CN113540697B - Composite diaphragm and preparation method thereof - Google Patents
Composite diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN113540697B CN113540697B CN202110721031.6A CN202110721031A CN113540697B CN 113540697 B CN113540697 B CN 113540697B CN 202110721031 A CN202110721031 A CN 202110721031A CN 113540697 B CN113540697 B CN 113540697B
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- composite
- monomer
- lithium
- diaphragm
- 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
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a composite diaphragm and a preparation method thereof, wherein the composite diaphragm comprises a base membrane, and the surface of the base membrane is coated with a LICION type composite solid electrolyte coating; the LISICON type composite solid electrolyte coating contains a LISICON type composite solid electrolyte, and the electrolyte is obtained by in-situ polymerization of a hydrophobic monomer and an ionic conductor monomer on the surface of the LISICON type solid electrolyte. On one hand, the organic polymer polymerized by the hydrophobic monomer can better improve the wettability between the diaphragm and the electrolyte; on the other hand, the ion conductor polymer polymerized by the ion conductor monomer can construct an ion transmission passage between non-compact LISICON type solid electrolyte particles, so that the ion transmission rate is improved; in addition, the LISICON type solid electrolyte belongs to an inorganic material, has high thermal stability, can stabilize a low-melting-point basement membrane at high temperature, and reduces the thermal shrinkage and the short circuit risk of the cell at high temperature.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite diaphragm and a preparation method thereof.
Background
Because of the advantages of high power density, low self-discharge rate, no memory effect, stable discharge voltage and the like, the lithium battery becomes the main choice of the power battery. The diaphragm is a key component of the lithium ion battery, and plays an important role in blocking the electronic conductance of the positive electrode and the negative electrode and allowing electrolyte ions to freely pass through in the battery.
The safety problem of the power battery is very complicated, the diaphragm plays a vital role in the safety of the battery, and in the using process, the lithium dendrite pierces the diaphragm or the internal temperature of the battery core rises to cause the internal short circuit of the diaphragm, so that the anode and the cathode are in direct contact, a large amount of heat is emitted in a short time, and finally the thermal runaway of the battery is caused.
At present, the inorganic ceramic electrolyte with high thermal stability and high ionic conductivity is taken as a coating layer to become a hot point of research, and the diaphragm taking the inorganic ceramic solid electrolyte as the coating layer has the advantages of good liquid absorption, high temperature resistance, high ionic conductivity, lithium dendrite inhibition and the like, and can be used in liquid, semi-solid, quasi-solid and all-solid lithium batteries and metal lithium batteries. However, in the preparation process of the inorganic solid electrolyte coating diaphragm, the coating layer is very easy to absorb water, so that the moisture of the diaphragm is increased, and the diaphragm needs to be baked for a long time in the subsequent use process, so that the production efficiency is reduced.
Disclosure of Invention
The invention aims to provide a composite diaphragm and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a composite separator comprising a base film, the surface of which is coated with a LISICON-type composite solid electrolyte coating; the LISICON-type composite solid electrolyte coating comprises a LISICON-type composite solid electrolyte, and the LISICON-type composite solid electrolyte is prepared by in-situ polymerization of a LISICON-type solid electrolyte, a hydrophobic monomer and an ionic conductor monomer. Further, the base film is made of polyethylene or polypropylene; the thickness of the LISICON type composite solid electrolyte coating is 0.2-20 mu m.
As a preferred technical scheme, the LISICON-type composite solid electrolyte is prepared by the following steps:
s1, dissolving a hydrophobic monomer and an ionic conductor monomer in a solvent to obtain a reaction solution; more preferably, the hydrophobic monomer is at least one of methyl methacrylate, vinyl trimethylsilane, alkyl silane coupling agent, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, 2, 2, 2-trifluoroethyl methacrylate, dodecafluoro heptyl acrylate, tridecafluorooctyl methacrylate and tridecafluorooctyl acrylate; the ion conductor monomer is at least one of lithium acrylate, lithium methacrylate, lithium maleate, (methyl vinyl ether copolymerized maleic acid) lithium and lithium fumarate; the mass ratio of the hydrophobic monomer to the ionic conductor monomer is 0.01-1; the solvent is at least one of deionized water, DMF, DMSO, N-methyl pyrrolidone, methanol, ethanol, toluene or tetrahydrofuran.
S2, adding the LICION type solid electrolyte into the reaction liquid in S1, and adding an initiator to perform in-situ polymerization reaction; further, the mass ratio of the total mass of the hydrophobic monomer and the ionic conductor monomer to the mass of the LISICON type solid electrolyte is 0.001-0.02.
And S3, carrying out suction filtration, washing and vacuum drying on a product obtained by the in-situ polymerization reaction to finally obtain the LISICON type solid electrolyte, namely the LISICON type composite solid electrolyte, which is coated by the hydrophobic polymer and the ionic conductor polymer.
As a preferred technical solution, the LISICON-type solid electrolyte has a particle size distribution of: d 50 Greater than or equal to 200 nm, dispersion
(ii) a The chemical formula of the LISICON type solid electrolyte is Li 1+x M x N 2-x (PO 4 ) 3 (ii) a Wherein: x is more than or equal to 0 and less than or equal to 0.5; m is selected from one of Al, Y, Ga, Cr and Fe; n is one selected from Ti, Ge, Ta, Zr, Sn and V.
The invention also provides a preparation method of the composite diaphragm, which comprises the following steps:
uniformly mixing a binder, a stabilizer, an organic solvent and a LICION type composite solid electrolyte to obtain a stable suspension; and coating the suspension on the surface of the base film, and drying to remove the organic solvent to obtain the composite diaphragm. Further, the binder is polyvinylidene fluoride; the stabilizer is at least one of carboxymethyl cellulose, sodium alginate, sodium polyacrylate and polyamide; the organic solvent is at least one of N-methyl pyrrolidone, acetonitrile and tetrahydrofuran.
The invention has the beneficial effects that:
the performance of the base membrane is improved by coating the LISICON type composite solid electrolyte coating on the surface of the base membrane, wherein the LISICON type composite solid electrolyte coating contains the LISICON type composite solid electrolyte, and the LISICON type composite solid electrolyte is obtained by in-situ polymerization of a hydrophobic monomer and an ionic conductor monomer on the surface of the LISICON type solid electrolyte. On one hand, the organic polymer polymerized by the hydrophobic monomer can better improve the wettability between the diaphragm and the electrolyte; on the other hand, the ion conductor polymer polymerized by the ion conductor monomer can construct an ion transmission passage between non-compact LISICON type solid electrolyte particles, so that the ion transmission rate is improved; in addition, the LISICON type solid electrolyte belongs to an inorganic material, has high thermal stability, can stabilize a low-melting-point basement membrane at high temperature, and reduces the thermal shrinkage and the short circuit risk of the cell at high temperature.
The composite diaphragm provided by the invention has the advantages of good hydrophobicity, high ionic conductivity, good electrolyte wettability and low thermal shrinkage rate. The battery pack is applied to the production of lithium ion batteries, the baking cost of the diaphragm can be saved, the charge-discharge rate performance of the battery cell is ensured, and the short circuit risk of the battery cell caused by the contraction of the diaphragm is reduced.
Drawings
FIG. 1 shows Li complexed in example 1 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Solid electrolyte sheet contact angle test pictures;
FIG. 2 shows Li in comparative example 1 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Contact angle test pictures of solid electrolyte sheets.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the composite diaphragm specifically comprises the following steps:
(1) hexafluorobutyl acrylate: lithium acrylate = 1: 1 (the amount ratio of the substances) is placed in toluene/methanol to be stirred and dissolved, and D is added 50 Li of =500 nm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Powder (Li) 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Mass of powder: total mass of hexafluorobutyl acrylate and lithium methacrylate = 99: 1) stirring for 1h, adding an Azobisisobutyronitrile (AIBN) initiator, carrying out in-situ polymerization reaction under the condition of 70 ℃ water bath, after 3h, finishing the reaction, carrying out suction filtration on a product, washing with absolute ethyl alcohol, and drying in vacuum at 120 ℃ for 12 h. Finally obtaining the composite Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Solid electrolyte and its tablets were subjected to contact angle test (against water). The specific data are shown in Table 1.
(2) Taking the above-mentioned compound Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Solid electrolyte, polyvinylidene fluoride (PVDF), polyamide and N-methylpyrrolidone (NMP), wherein the mass ratio of the PVDF to the NMP is 9: 0.5: 0.5: and 25, dispersing the four materials by using a planetary ball mill for 3 hours to obtain stable slurry.
(3) And (3) coating the stable slurry on a polyethylene base film through a micro concave roller, wherein the coating thickness is 3 micrometers, and drying at 80 ℃ to obtain the composite diaphragm.
The obtained composite diaphragm is subjected to moisture content test and thermal shrinkage rate of 1h at 130 ℃. The specific data are shown in Table 2.
Example 2
The preparation method of the composite diaphragm specifically comprises the following steps:
(1) vinyl trimethylsilane: lithium methacrylate = 1: 1 (the amount ratio of the substances) is put into methanol to be stirred and dissolved, and D is added 50 Li of =500 nm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Powder (Li) 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Powder mass: total mass of vinyltrimethylsilane and lithium methacrylate = 99: 1) stirring for 1h, adding Azobisisobutyronitrile (AIBN), carrying out in-situ polymerization reaction in a water bath at 70 ℃, finishing the reaction after 3h, carrying out suction filtration on a product, washing with absolute ethyl alcohol, and drying in vacuum at 120 ℃ for 12 h. Finally, composite Li is obtained 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Solid electrolyte and its tablets were subjected to contact angle test (against water). The specific data are shown in Table 1.
(2) Taking the above-mentioned compound Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Solid electrolyte, polyvinylidene fluoride (PVDF), sodium alginate and N-methylpyrrolidone (NMP), wherein the mass ratio of the PVDF to the solid electrolyte is 9: 0.5: 0.5: and 25, dispersing the four materials by using a planetary ball mill for 3 hours to obtain stable slurry.
(3) And (3) coating the stable slurry on a polyethylene base film through a micro-concave roller, wherein the coating thickness is 3 microns, and drying at 80 ℃ to obtain the composite diaphragm.
The obtained composite diaphragm is subjected to moisture content test and thermal shrinkage rate of 1h at 130 ℃. The specific data are shown in Table 2.
Example 3
The preparation method of the composite diaphragm specifically comprises the following steps:
(1) mixing methyl methacrylate: lithium methacrylate = 3: 2 (mass ratio) is placed in methanol to be stirred and dissolved, and D is added 50 Li of =500 nm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Powder (Li) 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Mass of powder: total mass of methyl methacrylate and lithium maleate = 98: 2) stirring for 1h, adding Azobisisobutyronitrile (AIBN), carrying out in-situ polymerization reaction under the condition of 70 ℃ water bath, finishing reaction for 3h, carrying out suction filtration on a product, washing with absolute ethyl alcohol, and drying in vacuum at 120 ℃ for 12 h. Finally obtaining the composite Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Solid electrolyte and tabletting thereofThe contact angle test (for water) was performed. The specific data are shown in Table 1.
(2) Taking the above-mentioned compound Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Solid electrolyte, polyvinylidene fluoride (PVDF), sodium alginate and N-methylpyrrolidone (NMP), wherein the mass ratio of the PVDF to the solid electrolyte is 9: 0.5: 0.5: and 25, dispersing the mixture for 3 hours by using a planetary ball mill to obtain stable slurry.
(3) And (3) coating the stable slurry on a polyethylene diaphragm through a micro concave roller, wherein the coating thickness is 2 microns, and drying at 80 ℃ to obtain the composite diaphragm.
The obtained composite diaphragm is subjected to moisture content test and thermal shrinkage rate of 1h at 130 ℃. The specific data are shown in Table 2.
Comparative example 1
Selection of D not to be complexed 50 Li of =500 nm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Powders, likewise tableted, were tested for contact angle (to water). The specific data are shown in Table 1.
Comparative example 2
A polyethylene-based diaphragm is selected, and the specific material structure is polypropylene-polyethylene-polypropylene. The test of moisture content and the test of heat shrinkage at 130 ℃ for 1 hour were also carried out, and the results are shown in Table 2.
The method for testing the water content refers to the method for determining the water content in chemical products GB/T6283 and 2008, namely the Karl Fischer method (general method).
The results of testing the products prepared in the above examples and comparative examples are shown in tables 1 and 2 below:
TABLE 1 contact Angle (to Water) test results in examples and comparative examples
TABLE 2 moisture and Heat shrinkage test results in examples and comparative examples
From table 1, it can be seen that the LISICON-type solid electrolyte treated by the hydrophobic monomer has good hydrophobic property, the diaphragm coated by the LISICON-type solid electrolyte can effectively resist moisture in the air, and meanwhile, the organic component can improve the wettability of the organic electrolyte. As can be seen from table 2, the moisture content of the composite separator is lower than that of a common separator, which is beneficial to reducing the baking cost of the separator and the battery cell; and the thermal shrinkage rate is obviously reduced, and the safety risk of the battery cell caused by the shrinkage of the diaphragm can be reduced.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A composite separator comprising a base film, characterized in that: the surface of the base film is coated with a composite solid electrolyte coating; the composite solid electrolyte coating comprises a composite solid electrolyte, and the composite solid electrolyte is prepared from a solid electrolyte, a hydrophobic monomer and an ionic conductor monomer through in-situ polymerization;
the composite solid electrolyte is prepared by the following steps:
s1, dissolving a hydrophobic monomer and an ionic conductor monomer in a solvent to obtain a reaction solution;
s2, adding the solid electrolyte into the reaction liquid in the S1, and carrying out in-situ polymerization reaction after adding the initiator;
s3, carrying out suction filtration, washing and vacuum drying on a product obtained by the in-situ polymerization reaction to finally obtain a solid electrolyte, namely a composite solid electrolyte, coated by the hydrophobic polymer and the ionic conductor polymer;
the hydrophobic monomer is at least one of methyl methacrylate, vinyl trimethylsilane, alkyl silane coupling agent, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, 2, 2, 2-trifluoroethyl methacrylate, dodecafluoro heptyl acrylate, tridecafluorooctyl methacrylate and tridecafluorooctyl acrylate; the ion conductor monomer is at least one of lithium acrylate, lithium methacrylate, lithium maleate, (methyl vinyl ether copolymerized maleic acid) lithium and lithium fumarate;
the chemical formula of the solid electrolyte is Li 1+x M x N 2-x (PO 4 ) 3 (ii) a Wherein: x is more than or equal to 0 and less than or equal to 0.5; m is selected from one of Al, Y, Ga, Cr and Fe; n is selected from one of Ti, Ge, Ta, Zr, Sn and V.
2. The composite membrane of claim 1, wherein: the mass ratio of the hydrophobic monomer to the ionic conductor monomer is 0.01-1; the mass ratio of the total mass of the hydrophobic monomer and the ionic conductor monomer to the solid electrolyte is 0.001-0.02.
3. The composite membrane of claim 1, wherein: the solvent is at least one of deionized water, DMF, DMSO, N-methyl pyrrolidone, methanol, ethanol, toluene or tetrahydrofuran.
4. The composite membrane of claim 1, wherein: the base film is made of polyethylene or polypropylene.
5. The composite membrane of claim 1, wherein: the thickness of the composite solid electrolyte coating is 0.2-20 mu m.
6. The composite membrane of claim 1, wherein: the particle size distribution of the solid electrolyte is as follows: d 50 Greater than or equal to 200 nm, dispersion
。
7. The method for producing a composite separator according to any one of claims 1 to 6, wherein: the method comprises the following steps:
uniformly mixing a binder, a stabilizer, an organic solvent and a composite solid electrolyte to obtain a stable suspension; and coating the suspension on the surface of the base film, and drying to remove the organic solvent to obtain the composite diaphragm.
8. The method for producing a composite separator according to claim 7, wherein: the binder is polyvinylidene fluoride; the stabilizer is at least one of carboxymethyl cellulose, sodium alginate, sodium polyacrylate and polyamide; the organic solvent is at least one of N-methyl pyrrolidone, acetonitrile and tetrahydrofuran.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110721031.6A CN113540697B (en) | 2021-06-28 | 2021-06-28 | Composite diaphragm and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110721031.6A CN113540697B (en) | 2021-06-28 | 2021-06-28 | Composite diaphragm and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113540697A CN113540697A (en) | 2021-10-22 |
| CN113540697B true CN113540697B (en) | 2022-09-09 |
Family
ID=78126024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110721031.6A Active CN113540697B (en) | 2021-06-28 | 2021-06-28 | Composite diaphragm and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113540697B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117174988B (en) * | 2023-09-01 | 2024-04-30 | 哈尔滨工业大学 | Preparation method of lithium/sodium ion battery material and application of lithium/sodium ion battery material in lithium/sodium ion battery |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7550216B2 (en) * | 1999-03-03 | 2009-06-23 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
| CN100583536C (en) * | 2006-06-29 | 2010-01-20 | 肇庆市风华锂电池有限公司 | Polymer lithium ion battery preparation technique and products |
| DE102007005156A1 (en) * | 2007-01-29 | 2008-08-14 | Evonik Degussa Gmbh | Ceramic membrane with improved adhesion to plasma-treated polymeric support material, as well as their preparation and use |
| CN101226994B (en) * | 2007-12-21 | 2010-06-30 | 成都中科来方能源科技有限公司 | Non-woven cloth increasing micropore polymer diaphragm and usage as well as preparation method thereof |
| CN101841013B (en) * | 2010-02-11 | 2012-07-04 | 华南师范大学 | Polymer isolating membrane and lithium ion battery applying same |
| CN102487132A (en) * | 2010-12-01 | 2012-06-06 | 徐亮良 | Battery diaphragm |
| CN108987801A (en) * | 2017-08-09 | 2018-12-11 | 浙江林奈新能源有限公司 | A kind of film for electrochemical cell electrolyte |
| CN108630871B (en) * | 2018-05-16 | 2021-05-28 | 深圳市星源材质科技股份有限公司 | Battery, battery diaphragm and preparation method thereof |
| CN109546212B (en) * | 2018-11-26 | 2022-05-20 | 广东聚圣科技有限公司 | Solid polymer electrolyte preparation method and solid secondary battery thereof |
| CN110233286B (en) * | 2019-03-22 | 2022-01-18 | 华南理工大学 | In-situ polymerization composite organic solid electrolyte and preparation method and application thereof |
| CN111933894B (en) * | 2020-08-12 | 2022-04-29 | 安普瑞斯（无锡）有限公司 | In-situ polymerized organic-inorganic composite solid battery |
-
2021
- 2021-06-28 CN CN202110721031.6A patent/CN113540697B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113540697A (en) | 2021-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110085904B (en) | Flexible composite solid electrolyte, all-solid-state lithium ion battery and preparation method thereof | |
| CN107591536B (en) | Gel composite positive plate, preparation method thereof and method for preparing all-solid-state lithium battery | |
| CN109119592B (en) | Lithium titanate negative electrode piece, preparation method and lithium titanate battery | |
| CN111063884B (en) | Water-based ion battery negative electrode material, water-based ion battery negative electrode and preparation method thereof, and water-based ion battery | |
| CN112117435B (en) | All-solid-state lithium battery positive plate, preparation method thereof and all-solid-state lithium battery | |
| CN106450422A (en) | Lithium-sulfur battery with multi-protection layer structure | |
| CN110311130B (en) | Titanium niobate negative electrode material and preparation method thereof | |
| CN110247009A (en) | A kind of anti-overcharge diaphragm and preparation method thereof and lithium ion battery | |
| CN109920991A (en) | Tertiary cathode material and preparation method thereof and lithium ion battery comprising the material | |
| CN110600680A (en) | Positive electrode slurry, positive plate comprising positive electrode slurry and lithium ion battery | |
| CN108598419A (en) | A kind of lithium carbon compound cathode piece and preparation method thereof and lithium secondary battery | |
| CN115566170A (en) | Preparation method of high-energy-density quick-charging lithium ion battery cathode material | |
| CN106711428A (en) | Lithium-rich ternary composite material and preparation method thereof | |
| CN115377353A (en) | Negative plate and battery using same | |
| CN113540697B (en) | Composite diaphragm and preparation method thereof | |
| CN109616655B (en) | Double-layer coated lithium iron borate/nickel pyrophosphate lithium battery positive electrode material and preparation method thereof | |
| CN113067100A (en) | Water-based PVDF (polyvinylidene fluoride) coated lithium ion battery diaphragm and preparation method thereof | |
| CN113235300B (en) | Preparation method of high-temperature-resistant lithium ion battery composite diaphragm | |
| CN116190565B (en) | Lithium ion battery | |
| WO2021088734A1 (en) | Lithium negative electrode with protective layer, preparation method therefor and use thereof | |
| WO2024012023A1 (en) | Ionic conductive agent, electrode sheet group, and lithium-ion battery | |
| CN112687839A (en) | Pole piece, preparation method thereof and lithium ion battery | |
| CN111900458A (en) | Composite solid electrolyte and preparation method thereof | |
| CN111682262A (en) | Three-dimensional cross-linked network gel polymer electrolyte membrane and preparation method and application thereof | |
| JP7413482B2 (en) | Manufacturing method for lithium ion battery negative electrode material |
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 |