CN114824665A - Solid electrolyte diaphragm and preparation method and application thereof - Google Patents
Solid electrolyte diaphragm and preparation method and application thereof Download PDFInfo
- Publication number
- CN114824665A CN114824665A CN202210354776.8A CN202210354776A CN114824665A CN 114824665 A CN114824665 A CN 114824665A CN 202210354776 A CN202210354776 A CN 202210354776A CN 114824665 A CN114824665 A CN 114824665A
- Authority
- CN
- China
- Prior art keywords
- inorganic
- solid electrolyte
- parts
- coating layer
- ceramic powder
- 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
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000011247 coating layer Substances 0.000 claims abstract description 54
- 239000012528 membrane Substances 0.000 claims abstract description 50
- 239000010410 layer Substances 0.000 claims abstract description 39
- 239000010416 ion conductor Substances 0.000 claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 54
- 239000011248 coating agent Substances 0.000 claims description 52
- 239000000919 ceramic Substances 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 50
- 239000002002 slurry Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 30
- 239000002270 dispersing agent Substances 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 239000002562 thickening agent Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 229920001522 polyglycol ester Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 238000000498 ball milling Methods 0.000 description 16
- 238000007765 extrusion coating Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000006255 coating slurry Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
-
- 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
- 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
- H01M50/431—Inorganic 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- 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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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 particularly relates to a solid electrolyte diaphragm and a preparation method and application thereof, belonging to the technical field of lithium batteries, wherein the electrolyte diaphragm comprises: the ion-conducting membrane comprises a membrane body, a first inorganic coating layer, a second inorganic coating layer and an ion conductor layer, wherein the first inorganic coating layer is coated on one surface of the membrane body; the second inorganic coating layer is coated on the other surface of the membrane body away from the first inorganic coating layer; the ion conductor layer is coated on one surface, far away from the membrane body, of the second inorganic coating layer; wherein the ion conductor layer has ion conductivity; by covering the inorganic coating layer with an ion conductor layer, the side of the ion conductor layer is in contact with the negative electrode, and the ion conductor layer has ion conduction capability, so that the ion conductivity of the diaphragm is improved.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a solid electrolyte diaphragm and a preparation method and application thereof.
Background
Applications in (hybrid) electric vehicles and energy storage present challenges to the development of lithium ion batteries. The development of advanced high energy/high power density lithium ion batteries is one of the most important and attractive issues in modern electrochemistry. The diaphragm is used as an important component of a high-voltage lithium ion battery, and is required to have sufficient chemical stability and thermal stability so as to ensure the safety and the cycle performance of the battery.
So far, polyolefin-based separators have become the most widely used separators in lithium ion batteries due to their advantages of low cost, moderate mechanical strength, and the like. However, the main disadvantage of such a separator is its inherent hydrophobicity and poor thermal stability. The hydrophobicity and low surface energy result in weak interaction between the separator and the highly polar liquid electrolyte and poor wettability, which will have serious adverse effects on the manufacturing cost and the battery performance. The melting point of the polyolefin material is only between 135 and 165 ℃. In case of heating of the battery, the separator may shrink or break, resulting in internal short circuit, thermal runaway and even explosion, seriously threatening the safety of the battery.
To overcome the above problems, the introduction of inorganic coatings is considered to be an ideal solution. First, inorganic nanoparticles can provide enhanced wettability. Second, the inorganic coating layer generally has excellent heat resistance, which may provide the separator with better thermal stability. In addition, the excellent flame retardancy of the inorganic nanoparticles can provide higher safety for the lithium ion battery. The most widely used inorganic ceramics include SiO 2 、Al 2 O 3 、ZrO 2 NaY zeolite, TiO 2 And the like. However, the introduction of inorganic coatings typically results in reduced ionic conductivity and reduced capacity due to the increased electrical resistance of the lithium ions in the coating.
Disclosure of Invention
The application aims to provide a solid electrolyte diaphragm, a preparation method and application thereof, so as to solve the problem that the ionic conductivity is reduced due to the introduction of an inorganic coating.
An embodiment of the present invention provides a solid electrolyte membrane, including:
a membrane body;
the first inorganic coating layer is coated on one surface of the membrane body;
the second inorganic coating layer is coated on the other surface of the membrane body away from the first inorganic coating layer;
the ion conductor layer is coated on one surface, far away from the membrane body, of the second inorganic coating layer;
wherein the ion conductor layer has ion conductivity.
Optionally, the coating raw material of the ion conductor layer includes a third inorganic ceramic powder having ion conductivity.
Optionally, the third inorganic ceramic powder with ion conductivity includes at least one of LATP and LLZO.
Optionally, the third inorganic ceramic powder has a set particle size, and the value range of the set particle size is 0.1 μm to 2 μm.
Optionally, the coating raw material of the first inorganic coating layer includes, in mass fraction: 20-40 parts of first inorganic ceramic powder, 60-80 parts of first solvent, 2-5 parts of first binder, 0.2-0.5 part of first dispersant and 0.2-0.5 part of first thickener;
the coating raw material of the second inorganic coating layer comprises the following components in percentage by mass: 20-40 parts of second inorganic ceramic powder, 60-80 parts of second solvent, 2-5 parts of second binder, 0.2-0.5 part of second dispersant and 0.2-0.5 part of second thickener;
the coating raw material of the ion conductor layer comprises the following components in percentage by mass: 20-40 parts of third inorganic ceramic powder, 60-80 parts of third solvent, 2-5 parts of third binder, 0.2-0.5 part of third dispersant and 0.2-0.5 part of third thickener.
Optionally, the first inorganic ceramic powder and the second inorganic ceramic powder respectively include at least one of alumina, boehmite, silica and titania;
the first adhesive, the second adhesive and the third adhesive respectively comprise at least one of styrene-butadiene rubber emulsion, acrylonitrile and acrylate emulsion;
the first dispersant, the second dispersant and the third dispersant respectively comprise at least one of polyacrylamide, fatty acid polyglycol ester and cellulose derivative;
the first, second and third thickeners comprise at least one of CMC and bentonite, respectively.
Optionally, the particle size of the first inorganic ceramic powder is 0.1 μm to 2 μm; the granularity of the second inorganic ceramic powder is 0.1-2 μm.
Optionally, the particle size of the second inorganic ceramic powder is smaller than the particle size of the third inorganic ceramic powder.
Optionally, the thicknesses of the first inorganic coating layer, the second inorganic coating layer and the ion conductor layer are respectively 1 μm to 5 μm.
Optionally, the film body is a PP film or a PE film.
Optionally, the thickness of the membrane body is 9 μm to 16 μm.
Based on the same inventive concept, the embodiment of the invention also provides a lithium ion battery, and the lithium ions adopt the solid electrolyte membrane.
Based on the same inventive concept, embodiments of the present invention also provide a method for preparing the solid electrolyte membrane, including:
coating the first slurry and the second slurry on the membrane body, and then drying to obtain an intermediate product containing a first inorganic coating layer and a second inorganic coating layer;
coating the third slurry on a second inorganic coating of the intermediate product, and then drying to obtain an electrolyte diaphragm;
the first slurry is a slurry for preparing the first inorganic coating layer, the second slurry is a slurry for preparing the second inorganic coating layer, and the third slurry is a slurry for preparing the ion conductor layer.
Optionally, the drying temperature is 50-70 ℃, and the drying time is 4-6 h.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
according to the solid electrolyte membrane provided by the embodiment of the invention, the ion conductor layer is covered outside the inorganic coating layer, the side of the ion conductor layer is in contact with the negative electrode, and the ion conductor layer has ion conduction capability, so that the ion conductivity of the membrane is improved.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a flow chart of a method provided by an embodiment of the present invention;
fig. 2 is a schematic structural view of an electrolyte separator provided in an embodiment of the present invention;
reference numerals are as follows: 1-a membrane body, 2-a first inorganic coating layer, 3-a second inorganic coating layer, 4-an ion conductor layer.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, 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. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, there is provided a solid electrolyte membrane including: the membrane comprises a membrane body, a first inorganic coating layer, a second inorganic coating layer and an ion conductor layer;
the first inorganic coating layer is coated on one surface of the membrane body;
the second inorganic coating layer is coated on the other surface of the membrane body away from the first inorganic coating layer;
the ion conductor layer is coated on one surface, far away from the membrane body, of the second inorganic coating layer;
wherein the ion conductor layer has ion conductivity.
Since the ion conductor layer has ion conductivity, the ion conductivity of the separator is improved. Meanwhile, the applicant finds that: the thermal stability of the diaphragm is improved and the safety is improved through the increase of the ion conductor layer and the inorganic coating layer; the ion conductor layer can provide protection for the cathode, inhibit the growth of lithium dendrites and prolong the cycle life of the battery.
In some embodiments, the coating material of the ion conductor layer includes a third inorganic ceramic powder with ion conductivity, and the third inorganic ceramic powder may be at least one selected from LATP and LLZO, and it should be noted that LATP is lithium ionSub-conductors, i.e. Li 1+x Al 2-x (PO 4 ) 3 LLZO is Li 7 La 3 Zr 2 O 12 。
In some embodiments, the third inorganic ceramic powder has a particle size of 0.1 μm to 2 μm, including but not limited to 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, and the like.
In some embodiments, the coating raw material of the first inorganic coating layer includes, in mass fraction: 20-40 parts of first inorganic ceramic powder, wherein the parts of the first inorganic ceramic powder include but are not limited to: 20 parts, 25 parts, 30 parts, 35 parts and 40 parts of a first solvent, wherein the values of the parts of the first solvent include but are not limited to: 60 parts, 65 parts, 70 parts, 75 parts and 80 parts, and 2-5 parts of a first binder, wherein the values of the parts of the first binder include but are not limited to: 2, 3, 4 and 5 parts, and 0.2-0.5 part of first dispersing agent, wherein the values of the first dispersing agent in parts include but are not limited to: 0.2 part, 0.3 part, 0.4 part and 0.5 part, and 0.2-0.5 part of first thickening agent, wherein the parts of the first thickening agent include but are not limited to: 0.2 parts, 0.3 parts, 0.4 parts and 0.5 parts;
the coating raw material of the second inorganic coating layer comprises the following components in percentage by mass: 20-40 parts of second inorganic ceramic powder, wherein the parts of the second inorganic ceramic powder include but are not limited to: 20 parts, 25 parts, 30 parts, 35 parts and 40 parts of a second solvent, wherein the values of the parts of the second solvent include but are not limited to: 60 parts, 65 parts, 70 parts, 75 parts and 80 parts, and 2-5 parts of a second binder, wherein the values of the parts of the second binder include but are not limited to: 2, 3, 4 and 5 parts, and 0.2-0.5 part of second dispersing agent, wherein the values of the second dispersing agent include but are not limited to: 0.2 part, 0.3 part, 0.4 part and 0.5 part, and 0.2-0.5 part of second thickening agent, wherein the values of the parts of the second thickening agent include but are not limited to: 0.2 parts, 0.3 parts, 0.4 parts and 0.5 parts;
the coating raw material of the ion conductor layer comprises the following components in percentage by mass: 20-40 parts of third inorganic ceramic powder, wherein the parts of the third inorganic ceramic powder include but are not limited to: 20 parts, 25 parts, 30 parts, 35 parts and 40 parts of a third solvent, wherein the values of the parts of the third solvent include but are not limited to: 60 parts, 65 parts, 70 parts, 75 parts and 80 parts, and 2-5 parts of a third binder, wherein the values of the parts of the third binder include but are not limited to: 2, 3, 4 and 5 parts, and 0.2-0.5 part of third dispersing agent, wherein the values of the third dispersing agent include but are not limited to: 0.2 part, 0.3 part, 0.4 part and 0.5 part, and 0.2-0.5 part of third thickening agent, wherein the values of the parts of the third thickening agent include but are not limited to: 0.2 part, 0.3 part, 0.4 part and 0.5 part.
Specifically, the first inorganic ceramic powder and the second inorganic ceramic powder may be at least one selected from alumina, boehmite, silica, and titania, respectively;
the first binder, the second binder and the third binder can be respectively selected from at least one of styrene-butadiene rubber emulsion, acrylonitrile and acrylate emulsion;
the first dispersant, the second dispersant and the third dispersant may be at least one selected from polyacrylamide, fatty acid polyglycol ester and cellulose derivative, respectively;
the first thickener, the second thickener and the third thickener may be selected from at least one of CMC (sodium carboxymethyl cellulose) and bentonite, respectively;
the first solvent, the first solvent and the first solvent may be respectively selected from any one of water, methanol and ethanol.
In some embodiments, the first inorganic ceramic powder has a particle size of 0.1 μm to 2 μm, the first inorganic ceramic powder has a particle size including, but not limited to, 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, etc., the second inorganic ceramic powder has a particle size of 0.1 μm to 2 μm, the second inorganic ceramic powder has a particle size including, but not limited to, 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, etc.
The particle size of the first inorganic ceramic powder, the second inorganic ceramic powder and the third inorganic ceramic powder is controlled to be 0.1-2 microns so that the inorganic ceramic powder can be uniformly dispersed, the coating thickness can be conveniently controlled, the air permeability and the thermal stability of the coated diaphragm are ensured, if the particle size is too large, the integral thickness of the diaphragm is increased, the diaphragm is easy to fall off after coating, and if the particle size is too small, the air permeability of the diaphragm is reduced.
In some embodiments, the third inorganic ceramic powder has a particle size greater than a particle size of the second inorganic ceramic powder.
The particle diameters of the coating particles of the ion conductor layer and the inorganic coating layer are different, so that a gap gradient is manufactured, and the washing rate of the diaphragm can be improved.
In some embodiments, the thicknesses of the first inorganic coating layer, the second inorganic coating layer and the ion conductor layer are respectively 1 μm to 5 μm, and the thicknesses include, but are not limited to, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, and the like.
In some embodiments, the film body is a polyolefin-based separator, and particularly, the polyolefin-based separator may be a PP film or a PE film, the thickness of the film body is 9 μm to 16 μm, and the thickness of the film body includes, but is not limited to, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, and the like.
According to another exemplary embodiment of the present invention, there is provided a method of manufacturing the solid electrolyte separator as described above, including:
s0. preparing slurry of each layer;
specifically, adding a certain amount of thickener (first thickener, second thickener or third thickener) into a solvent (first solvent, second solvent or third solvent), and starting a stirring device to prepare a solution with a certain viscosity; then putting a certain amount of inorganic ceramic powder (first inorganic ceramic powder, second inorganic ceramic powder or third inorganic ceramic powder) into a solution with a certain viscosity, and starting a stirring device to dissolve the inorganic ceramic powder to obtain a suspension; then, adding a proper amount of binder (first binder, second binder or third binder) and dispersant (first dispersant, second dispersant or third dispersant) into the suspension, wherein the ball milling speed is 300-500 r/min, and the ball milling time is 4-6 h, so as to obtain uniform and stable coating slurry (first slurry, second slurry or third slurry);
s1, coating the first slurry and the second slurry on a membrane body, and then drying to obtain an intermediate product containing a first inorganic coating layer and a second inorganic coating layer;
s2, coating the third slurry on a second inorganic coating of the intermediate product, and then drying to obtain an electrolyte diaphragm;
the first slurry is a slurry for preparing the first inorganic coating layer, the second slurry is a slurry for preparing the second inorganic coating layer, and the third slurry is a slurry for preparing the ion conductor layer.
In some embodiments, the drying temperature is 50 ℃ to 70 ℃, the drying temperature includes, but is not limited to, 50 ℃, 55 ℃, 60 ℃, 65 ℃ and 70 ℃, the drying time is 4h to 6h, and the drying time includes, but is not limited to, 4h, 4.5h, 5h, 5.5h and 6 h.
The solid electrolyte separator of the present application, and the preparation method and application thereof will be described in detail below with reference to examples, comparative examples, and experimental data.
Example 1
A method of making a solid electrolyte membrane, the method comprising:
1) CMC0.15g was added to 16.2g of water, and the mixture was stirred in a magnetic stirrer at 500r/min to obtain a viscous solution.
2) Selecting 12g of alumina with the particle size of 0.5 mu m, adding the alumina into the viscous solution, and uniformly stirring;
3) adding 0.15g of polyacrylamide and the solution in the step (2) into a ball milling tank, and carrying out ball milling at the rotating speed of 500r/min for 4h to obtain coating slurry;
4) coating the slurry on the surface of PE film with thickness of 12 μm by extrusion coating, and adding 60 ℃ And drying in an oven for 6h to obtain a coating diaphragm 1 with the coating thickness of 3 mu m.
5) And (3) coating the slurry in the step (3) on the uncoated surface of the diaphragm in the step (4) by extrusion coating, and drying in a 60 ℃ oven for 6h to obtain a coated diaphragm 2 with the coating thickness of 2 microns.
6) CMC0.15g was added to 16.2g of water, and the mixture was stirred in a magnetic stirrer at 500r/min to obtain a viscous solution.
7) Selecting 12g of LATP with the particle size of 0.3 mu m, adding the LATP into the viscous solution, and uniformly stirring;
8) adding 0.15g of polyacrylamide and the solution in the step (2) into a ball milling tank, and carrying out ball milling at the rotating speed of 500r/min for 4h to obtain coating slurry;
9) the slurry is coated on a 2-micron coated surface in a coating diaphragm 2 by extrusion coating, and the coated diaphragm 3 is obtained by drying in a 60-DEG C oven for 6h, so that the coating thickness reaches 3 microns.
Example 2
A method of making a solid electrolyte membrane, the method comprising:
1) CMC0.15g was added to 16.2g of water, and the mixture was stirred in a magnetic stirrer at 500r/min to obtain a viscous solution.
2) Selecting 12g of alumina with the particle size of 1 mu m, adding the alumina into the viscous solution, and uniformly stirring;
3) adding 0.15g of polyacrylamide and the solution in the step (2) into a ball milling tank, and carrying out ball milling for 4 hours at the rotating speed of 500r/min to obtain coating slurry;
4) coating the slurry on the surface of PE film with thickness of 12 μm by extrusion coating, and adding 60 ℃ And drying in an oven for 6h to obtain a coating diaphragm 1 with the coating thickness of 3 mu m.
5) And (3) coating the slurry in the step (3) on the uncoated surface of the diaphragm in the step (4) by extrusion coating, and drying in a 60 ℃ oven for 6h to obtain a coated diaphragm 2 with the coating thickness of 2 microns.
6) CMC0.15g was added to 16.2g of water, and the mixture was stirred in a magnetic stirrer at 500r/min to obtain a viscous solution.
7) Selecting 12g of LATP with the particle size of 0.3 mu m, adding the LATP into the viscous solution, and uniformly stirring;
8) adding 0.15g of polyacrylamide and the solution in the step (2) into a ball milling tank, and carrying out ball milling at the rotating speed of 500r/min for 4h to obtain coating slurry;
9) the slurry is coated on a 2-micron coated surface in a coating diaphragm 2 by extrusion coating, and the coated diaphragm 3 is obtained by drying in a 60-DEG C oven for 6h, so that the coating thickness reaches 3 microns.
Example 3
A method of making a solid electrolyte membrane, the method comprising:
1) CMC0.15g was added to 16.2g of water and stirred in a magnetic stirrer at 500r/min to give a viscous solution.
2) Selecting 12g of alumina with the particle size of 0.5 mu m, adding the alumina into the viscous solution, and uniformly stirring;
3) adding 0.15g of polyacrylamide and the solution in the step (2) into a ball milling tank, and carrying out ball milling at the rotating speed of 500r/min for 4h to obtain coating slurry;
4) coating the slurry on the surface of PE film with thickness of 12 μm by extrusion coating, and adding 60 ℃ And drying in an oven for 6h to obtain a coating diaphragm 1 with the coating thickness of 3 mu m.
5) And (3) coating the slurry in the step (3) on the uncoated surface of the diaphragm in the step (4) by extrusion coating, and drying in a 60 ℃ oven for 6h to obtain a coated diaphragm 2 with the coating thickness of 2 microns.
6) CMC0.15g was added to 16.2g of water, and the mixture was stirred in a magnetic stirrer at 500r/min to obtain a viscous solution.
7) Selecting 12g of LATP with the particle size of 0.5 mu m, adding the LATP into the viscous solution, and uniformly stirring;
8) adding 0.15g of polyacrylamide and the solution in the step (2) into a ball milling tank, and carrying out ball milling at the rotating speed of 500r/min for 4h to obtain coating slurry;
9) the slurry is coated on a 2-micron coated surface in a coating diaphragm 2 by extrusion coating, and the coated diaphragm 3 is obtained by drying in a 60-DEG C oven for 6h, so that the coating thickness reaches 3 microns.
Comparative example 1
A method of making a solid electrolyte membrane, the method comprising:
1) CMC0.15g was added to 16.2g of water, and the mixture was stirred in a magnetic stirrer at 500r/min to obtain a viscous solution.
2) Selecting 12g of alumina with the particle size of 0.5 mu m, adding the alumina into the viscous solution, and uniformly stirring;
3) adding 0.15g of polyacrylamide and the solution in the step (2) into a ball milling tank, and carrying out ball milling at the rotating speed of 500r/min for 4h to obtain coating slurry;
4) coating the slurry on the surface of PE film with thickness of 12 μm by extrusion coating, and adding 60 ℃ Drying in an oven for 6h to obtain a coated diaphragm, coating on both sides, and coating thickness of 3 μm each.
Examples of the experiments
The solid electrolyte separators obtained in examples 1 to 3 and comparative example 1 were subjected to geometric and mechanical property tests, and the results are shown in the following table:
from the above table, the liquid absorption rate of the solid electrolyte prepared by the method provided in the examples of the present application is greater than 176%, and the ionic conductivity is 3.2 x 10 -3 S·cm -1 And 3.9 x 10 -3 S·cm -1 The capacity retention rate of 200 turns is more than 91%. As can be seen from comparison of the comparative example and the example, the liquid absorption rate, the ionic conductivity, and the battery cycle life of the solid electrolyte were all reduced without providing the ion conductor layer.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) the solid electrolyte provided by the embodiment of the invention improves the thermal stability of the diaphragm and increases the safety through the ion conductor layer and the inorganic coating layer;
(2) according to the solid electrolyte provided by the embodiment of the invention, the particle diameters of the coating particles of the ion conductor layer and the inorganic coating layer are different, so that a gap gradient is manufactured, and the washing rate of the diaphragm is improved;
(3) the ion conductor layer of the solid electrolyte provided by the embodiment of the invention has ion conduction capability, so that the ion conductivity of the diaphragm is improved;
(4) the ion conductor layer of the solid electrolyte provided by the embodiment of the invention can provide protection for a negative electrode, inhibit the growth of lithium dendrites and prolong the cycle life of a battery.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all changes and modifications that fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (15)
1. A solid electrolyte membrane, characterized in that the electrolyte membrane comprises:
a membrane body;
the first inorganic coating layer is coated on one surface of the membrane body;
the second inorganic coating layer is coated on the other surface of the membrane body away from the first inorganic coating layer;
the ion conductor layer is coated on one surface, far away from the membrane body, of the second inorganic coating layer;
wherein the ion conductor layer has ion conductivity.
2. The solid electrolyte membrane according to claim 1, wherein a coating raw material of the ion conductor layer includes a third inorganic ceramic powder having ion conductivity.
3. The solid electrolyte membrane according to claim 2, wherein the third inorganic ceramic powder having ion conductivity includes at least one of LATP and LLZO.
4. The solid electrolyte membrane of any one of claims 2 to 3, wherein the third inorganic ceramic powder has a set particle size, and the set particle size ranges from 0.1 μm to 2 μm.
5. The solid electrolyte membrane according to any one of claim 4, wherein the coating raw material of the second inorganic coating layer comprises a second inorganic ceramic powder having a particle size smaller than that of the third inorganic ceramic powder.
6. The solid electrolyte membrane according to any one of claims 1 to 5, wherein the ion conductor layer has a thickness of 1 μm to 5 μm.
7. The solid electrolyte membrane according to any one of claims 1 to 6, wherein the coating raw material of the ion conductor layer comprises, in mass fraction: 20-40 parts of third inorganic ceramic powder, 60-80 parts of third solvent, 2-5 parts of third binder, 0.2-0.5 part of third dispersant and 0.2-0.5 part of third thickener.
8. The solid electrolyte membrane according to any one of claim 7, wherein a coating raw material of the first inorganic coating layer comprises, in mass fraction: 20-40 parts of first inorganic ceramic powder, 60-80 parts of first solvent, 2-5 parts of first binder, 0.2-0.5 part of first dispersant and 0.2-0.5 part of first thickener;
the coating raw material of the second inorganic coating layer comprises the following components in percentage by mass: 20-40 parts of second inorganic ceramic powder, 60-80 parts of second solvent, 2-5 parts of second binder, 0.2-0.5 part of second dispersant and 0.2-0.5 part of second thickener.
9. The solid electrolyte separator according to claim 8, wherein the first inorganic ceramic powder and the second inorganic ceramic powder respectively include at least one of alumina, boehmite, silica, and titania;
the first binder, the second binder and the third binder respectively comprise at least one of styrene-butadiene rubber emulsion, acrylonitrile and acrylate emulsion;
the first dispersant, the second dispersant and the third dispersant respectively comprise at least one of polyacrylamide, fatty acid polyglycol ester and cellulose derivative;
the first, second and third thickeners comprise at least one of CMC and bentonite, respectively.
10. The solid electrolyte membrane according to claim 9, wherein the particle size of the first inorganic ceramic powder is 0.1 μm to 2 μm; the granularity of the second inorganic ceramic powder is 0.1-2 μm.
11. The solid electrolyte separator according to claim 1, wherein the first inorganic coating layer and the second inorganic coating layer each have a thickness of 1 μm to 5 μm.
12. The solid electrolyte separator according to any one of claims 1 to 11, wherein the membrane body is a PP membrane or a PE membrane, and the thickness of the membrane body is 9 μm to 16 μm.
13. A lithium ion battery, characterized in that the lithium ions employ the solid electrolyte membrane of any one of claims 1 to 12.
14. A method for producing a solid electrolyte membrane according to any one of claims 1 to 12, characterized in that the method comprises:
coating the first slurry and the second slurry on the membrane body, and then drying to obtain an intermediate product containing a first inorganic coating layer and a second inorganic coating layer;
coating the third slurry on a second inorganic coating of the intermediate product, and then drying to obtain an electrolyte diaphragm;
the first slurry is a slurry for preparing the first inorganic coating layer, the second slurry is a slurry for preparing the second inorganic coating layer, and the third slurry is a slurry for preparing the ion conductor layer.
15. The method for producing a solid electrolyte membrane according to claim 14, wherein the temperature of the baking is 50 ℃ to 70 ℃, and the time of the baking is 4h to 6 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210354776.8A CN114824665A (en) | 2022-04-06 | 2022-04-06 | Solid electrolyte diaphragm and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210354776.8A CN114824665A (en) | 2022-04-06 | 2022-04-06 | Solid electrolyte diaphragm and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114824665A true CN114824665A (en) | 2022-07-29 |
Family
ID=82533589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210354776.8A Pending CN114824665A (en) | 2022-04-06 | 2022-04-06 | Solid electrolyte diaphragm and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114824665A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107275550A (en) * | 2017-06-20 | 2017-10-20 | 深圳市星源材质科技股份有限公司 | A kind of ceramics and polymer composite coated lithium-ion membrane and preparation method thereof |
| CN108292728A (en) * | 2016-06-08 | 2018-07-17 | 株式会社Lg化学 | Diaphragm and the electrochemical appliance for including the diaphragm |
| CN112534636A (en) * | 2018-08-21 | 2021-03-19 | 应用材料公司 | Ultra-thin ceramic coating on separator for battery |
| CN113964455A (en) * | 2021-12-03 | 2022-01-21 | 东莞市魔方新能源科技有限公司 | Diaphragm for lithium ion battery and lithium ion battery |
| CN114050376A (en) * | 2021-10-21 | 2022-02-15 | 东风汽车集团股份有限公司 | Double-layer electrode supported inorganic diaphragm and preparation method thereof |
| CN114156602A (en) * | 2021-12-13 | 2022-03-08 | 溧阳天目先导电池材料科技有限公司 | Solid electrolyte diaphragm with multiple coatings, preparation method and application |
| CN114171848A (en) * | 2021-10-21 | 2022-03-11 | 东风汽车集团股份有限公司 | Solid electrolyte-electrode integrated diaphragm and preparation method thereof |
-
2022
- 2022-04-06 CN CN202210354776.8A patent/CN114824665A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108292728A (en) * | 2016-06-08 | 2018-07-17 | 株式会社Lg化学 | Diaphragm and the electrochemical appliance for including the diaphragm |
| CN107275550A (en) * | 2017-06-20 | 2017-10-20 | 深圳市星源材质科技股份有限公司 | A kind of ceramics and polymer composite coated lithium-ion membrane and preparation method thereof |
| CN112534636A (en) * | 2018-08-21 | 2021-03-19 | 应用材料公司 | Ultra-thin ceramic coating on separator for battery |
| CN114050376A (en) * | 2021-10-21 | 2022-02-15 | 东风汽车集团股份有限公司 | Double-layer electrode supported inorganic diaphragm and preparation method thereof |
| CN114171848A (en) * | 2021-10-21 | 2022-03-11 | 东风汽车集团股份有限公司 | Solid electrolyte-electrode integrated diaphragm and preparation method thereof |
| CN113964455A (en) * | 2021-12-03 | 2022-01-21 | 东莞市魔方新能源科技有限公司 | Diaphragm for lithium ion battery and lithium ion battery |
| CN114156602A (en) * | 2021-12-13 | 2022-03-08 | 溧阳天目先导电池材料科技有限公司 | Solid electrolyte diaphragm with multiple coatings, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109314207B (en) | Separator and electrochemical device comprising the same | |
| WO2018145666A1 (en) | High temperature-resistant lithium ion battery separator having a variety of coatings and preparation method therefor | |
| KR101198806B1 (en) | Electrode of secondary cell including por0us insulating layer and manufacturing thereof | |
| JP6972000B2 (en) | Non-porous separator and its use | |
| CN110071293B (en) | Battery cell and battery, liquid-retaining coating and battery pole piece and preparation method thereof | |
| CN113013549B (en) | Coating material for light-weight lithium ion battery diaphragm, preparation method of coating material and light-weight lithium ion battery composite diaphragm | |
| CN103311539A (en) | High-voltage high-energy-density lithium ion battery | |
| KR20150129669A (en) | Separator for nonaqueous secondary batteries, and nonaqueous secondary battery | |
| CN111725468B (en) | Silicon dioxide inorganic nanoparticle reinforced polyolefin diaphragm and application thereof | |
| CN113224263A (en) | Negative electrode and preparation method and application thereof | |
| CN112490584A (en) | Lithium ion battery diaphragm with alternate coating structure and preparation method thereof | |
| CN108822586B (en) | Preparation method of modified barium titanate material, battery diaphragm and lithium ion battery | |
| CN114050376A (en) | Double-layer electrode supported inorganic diaphragm and preparation method thereof | |
| CN114171848A (en) | Solid electrolyte-electrode integrated diaphragm and preparation method thereof | |
| Muchakayala et al. | Modified ceramic coated polyethylene separator–A strategy for using lithium metal as anode with superior electrochemical performance and thermal stability | |
| JP2015088430A (en) | Nonaqueous electrolyte secondary battery separator, and nonaqueous electrolyte secondary battery having the same | |
| EP3979360A1 (en) | All-solid-state battery and method for producing same | |
| WO2023179550A1 (en) | Composite oil-based separator and preparation method therefor, and secondary battery | |
| JP7226314B2 (en) | ELECTRODE, ELECTRODE, AND METHOD FOR MANUFACTURING ELECTRODE | |
| CN111682149A (en) | Lithium ion battery diaphragm and lithium ion battery | |
| CN114824665A (en) | Solid electrolyte diaphragm and preparation method and application thereof | |
| JP2006351365A (en) | Separator for electronic components, and the electronic component | |
| CN114865224A (en) | Diaphragm with high safety performance, coating layer thereof, preparation method and application | |
| CN109786620B (en) | Coating film and preparation method and application thereof | |
| EP4215591A1 (en) | Coating fluid composition, substrate with coating film, separator, secondary battery, and 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 |