CN113540697B - Composite diaphragm and preparation method thereof - Google Patents
Composite diaphragm and preparation method thereof Download PDFInfo
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- 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
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000010416 ion conductor Substances 0.000 claims abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- PMUKAEUGVCXPDF-UAIGNFCESA-L dilithium;(z)-but-2-enedioate Chemical compound [Li+].[Li+].[O-]C(=O)\C=C/C([O-])=O PMUKAEUGVCXPDF-UAIGNFCESA-L 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 150000001343 alkyl silanes Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- PMUKAEUGVCXPDF-SEPHDYHBSA-L dilithium;(e)-but-2-enedioate Chemical compound [Li+].[Li+].[O-]C(=O)\C=C\C([O-])=O PMUKAEUGVCXPDF-SEPHDYHBSA-L 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000002227 LISICON Substances 0.000 abstract description 17
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 210000004379 membrane Anatomy 0.000 abstract description 4
- 210000002469 basement membrane Anatomy 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- 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
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- 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.
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