CN116315455B - High-ion-conductivity high-temperature-resistant lithium battery diaphragm and preparation method thereof - Google Patents
High-ion-conductivity high-temperature-resistant lithium battery diaphragm and preparation method thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 85
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 85
- 229960004441 tyrosine Drugs 0.000 claims abstract description 64
- 239000011247 coating layer Substances 0.000 claims abstract description 56
- -1 tyrosine modified carbon nano tubes Chemical class 0.000 claims abstract description 52
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 47
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims abstract description 39
- 239000000919 ceramic Substances 0.000 claims abstract description 30
- 239000011246 composite particle Substances 0.000 claims abstract description 25
- 239000002033 PVDF binder Substances 0.000 claims abstract description 20
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000006255 coating slurry Substances 0.000 claims description 43
- 238000000498 ball milling Methods 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 37
- 239000011230 binding agent Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000002270 dispersing agent Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000080 wetting agent Substances 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 150000001263 acyl chlorides Chemical class 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000011324 bead Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical group CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 claims description 6
- 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 150000008431 aliphatic amides Chemical group 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 19
- 229910001416 lithium ion Inorganic materials 0.000 description 19
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 16
- 230000005540 biological transmission Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- 239000012528 membrane Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229940037312 stearamide Drugs 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- 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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- 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
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of lithium battery diaphragms, and discloses a high-ion conductivity high-temperature-resistant lithium battery diaphragm and a preparation method thereof, wherein the high-ion-conductivity high-temperature-resistant lithium battery diaphragm comprises a base film, a first coating layer and a second coating layer which are sequentially arranged on the surface of the base film; the first coating layer comprises composite particles, wherein the composite particles comprise tyrosine modified carbon nano tubes and ceramic particles in a mass ratio of 10-30:90-70; the second coating layer comprises PVDF powder; the preparation method of the tyrosine modified carbon nano tube comprises the following steps: and (3) carboxylating and acyl-chlorinating the carbon nano tube, and then reacting with L-tyrosine to obtain the tyrosine modified carbon nano tube. According to the invention, the tyrosine modified carbon nanotube in the first coating layer can effectively improve the ion conductivity of the diaphragm, and the ceramic particles can improve the high temperature resistance of the diaphragm; the PVDF powder in the second coating layer can improve the wettability of the diaphragm with electrolyte and the adhesiveness with an electrode, so that the diaphragm has good ion conductivity and high temperature resistance.
Description
Technical Field
The invention relates to the technical field of lithium battery diaphragms, in particular to a high-ion-conductivity high-temperature-resistant lithium battery diaphragm and a preparation method thereof.
Background
The lithium battery consists of four main parts of positive electrode, negative electrode, diaphragm and electrolyte. The diaphragm is used as an important component of the lithium battery, and has important significance for blocking electrons, preventing short circuit and ensuring internal ion permeation so as to ensure the battery to run efficiently, stably and safely. The structure and performance of the separator may affect the interface structure and internal resistance of the battery, and affect the overall electrical performance and safety of the battery.
The conventional lithium battery separator is mainly a polyolefin separator, which has problems of low ionic conductivity and low melting point. The ionic conductivity reflects the transmission capacity of lithium ions, and the low ionic conductivity of the diaphragm can influence the electrical performance of the lithium battery; the melting point of the diaphragm is related to the safety performance and the use environment of the battery, and the low melting point and the high temperature resistance are poor, so that the explosion and the combustion of the battery are easily caused. Therefore, the improvement of the ionic conductivity and the high temperature resistance of the polyolefin membrane has important significance.
At present, most manufacturers mainly improve the transmission capacity of the diaphragm to lithium ions by improving the wettability, the liquid absorption and retention capacity, the porosity of the diaphragm and other methods, and no good method for directly improving the ion conductivity of the polyolefin diaphragm exists. In the prior art, the high temperature resistance of the diaphragm is mainly improved by coating a ceramic coating on the polyolefin diaphragm, but the coating of the ceramic coating inevitably affects the porosity of the diaphragm, which is not beneficial to improving the lithium ion transmission capacity of the diaphragm.
Disclosure of Invention
The invention aims to overcome the problems of the lithium battery diaphragm in the prior art and provides a high-ion conductivity high-temperature-resistant lithium battery diaphragm and a preparation method thereof, wherein a first coating layer containing tyrosine modified carbon nano tubes and ceramic particles and a second coating layer containing PVDF powder are arranged on a base film; the tyrosine modified carbon nano tube in the first coating layer can effectively improve the ion conductivity of the diaphragm, and the ceramic particles can improve the high temperature resistance of the diaphragm; the PVDF powder in the second coating layer can improve the wettability of the diaphragm with electrolyte and the adhesiveness with an electrode, so that the diaphragm has good ion conductivity and high temperature resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a high-ion conductivity high-temperature-resistant lithium battery diaphragm comprises a base film, a first coating layer and a second coating layer which are sequentially arranged on the surface of the base film;
the first coating layer is coated with a first coating slurry, and the first coating slurry comprises the following components: composite particles, a dispersing agent, a wetting agent, a binder and a solvent; the composite particles comprise tyrosine modified carbon nano tubes and ceramic particles with the mass ratio of 10-30:90-70; the particle size of the ceramic particles is 50-100 nm;
the second coating layer is coated with a second coating slurry, the second coating slurry comprising the components: PVDF powder, a dispersing agent, a wetting agent, a binder and a solvent;
the preparation method of the tyrosine modified carbon nano tube comprises the following steps:
a) Reacting the carbon nanotubes with nitric acid to obtain carboxylated carbon nanotubes; the length-diameter ratio of the carbon nano tube is 10-30, and the inner diameter is 10-20 nm;
b) Reacting the carboxylated carbon nano tube with thionyl chloride to obtain an acyl chloride carbon nano tube;
c) And (3) reacting the acyl chloride carbon nano tube with L-tyrosine to obtain the tyrosine modified carbon nano tube.
The invention provides a first coating layer containing tyrosine modified carbon nano tubes and ceramic particles and a second coating layer containing PVDF powder on a base film. The ceramic particles in the first coating layer can improve the high temperature resistance of the diaphragm, and the carbon nano tube with high length-diameter ratio can be closely stacked with the ceramic particles, so that a structure with high specific surface area and high porosity is formed in the diaphragm, and the diffusion and transmission rate of ions can be increased, thereby improving the ion conductivity of the diaphragm and being beneficial to improving the power density and response speed of the battery. And the carbon nano tube and the ceramic particles have high chemical stability and corrosion resistance, can resist chemical corrosion and oxidative damage in the battery, and keep the stability and the service life of the material.
Meanwhile, tyrosine is grafted on the surface of the carbon nano tube through chemical reaction, a large number of polar groups which can coordinate with lithium ions such as hydroxyl, carboxyl and amide can be simultaneously introduced on the surface of the carbon nano tube, and a high-efficiency transmission structural unit of lithium ions is introduced on the surface of the carbon nano tube, so that a high-speed transmission channel of lithium ions is constructed in the diaphragm, the transmission efficiency of lithium ions is improved, the ionic conductivity of the diaphragm is greatly improved, and the electric performance of a battery is improved. The hydroxyl and aromatic ring structures in the tyrosine can improve the adhesiveness between the coating and the base film through hydrogen bonds, van der Waals forces and other modes; the aromatic ring structure contained in the membrane can also perform pi-pi stacking action with other molecules to form a cross-linked structure, so that the mechanical strength and stability of the coating are improved, and the membrane performance is further improved. The grafting of tyrosine is also beneficial to improving the dispersibility of the carbon nano tube in the coating slurry and avoiding the blocking of pores of the diaphragm caused by carbon nano tube agglomeration. The tyrosine grafting is also beneficial to improving the affinity between the diaphragm and the polar electrolyte, so that the electrolyte can be quickly soaked in the diaphragm, and the lithium ion quick transmission is also facilitated.
The invention selects ceramic particles with the particle size of 50-100 nm in the first coating layer, and the carbon nano tube can be blocked when the particle size of the ceramic particles is too small; if the particle size is too large, close packing between particles cannot be achieved, and even the gaps between carbon nanotubes cannot be filled with the particles, resulting in a decrease in ion conductivity of the separator. According to the invention, PVDF powder is added into the second coating layer, so that the wettability of the diaphragm and the electrolyte and the cohesiveness of the diaphragm and the positive and negative plates can be improved, the electrolyte can be facilitated to quickly infiltrate the whole diaphragm, lithium ions can be promoted to effectively penetrate through the diaphragm, and the electrical property of the lithium ion battery can be improved.
Preferably, the reaction conditions of step a) are: mixing the carbon nano tube with 1-2 mol/L nitric acid solution, performing hydrothermal reaction for 6-8 h at 115-125 ℃, washing and drying the product to obtain carboxylated carbon nano tube; the mass volume ratio of the carbon nano tube to the nitric acid solution is 1 g:50-60 mL.
Preferably, the reaction conditions of step B) are: and mixing the carboxylated carbon nano tube and thionyl chloride according to the mass volume ratio of 1g to 100-150 mL, stirring at 80-90 ℃ for reacting for 18-24 h, and drying the product to obtain the carbon nano tube.
Preferably, the reaction conditions of step C) are: dispersing an acyl chloride carbon nano tube in an organic solvent, then adding L-tyrosine and dicyclohexylcarbodiimide, stirring at 60-70 ℃ for reaction for 18-24 hours, washing and drying the product to obtain a tyrosine modified carbon nano tube; the mass ratio of the acyl chloride carbon nano tube to the L-tyrosine to the dicyclohexylcarbodiimide is 1:1-1.5:0.2-0.3.
Preferably, the first coating slurry comprises the following components in parts by weight: 100 parts of composite particles, 1-3 parts of dispersing agent, 3-5 parts of wetting agent, 10-40 parts of binder and 200-300 parts of solvent; the ceramic particles in the composite particles are selected from one or more of aluminum oxide, magnesium oxide, titanium dioxide, silicon dioxide and antimony trioxide; the dispersing agent is TNWDIS; the wetting agent is dodecyl sulfonate; the binder is a water-based acrylic ester binder, and the solid content is 30-50wt%; the solvent is water.
Preferably, the second coating slurry comprises the following components in parts by weight: 100 parts of PVDF powder, 5-10 parts of dispersing agent, 5-8 parts of wetting agent, 3-10 parts of binder and 200-300 parts of solvent; the dispersing agent is aliphatic amide dispersing agent, and the wetting agent is dodecyl sulfonate; the binder is a water-based acrylic ester binder, and the solid content is 30-50wt%; the solvent is water.
Preferably, the thickness of the base film is 9 to 16 μm, the thickness of the first coating layer is 2 to 4 μm, and the thickness of the second coating layer is 1 to 3 μm.
The invention also provides a preparation method of the high-ion conductivity high-temperature-resistant lithium battery diaphragm, which comprises the following steps:
(1) Preparing tyrosine modified carbon nano-tubes;
(2) Ball milling is carried out on the tyrosine modified carbon nano tube;
(3) Mixing the ball-milled tyrosine-modified carbon nanotubes with ceramic particles to obtain composite particles, adding the composite particles, a dispersing agent, a wetting agent and a binder into a solvent, and uniformly stirring and mixing to obtain first coating slurry;
(4) Adding PVDF powder, a dispersing agent, a wetting agent and a binder into a solvent, and uniformly stirring and mixing to obtain second coating slurry;
(5) Coating the first coating slurry on one side or two side surfaces of the base film, and drying to obtain a first coating layer;
(6) And coating the second coating slurry on the surface of the first coating layer, and drying to obtain the high-ion-conductivity high-temperature-resistant lithium battery diaphragm.
After the carbon nano tube is modified by tyrosine, ball milling is carried out on the modified carbon nano tube, and then the modified carbon nano tube is mixed with ceramic particles to prepare the first coating slurry. The ball milling can properly reduce the length-diameter ratio of the carbon nano tube, and the lower length-diameter ratio can better realize uniform and compact accumulation before the carbon nano tube and ceramic particles, thereby being beneficial to improving the diffusion and transmission rate of lithium ions and improving the ion conductivity of the diaphragm.
Preferably, the ball milling method in the step (2) is as follows: zirconium silicate beads or zirconium oxide beads are used as grinding balls, ethanol is used as a ball milling medium, and a surfactant is added to ball mill the tyrosine modified carbon nano tube, and then the carbon nano tube is cleaned and dried; the diameter of the grinding ball is 3-5 mm, the ball material mass ratio during ball milling is 3-5:1, the feed liquid ratio is 1 g:20-30 mL, the addition amount of the surfactant is 0.3-0.5% of the mass of ethanol, the ball milling rotating speed is 200-300 rpm, and the ball milling time is 30-60 min.
Preferably, the drying temperature in step (5) and step (6) is 115-125 ℃ and the drying time is 3-5 min.
Therefore, the invention has the following beneficial effects:
(1) Ceramic particles and tyrosine modified carbon nanotubes are added into the first coating layer, so that the high temperature resistance of the diaphragm can be improved, the carbon nanotubes with high length-diameter ratio can be closely stacked with the ceramic particles, a structure with high specific surface area and high porosity is formed in the diaphragm, and the diffusion and transmission rate of ions can be increased, so that the ion conductivity of the diaphragm is improved;
(2) Tyrosine is grafted on the surface of the carbon nano tube through chemical reaction, a large number of polar groups which can coordinate with lithium ions, such as hydroxyl groups, carboxyl groups, amide groups and the like, can be simultaneously introduced on the surface of the carbon nano tube, and a high-efficiency transmission structural unit of the lithium ions is introduced on the surface of the carbon nano tube, so that a high-speed transmission channel of the lithium ions is constructed in the diaphragm, the transmission efficiency of the lithium ions is improved, and the ion conductivity of the diaphragm is greatly improved;
(3) After the carbon nano tube is modified by tyrosine, ball milling is carried out on the modified carbon nano tube, and then the modified carbon nano tube is mixed with ceramic particles to prepare first coating slurry; the length-diameter ratio of the carbon nano tube can be properly reduced by ball milling, so that uniform and compact accumulation of the carbon nano tube and ceramic particles is better realized, and the ionic conductivity of the diaphragm is improved;
(4) The PVDF powder is added into the second coating layer, so that the wettability of the diaphragm and the electrolyte and the cohesiveness of the diaphragm and the positive and negative pole pieces can be improved, the electrolyte can be facilitated to quickly infiltrate the whole diaphragm, and lithium ions can be promoted to effectively penetrate through the diaphragm.
Detailed Description
The invention is further described below in connection with the following detailed description.
In the present invention, all the equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
The raw materials adopted in the embodiment of the invention are as follows:
carbon nanotubes, purchased from Hebei magnesium Xixi biological Co., ltd., with an aspect ratio of 10-30 and an inner diameter of 10-20 nm;
magnesium oxide particles and aluminum oxide particles, which are purchased from Hangzhou Hengge nanotechnology Co., ltd, have a particle size of 20-50 nm;
TNWDIS, available from Tesco chemical Co., ltd;
an aqueous acrylate binder having a solids content of 40wt% available from Tianjin Siepri corporation;
PVDF, france Amara HSV900.
General examples:
a high-ion conductivity high-temperature-resistant lithium battery diaphragm comprises a polyolefin-based film with the thickness of 9-16 mu m, a first coating layer with the thickness of 2-4 mu m and a second coating layer with the thickness of 1-3 mu m, which are sequentially arranged on the surface of the polyolefin-based film;
the polyolefin-based membrane is a polyethylene membrane, a polypropylene membrane or a three-layer co-extrusion film;
the first coating layer is made by coating a first coating slurry, and the components of the first coating slurry comprise, in parts by weight: 100 parts of composite particles, 1-3 parts of dispersing agent, 3-5 parts of wetting agent, 10-40 parts of binder and 200-300 parts of solvent; the composite particles comprise tyrosine modified carbon nano tubes and ceramic particles with the mass ratio of 10-30:90-70; the ceramic particles are selected from one or more of aluminum oxide, magnesium oxide, titanium dioxide, silicon dioxide and antimony trioxide, and the particle size of the ceramic particles is 50-100 nm; the dispersant is TNWDIS; the wetting agent is dodecyl sulfonate; the binder is a water-based acrylic ester binder, and the solid content is 30-50wt%; the solvent is water;
the second coating layer is coated by a second coating slurry, and the second coating slurry comprises the following components in parts by weight: 100 parts of PVDF powder, 5-10 parts of dispersing agent, 5-8 parts of wetting agent, 3-10 parts of binder and 200-300 parts of solvent; the dispersing agent is aliphatic amide dispersing agent, and the wetting agent is dodecyl sulfonate; the binder is a water-based acrylic ester binder, and the solid content is 30-50wt%; the solvent is water.
The preparation method of the high-ion conductivity high-temperature-resistant lithium battery diaphragm comprises the following steps:
(1) Preparing tyrosine modified carbon nano tubes:
a) Mixing the carbon nano tube with 1-2 mol/L nitric acid solution, performing hydrothermal reaction for 6-8 h at 115-125 ℃, washing and drying the product to obtain carboxylated carbon nano tube; the mass volume ratio of the carbon nano tube to the nitric acid solution is 1 g:50-60 mL; the length-diameter ratio of the carbon nano tube is 10-30, and the inner diameter is 10-20 nm;
b) Mixing carboxylated carbon nanotubes and thionyl chloride according to the mass volume ratio of 1g to 100-150 mL, stirring at 80-90 ℃ for reacting for 18-24 h, and drying the product to obtain the carbon acyl chloride nanotubes;
c) Dispersing an acyl chloride carbon nano tube in an organic solvent, then adding L-tyrosine and dicyclohexylcarbodiimide, stirring at 60-70 ℃ for reaction for 18-24 hours, washing and drying the product to obtain a tyrosine modified carbon nano tube; the mass ratio of the acyl chloride carbon nano tube to the L-tyrosine to the dicyclohexylcarbodiimide is 1:1-1.5:0.2-0.3;
(2) Ball milling is carried out on the tyrosine modified carbon nano tube: zirconium silicate beads or zirconium oxide beads are used as grinding balls, ethanol is used as a ball milling medium, and a surfactant is added to ball mill the tyrosine modified carbon nano tube, and then the carbon nano tube is cleaned and dried; the diameter of the grinding ball is 3-5 mm, the ball material mass ratio during ball milling is 3-5:1, the feed liquid ratio is 1 g:20-30 mL, the addition amount of the surfactant is 0.3-0.5% of the mass of ethanol, the ball milling rotating speed is 200-300 rpm, and the ball milling time is 30-60 min;
(3) Mixing the ball-milled tyrosine-modified carbon nanotubes with ceramic particles to obtain composite particles, adding the composite particles, a dispersing agent, a wetting agent and a binder into a solvent, and uniformly stirring and mixing to obtain first coating slurry;
(4) Adding PVDF powder, a dispersing agent, a wetting agent and a binder into a solvent, and uniformly stirring and mixing to obtain second coating slurry;
(5) Coating the first coating slurry on one side or two side surfaces of the base film, and drying for 3-5 min at 115-125 ℃ to obtain a first coating layer;
(6) And coating the second coating slurry on the surface of the first coating layer, and drying for 3-5 min at 115-125 ℃ to obtain the high-ion-conductivity high-temperature-resistant lithium battery diaphragm.
Example 1:
a preparation method of a high-ion conductivity high-temperature-resistant lithium battery diaphragm comprises the following steps:
(1) Preparing tyrosine modified carbon nano tubes:
a) Mixing carbon nano tubes (length-diameter ratio is 10-30, inner diameter is 10-20 nm) with 1.5mol/L nitric acid solution, performing hydrothermal reaction for 7h at 120 ℃, washing and drying the product to obtain carboxylated carbon nano tubes; the mass volume ratio of the carbon nano tube to the nitric acid solution is 1g:55mL;
b) Mixing carboxylated carbon nanotubes and thionyl chloride according to the mass-volume ratio of 1g to 120mL, stirring at 85 ℃ for reaction for 24 hours, and drying the product to obtain the acyl chloride carbon nanotubes;
c) Dispersing an acyl chloride carbon nano tube in a DMF solvent, then adding L-tyrosine and dicyclohexylcarbodiimide, stirring at 65 ℃ for reaction for 24 hours, washing and drying a product to obtain a tyrosine modified carbon nano tube; the mass ratio of the acyl chloride carbon nano tube to the L-tyrosine to the dicyclohexylcarbodiimide is 1:1.2:0.25;
(2) Ball milling is carried out on the tyrosine modified carbon nano tube: using zirconia beads with the diameter of 3mm as grinding balls, using absolute ethyl alcohol as a ball milling medium, adding a surfactant SDS (sodium dodecyl sulfate) to ball mill the tyrosine modified carbon nano tube, and then cleaning and drying; the ball material mass ratio during ball milling is 3:1, the feed liquid ratio is 1g:25mL, the addition amount of SDS is 0.4% of the ethanol mass, the ball milling rotating speed is 250rpm, and the ball milling time is 40min;
(3) Mixing the ball-milled tyrosine-modified carbon nanotubes with magnesium oxide particles according to a mass ratio of 10:90 to obtain composite particles, adding 100 parts of composite particles, 2 parts of TNWDIS, 4 parts of sodium dodecyl sulfate and 30 parts of aqueous acrylate binder into 250 parts of water according to parts by weight, and uniformly stirring and mixing to obtain first coating slurry;
(4) Adding 100 parts of PVDF powder, 8 parts of stearamide, 6 parts of sodium dodecyl sulfate and 8 parts of aqueous acrylic ester binder into 250 parts of water, and uniformly stirring and mixing to obtain second coating slurry;
(5) Coating the first coating slurry on one side surface of a PE base film with the thickness of 12 mu m, and drying for 4min at 120 ℃ to obtain a first coating layer with the thickness of 2 mu m;
(6) And coating the second coating slurry on the surface of the first coating layer, and drying for 4min at 120 ℃ to obtain a second coating layer with the thickness of 2 mu m, thereby finally obtaining the high-ion-conductivity high-temperature-resistant lithium battery diaphragm.
Example 2:
a preparation method of a high-ion conductivity high-temperature-resistant lithium battery diaphragm comprises the following steps:
(1) Preparing tyrosine modified carbon nano tubes:
a) Mixing carbon nano tubes (length-diameter ratio is 10-30, inner diameter is 10-20 nm) with 1mol/L nitric acid solution, performing hydrothermal reaction for 6 hours at 125 ℃, washing and drying the product to obtain carboxylated carbon nano tubes; the mass volume ratio of the carbon nano tube to the nitric acid solution is 1g to 50mL;
b) Mixing carboxylated carbon nanotubes and thionyl chloride according to the mass volume ratio of 1g to 100mL, stirring at 90 ℃ for reaction for 18 hours, and drying the product to obtain the acyl chloride carbon nanotubes;
c) Dispersing an acyl chloride carbon nano tube in a DMF solvent, then adding L-tyrosine and dicyclohexylcarbodiimide, stirring at 60 ℃ for reaction for 24 hours, washing and drying a product to obtain a tyrosine modified carbon nano tube; the mass ratio of the acyl chloride carbon nano tube to the L-tyrosine to the dicyclohexylcarbodiimide is 1:1:0.2;
(2) Ball milling is carried out on the tyrosine modified carbon nano tube: using zirconia beads with the diameter of 3mm as grinding balls, using absolute ethyl alcohol as a ball milling medium, adding a surfactant SDS (sodium dodecyl sulfate) to ball mill the tyrosine modified carbon nano tube, and then cleaning and drying; the ball material mass ratio during ball milling is 4:1, the feed liquid ratio is 1g:20mL, the addition amount of SDS is 0.3% of the ethanol mass, the ball milling rotating speed is 200rpm, and the ball milling time is 60min;
(3) Mixing the ball-milled tyrosine-modified carbon nanotubes with magnesium oxide particles according to a mass ratio of 20:80 to obtain composite particles, adding 100 parts of composite particles, 1 part of TNWDIS, 3 parts of sodium dodecyl sulfate and 10 parts of aqueous acrylate binder into 200 parts of water according to parts by weight, and stirring and mixing uniformly to obtain first coating slurry;
(4) Adding 100 parts of PVDF powder, 5 parts of stearamide, 5 parts of sodium dodecyl sulfate and 3 parts of aqueous acrylic ester binder into 200 parts of water, and uniformly stirring and mixing to obtain second coating slurry;
(5) Coating the first coating slurry on one side surface of a PE base film with the thickness of 12 mu m, and drying for 5min at 115 ℃ to obtain a first coating layer with the thickness of 2 mu m;
(6) And coating the second coating slurry on the surface of the first coating layer, and drying for 5min at 115 ℃ to obtain a second coating layer with the thickness of 2 mu m, thereby finally obtaining the high-ion-conductivity high-temperature-resistant lithium battery diaphragm.
Example 3:
a preparation method of a high-ion conductivity high-temperature-resistant lithium battery diaphragm comprises the following steps:
(1) Preparing tyrosine modified carbon nano tubes:
a) Mixing carbon nano tubes (length-diameter ratio is 10-30, inner diameter is 10-20 nm) with 2mol/L nitric acid solution, performing hydrothermal reaction for 8 hours at 115 ℃, washing and drying the product to obtain carboxylated carbon nano tubes; the mass volume ratio of the carbon nano tube to the nitric acid solution is 1g to 60mL;
b) Mixing carboxylated carbon nanotubes and thionyl chloride according to the mass-volume ratio of 1g to 150mL, stirring at 80 ℃ for reaction for 24 hours, and drying the product to obtain the acyl chloride carbon nanotubes;
c) Dispersing an acyl chloride carbon nano tube in a DMF solvent, then adding L-tyrosine and dicyclohexylcarbodiimide, stirring at 70 ℃ for reaction for 18 hours, washing and drying a product to obtain a tyrosine modified carbon nano tube; the mass ratio of the acyl chloride carbon nano tube to the L-tyrosine to the dicyclohexylcarbodiimide is 1:1.5:0.3;
(2) Ball milling is carried out on the tyrosine modified carbon nano tube: using zirconia beads with the diameter of 3mm as grinding balls, using absolute ethyl alcohol as a ball milling medium, adding a surfactant SDS (sodium dodecyl sulfate) to ball mill the tyrosine modified carbon nano tube, and then cleaning and drying; the ball material mass ratio during ball milling is 5:1, the feed liquid ratio is 1g:30mL, the addition amount of SDS is 0.5% of the ethanol mass, the ball milling rotating speed is 300rpm, and the ball milling time is 30min;
(3) Mixing the ball-milled tyrosine-modified carbon nanotubes with magnesium oxide particles according to a mass ratio of 30:70 to obtain composite particles, adding 100 parts of composite particles, 3 parts of TNWDIS, 5 parts of sodium dodecyl sulfate and 40 parts of aqueous acrylate binder into 300 parts of water according to parts by weight, and stirring and mixing uniformly to obtain first coating slurry;
(4) Adding 100 parts of PVDF powder, 10 parts of stearamide, 8 parts of sodium dodecyl sulfate and 10 parts of aqueous acrylic ester binder into 300 parts of water, and uniformly stirring and mixing to obtain second coating slurry;
(5) Coating the first coating slurry on one side surface of a PE base film with the thickness of 12 mu m, and drying for 3min at 125 ℃ to obtain a first coating layer with the thickness of 2 mu m;
(6) And coating the second coating slurry on the surface of the first coating layer, and drying for 3min at 125 ℃ to obtain a second coating layer with the thickness of 2 mu m, thereby finally obtaining the high-ion-conductivity high-temperature-resistant lithium battery diaphragm.
Example 4:
example 4 differs from example 1 in that alumina particles are used as ceramic particles, and the remainder is the same as in example 1.
Comparative example 1:
comparative example 1 is a PE base film not coated with the first and second coating layers.
Comparative example 2:
comparative example 2 is different from example 1 in that the second coating layer is not applied, and the rest is the same as in example 1.
Comparative example 3:
comparative example 3 is different from example 1 in that tyrosine-modified carbon nanotubes are not added to the first coating paste, and the components of the first coating paste include, in parts by weight: 100 parts of magnesium oxide particles, 2 parts of TNWDIS, 4 parts of sodium dodecyl sulfate, 30 parts of a water-based acrylate binder and 250 parts of water; the remainder was the same as in example 1.
Comparative example 4:
comparative example 4 is different from example 1 in that the carbon nanotubes in the first coating paste are not tyrosine-modified; directly ball-milling the carbon nano tube and then mixing the carbon nano tube with magnesium oxide particles to obtain composite particles; the remainder was the same as in example 1.
Comparative example 5:
comparative example 5 was different from example 1 in that tyrosine-modified carbon nanotubes were not ball-milled, and the rest was the same as in example 1.
The performance of the separators produced in the above examples and comparative examples was tested and the results are shown in table 1. The test items are as follows:
(1) Liquid absorption rate:
soaking the diaphragm in electrolyte (for reducing pollution, the EC/DMC/DEC mixed solution with the volume ratio of 1:1:1 is selected to replace the solution), taking out the diaphragm, wiping off superfluous liquid on the surface by using filter paper, and calculating the liquid absorption rate;
(2) Rupture of membranes temperature:
measuring the rupture temperature by adopting a resistance mutation method, wherein the point of suddenly increased resistance is the rupture temperature;
(3) Ionic conductivity:
the body resistance is tested by adopting an assembly mode of steel sheets/diaphragms/steel sheets and an Electrochemical Impedance Spectroscopy (EIS) mode of a VMP3B-10 electrochemical workstation (Bio-Logic Science Instruments), wherein the disturbance voltage amplitude is 5mV, and the frequency is 10 mHz-1 MHz; the calculation relation between the bulk resistance and the ion conductivity is as follows: the ionic conductivity is equal to the ratio of the membrane thickness to the product of the membrane resistance and the effective contact area.
Table 1: diaphragm performance test results.
| Liquid absorption (%) | Rupture temperature (. Degree. C.) | Ion conductivity (mS.cm) -1 ) | |
| Example 1 | 192 | 158 | 0.83 |
| Example 2 | 195 | 155 | 0.91 |
| Example 3 | 197 | 151 | 0.85 |
| Example 4 | 194 | 152 | 0.90 |
| Comparative example 1 | 60 | 120 | 0.36 |
| Comparative example 2 | 156 | 144 | 0.73 |
| Comparative example 3 | 183 | 155 | 0.48 |
| Comparative example 4 | 193 | 154 | 0.66 |
| Comparative example 5 | 191 | 157 | 0.71 |
As can be seen from Table 1, compared with the base film without the coating layer in comparative example 1, the liquid absorption rate, the film breaking temperature and the ion conductivity of the separator prepared by the method in examples 1 to 4 are all greatly improved, the transmission capacity and the high temperature resistance of lithium ions are good, and the electric performance and the safety performance of the lithium battery are improved.
The separator of comparative example 2, in which only the first coating layer was coated, lacks the effect of PVDF in the second coating layer, and both the liquid absorption and the ionic conductivity of the separator were reduced as compared with those of example 1.
The first coating layer of comparative example 3 was free of tyrosine modified carbon nanotubes, and the ionic conductivity of the separator was significantly reduced as compared with example 1, as well as the imbibition rate was reduced, indicating that the addition of carbon nanotubes having a certain aspect ratio improved the ion transport properties and imbibition capacity of the separator.
In comparative example 4, the carbon nanotubes in the first coating layer were modified without tyrosine, and the ionic conductivity of the separator was improved compared to that of comparative example 3 without carbon nanotubes, but there was a significant difference from that of example 1, indicating that grafting of tyrosine can promote ion transport.
In comparative example 5, the ion conductivity of the separator was also reduced as compared with example 1 without ball milling of the tyrosine-modified carbon nanotube. Probably because the length-diameter ratio of the carbon nano tube without ball milling is too long, ceramic particles are not easy to form a uniform and compact stacking structure, and uniform and rapid transmission of lithium ions is not facilitated; moreover, due to the uneven transmission of lithium ions, damage to the separator caused by lithium dendrites may also be caused, and the service life is affected.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention. All equivalent changes and modifications made in accordance with the present invention are intended to be covered by the scope of the appended claims.
Claims (10)
1. The high-ion conductivity high-temperature-resistant lithium battery diaphragm is characterized by comprising a base film, a first coating layer arranged on the surface of the base film and a second coating layer arranged on the surface of the first coating layer;
the first coating layer is coated with a first coating slurry, and the first coating slurry comprises the following components: composite particles, a dispersing agent, a wetting agent, a binder and a solvent; the composite particles are obtained by mixing tyrosine modified carbon nanotubes and ceramic particles in a mass ratio of 10-30:90-70; the particle size of the ceramic particles is 50-100 nm;
the second coating layer is coated with a second coating slurry, the second coating slurry comprising the components: PVDF powder, a dispersing agent, a wetting agent, a binder and a solvent;
the preparation method of the tyrosine modified carbon nano tube comprises the following steps:
a) Reacting the carbon nanotubes with nitric acid to obtain carboxylated carbon nanotubes; the length-diameter ratio of the carbon nano tube is 10-30, and the inner diameter is 10-20 nm;
b) Reacting the carboxylated carbon nano tube with thionyl chloride to obtain an acyl chloride carbon nano tube;
c) And (3) reacting the acyl chloride carbon nano tube with L-tyrosine to obtain the tyrosine modified carbon nano tube.
2. The high ionic conductivity high temperature resistant lithium battery separator of claim 1, wherein the reaction conditions of step a) are: mixing the carbon nano tube with 1-2 mol/L nitric acid solution, performing hydrothermal reaction for 6-8 hours at 115-125 ℃, washing and drying the product to obtain carboxylated carbon nano tube; the mass volume ratio of the carbon nano tube to the nitric acid solution is 1 g:50-60 mL.
3. The high ionic conductivity high temperature resistant lithium battery separator of claim 1, wherein the reaction conditions of step B) are: and mixing the carboxylated carbon nano tube and thionyl chloride according to the mass volume ratio of 1g to 100-150 mL, stirring at 80-90 ℃ for reacting for 18-24 h, and drying the product to obtain the carbon nano tube.
4. The high ionic conductivity high temperature resistant lithium battery separator of claim 1, wherein the reaction conditions of step C) are: dispersing an acyl chloride carbon nano tube in an organic solvent, then adding L-tyrosine and dicyclohexylcarbodiimide, stirring at 60-70 ℃ for reaction for 18-24 hours, washing and drying the product to obtain a tyrosine modified carbon nano tube; the mass ratio of the acyl chloride carbon nano tube to the L-tyrosine to the dicyclohexylcarbodiimide is 1:1-1.5:0.2-0.3.
5. The high ionic conductivity high temperature resistant lithium battery separator of claim 1, wherein the first coating slurry comprises the following components in parts by weight: 100 parts of composite particles, 1-3 parts of dispersing agent, 3-5 parts of wetting agent, 10-40 parts of binder and 200-300 parts of solvent;
the ceramic particles in the composite particles are selected from one or more of aluminum oxide, magnesium oxide, titanium dioxide, silicon dioxide and antimony trioxide; the dispersing agent is TNWDIS; the wetting agent is dodecyl sulfonate; the binder is an aqueous acrylic ester binder, and the solid content is 30-50wt%; the solvent is water.
6. The high ionic conductivity high temperature resistant lithium battery separator of claim 1, wherein the second coating slurry comprises the following components in parts by weight: 100 parts of PVDF powder, 5-10 parts of dispersing agent, 5-8 parts of wetting agent, 3-10 parts of binder and 200-300 parts of solvent;
the dispersing agent is aliphatic amide dispersing agent, and the wetting agent is dodecyl sulfonate; the binder is an aqueous acrylic ester binder, and the solid content is 30-50wt%; the solvent is water.
7. The high-ion-conductivity high-temperature-resistant lithium battery diaphragm according to claim 1, wherein the thickness of the base film is 9-16 μm, the thickness of the first coating layer is 2-4 μm, and the thickness of the second coating layer is 1-3 μm.
8. A method for preparing the high ion conductivity high temperature resistant lithium battery diaphragm according to any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) Preparing tyrosine modified carbon nano-tubes;
(2) Ball milling is carried out on the tyrosine modified carbon nano tube;
(3) Mixing the ball-milled tyrosine-modified carbon nanotubes with ceramic particles to obtain composite particles, adding the composite particles, a dispersing agent, a wetting agent and a binder into a solvent, and uniformly stirring and mixing to obtain first coating slurry;
(4) Adding PVDF powder, a dispersing agent, a wetting agent and a binder into a solvent, and uniformly stirring and mixing to obtain second coating slurry;
(5) Coating the first coating slurry on one side or two side surfaces of the base film, and drying to obtain a first coating layer;
(6) And coating the second coating slurry on the surface of the first coating layer, and drying to obtain the high-ion-conductivity high-temperature-resistant lithium battery diaphragm.
9. The method of claim 8, wherein the ball milling method in step (2) is: zirconium silicate beads or zirconium oxide beads are used as grinding balls, ethanol is used as a ball milling medium, and a surfactant is added to ball mill the tyrosine modified carbon nano tube, and then the carbon nano tube is cleaned and dried; the diameter of the grinding ball is 3-5 mm, the ball material mass ratio during ball milling is 3-5:1, the feed liquid ratio is 1 g:20-30 mL, the addition amount of the surfactant is 0.3-0.5% of the mass of ethanol, the ball milling rotating speed is 200-300 rpm, and the ball milling time is 30-60 min.
10. The method according to claim 8, wherein the drying temperature in step (5) and step (6) is 115 to 125 ℃ and the drying time is 3 to 5 minutes.
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