CN114725615A - Battery diaphragm and preparation method and application thereof - Google Patents
Battery diaphragm and preparation method and application thereof Download PDFInfo
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- CN114725615A CN114725615A CN202210363663.4A CN202210363663A CN114725615A CN 114725615 A CN114725615 A CN 114725615A CN 202210363663 A CN202210363663 A CN 202210363663A CN 114725615 A CN114725615 A CN 114725615A
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- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 63
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 60
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 60
- 239000010455 vermiculite Substances 0.000 claims abstract description 60
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 238000000576 coating method Methods 0.000 claims abstract description 52
- 239000002135 nanosheet Substances 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 239000000080 wetting agent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- -1 polyethylene Polymers 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000004698 Polyethylene Substances 0.000 claims description 17
- 229920000573 polyethylene Polymers 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 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 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- BBZQHVYNSCMSCC-UHFFFAOYSA-N C1(=CC=CC2=CC=CC=C12)S(=O)(=O)O.C(C)(C)[Na] Chemical compound C1(=CC=CC2=CC=CC=C12)S(=O)(=O)O.C(C)(C)[Na] BBZQHVYNSCMSCC-UHFFFAOYSA-N 0.000 claims 1
- INBMQYRWBRXTJA-UHFFFAOYSA-N C1(=CC=CC2=CC=CC=C12)S(=O)(=O)O.C(CCC)[Na] Chemical compound C1(=CC=CC2=CC=CC=C12)S(=O)(=O)O.C(CCC)[Na] INBMQYRWBRXTJA-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 12
- 238000001132 ultrasonic dispersion Methods 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006250 one-dimensional material Substances 0.000 description 2
- FGDMJJQHQDFUCP-UHFFFAOYSA-M sodium;2-propan-2-ylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(C(C)C)=CC=C21 FGDMJJQHQDFUCP-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- LRJNNJLCNGFADW-UHFFFAOYSA-N diethyl carbonate;1,3-dioxolan-2-one Chemical compound O=C1OCCO1.CCOC(=O)OCC LRJNNJLCNGFADW-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide 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
- H01M50/409—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
- 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
- H01M50/434—Ceramics
-
- 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
-
- 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)
- Ceramic Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a battery diaphragm and a preparation method and application thereof. The battery diaphragm comprises a diaphragm base material and a vermiculite nanosheet-nano ceramic particle composite coating attached to one side or two sides of the diaphragm base material. The preparation method of the battery diaphragm comprises the following steps: 1) dispersing vermiculite nanosheets, nano ceramic particles, a binder and a wetting agent in a solvent to obtain a coating liquid; 2) and coating the coating solution on one side or two sides of the diaphragm substrate, and drying to obtain the battery diaphragm. The battery diaphragm disclosed by the invention has the advantages of excellent thermal stability, lithium dendrite resistance, good lithium ion transmission performance and the like, and the preparation process is simple, environment-friendly and suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a battery diaphragm and a preparation method and application thereof.
Background
The lithium metal negative electrode has high reversible capacity (3860mAh/g) and low electrochemical oxidation-reduction potential (-3.040V vs. SHE), and is an ideal negative electrode material. However, lithium metal has a serious dendrite problem, and a large amount of grown lithium dendrites can pierce a separator and cause a short circuit, which can eventually cause fire or even explosion, seriously threatening the safe operation of a battery. In addition, polyolefin diaphragms are commonly adopted in the conventional lithium ion batteries, are poor in thermal stability, and are easy to generate thermal shrinkage when the temperature rises to cause short circuit, so that safety accidents can be caused finally.
Inorganic ceramic particles such as alumina and silica modify the polyolefin separator to improve the thermal stability, wettability and mechanical strength, but do not have the effect of suppressing or reducing lithium dendrites. Two-dimensional materials such as vermiculite, graphene, MOF, montmorillonite and the like generally have higher Young modulus, can resist penetration of lithium dendrites, and further can improve the safety performance of the battery, but the two-dimensional nanosheets are easy to gather when forming a film, so that the specific surface area and the interlayer spacing of the materials are reduced, and the transmission of lithium ions is not facilitated. The polyolefin diaphragm is compositely modified by the two-dimensional material and the one-dimensional material or the zero-dimensional material, the one-dimensional material or the zero-dimensional material can be uniformly embedded between two-dimensional nanosheets, the two-dimensional nanosheets are prevented from being densely stacked, the regulating capability of a two-dimensional plane on lithium ion transmission is enhanced, but the thermal stability of the two-dimensional material is unsatisfactory, and the safe operation of a lithium ion battery at a higher temperature (130 ℃) cannot be guaranteed. In conclusion, the existing battery diaphragm is difficult to completely meet the practical application requirements.
Therefore, the development of the battery diaphragm with excellent thermal stability, lithium dendrite resistance and good lithium ion transmission performance is of great significance.
Disclosure of Invention
The invention aims to provide a battery diaphragm and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a battery diaphragm comprises a diaphragm substrate and a vermiculite nanosheet-nano ceramic particle composite coating attached to one or two sides of the diaphragm substrate.
Preferably, the membrane substrate is selected from one of a polyethylene membrane, a polypropylene membrane and a polyethylene film-polypropylene film composite membrane.
Preferably, the thickness of the separator substrate is 5 to 20 μm.
Preferably, the mass ratio of the vermiculite nanosheets to the nano ceramic particles in the vermiculite nanosheet-nano ceramic particle composite coating is 5.3-25: 100.
Preferably, the vermiculite nanosheets and the nano ceramic particles in the vermiculite nanosheet-nano ceramic particle composite coating are stacked in a staggered manner to form a sandwich structure.
Preferably, the flake diameter of the vermiculite nanosheet is 1-50 μm, and the thickness is 0.5-10 nm.
Preferably, the vermiculite nanosheet is prepared by the following method: adding vermiculite into a saturated sodium chloride solution, heating and refluxing, filtering, washing the filtered solid with water and ethanol, adding into a lithium chloride solution, heating and refluxing, filtering, washing the filtered solid with water and ethanol, re-dispersing in water, centrifuging, and washing the lower layer of solid with water and ethanol to obtain the vermiculite nanosheet.
Preferably, the centrifugation is carried out at the rotating speed of the centrifuge of 6000r/min to 8000r/min for 10min to 30 min.
Preferably, the nano ceramic particles are selected from at least one of nano silica particles, nano alumina particles, nano titania particles and nano zirconia particles.
Preferably, the particle size of the nano ceramic particles is 20nm to 50 nm.
Preferably, the thickness of the vermiculite nanosheet-nano ceramic particle composite coating is 0.5-2 μm.
Preferably, the composition of the vermiculite nanosheet-nano ceramic particle composite coating further comprises a binder and a wetting agent.
The preparation method of the battery diaphragm comprises the following steps:
1) dispersing vermiculite nanosheets, nano ceramic particles, a binder and a wetting agent in a solvent to obtain a coating liquid;
2) and coating the coating solution on one side or two sides of the diaphragm substrate, and drying to obtain the battery diaphragm.
Preferably, the binder in step 1) is selected from at least one of lithium polyacrylate, sodium carboxymethyl cellulose, sodium alginate and polyvinyl alcohol.
Preferably, the wetting agent in step 1) is at least one selected from sodium alkyl sulfate, sodium butyl naphthalene sulfonate, sodium isopropyl naphthalene sulfonate, sodium aryl naphthalene sulfonate and sodium dodecyl benzene sulfonate.
Preferably, the dispersing mode in the step 1) is ultrasonic dispersing.
Preferably, the ultrasonic dispersion is carried out under the conditions that the ultrasonic power is 10W-50W and the ultrasonic frequency is 40 Hz-60 Hz, and the ultrasonic dispersion time is 2 h-6 h.
Preferably, the drying in the step 2) is carried out at the temperature of 40-80 ℃, and the drying time is 6-12 h.
The lithium ion battery comprises the battery diaphragm.
The invention has the beneficial effects that: the battery diaphragm disclosed by the invention has the advantages of excellent thermal stability, lithium dendrite resistance, good lithium ion transmission performance and the like, and the preparation process is simple, environment-friendly and suitable for large-scale industrial production.
Specifically, the method comprises the following steps: the battery diaphragm of the invention takes the nano ceramic particles as a main body frame, can prevent vermiculite nano sheets from being stacked while ensuring low thickness and excellent thermal stability of the battery diaphragm, forms a porous sandwich structure, realizes high lithium ion conductivity, can promote dissociation of lithium salt and conduction of lithium ions by the vermiculite nano sheets, promotes uniform transmission of the lithium ions, reduces generation of lithium dendrites, has ultrahigh Young modulus, can resist piercing of the lithium dendrites, and prolongs the service life of a lithium battery (the cycle life of an assembled lithium symmetrical battery is greatly prolonged).
Drawings
Fig. 1 is an SEM image of a cross section of the battery separator in example 1.
FIG. 2 shows the current density of 0.5mA/cm for a lithium symmetrical battery assembled by the polyethylene separator and the battery separator in example 12The capacity is 0.5mAh/cm2Strip ofAnd (5) a cycle performance test result chart under the condition.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
The vermiculite nanosheet dispersions of examples 1-6 and comparative examples 2-3 were prepared by the following method:
adding vermiculite into a saturated sodium chloride solution, heating and refluxing for 24h, filtering, repeatedly washing the filtered solid with water and ethanol, adding into a lithium chloride solution, heating and refluxing for 24h, filtering, repeatedly washing the filtered solid with water and ethanol, re-dispersing in water, centrifuging at the rotating speed of 6000r/min in a centrifuge for 30min, washing the lower-layer solid with water and ethanol, adding water, and performing ultrasonic dispersion to obtain the vermiculite nanosheet dispersion liquid.
Example 1:
a battery separator, the preparation method of which comprises the following steps:
1) adding 13.3mL of 1.5mg/mL vermiculite nanosheet (with the sheet diameter of 1-50 micrometers and the thickness of 0.5-10 nm) dispersion liquid and 0.38g of 50 nm-sized nano alumina particles into 26.2g of deionized water, stirring for 8 hours, then carrying out ultrasonic treatment for 0.5 hour, carrying out ultrasonic treatment with the ultrasonic power of 40W, the ultrasonic frequency of 50Hz and the ultrasonic dispersion time of 4 hours to obtain a vermiculite nanosheet-nano alumina particle dispersion liquid (the total mass percentage of the vermiculite nanosheet and the nano alumina particles is about 1%), adding 0.044g of lithium polyacrylate, 0.08g of sodium hydroxyethyl cellulose and 0.04g of sodium dodecyl sulfate, and stirring for 8 hours to obtain a coating liquid;
2) and (3) blade-coating the coating liquid on one surface of a polyethylene diaphragm with the thickness of 9 mu m (the thickness of the vermiculite nanosheet-nano alumina particle composite coating is 1.8 mu m), and drying at 70 ℃ for 12h to obtain the battery diaphragm.
Example 2:
a battery separator, the preparation method of which comprises the following steps:
1) adding 20mL of vermiculite nanosheet (1-50 μm in flake diameter and 0.5-10 nm in thickness) dispersion liquid with the concentration of 2mg/mL and 0.36g of nano titanium dioxide particles with the particle size of 40nm into 19.5g of deionized water, stirring for 8 hours, then carrying out ultrasonic treatment for 0.5 hour, wherein the ultrasonic power is 40W, the ultrasonic frequency is 50Hz, and the ultrasonic dispersion time is 2 hours to obtain the vermiculite nanosheet-nano titanium dioxide particle dispersion liquid (the total mass percentage content of the vermiculite nanosheet and the nano titanium dioxide particles is about 1%), adding 0.1g of sodium carboxymethylcellulose, 0.08g of sodium hydroxyethyl cellulose and 0.04g of sodium butylnaphthalene sulfonate, and stirring for 8 hours to obtain a coating liquid;
2) and (3) coating the coating liquid on one surface of a polyethylene diaphragm with the thickness of 9 mu m (the thickness of the vermiculite nanosheet-nano titanium dioxide particle composite coating is 1.7 mu m), and drying at 70 ℃ for 12h to obtain the battery diaphragm.
Example 3:
a battery separator, the preparation method of which comprises the following steps:
1) adding 26.7mL of vermiculite nanosheet (with the flake diameter of 1-50 micrometers and the thickness of 0.5-10 nm) dispersion liquid with the concentration of 3mg/mL and 0.32g of nano silicon dioxide particles with the particle diameter of 50nm into 19.5g of deionized water, stirring for 8 hours, then carrying out ultrasonic treatment for 0.5 hour, carrying out ultrasonic treatment at the ultrasonic power of 40W and the ultrasonic frequency of 50Hz, and carrying out ultrasonic dispersion for 2 hours to obtain vermiculite nanosheet-nano silicon dioxide particle dispersion liquid (the total mass percentage of the vermiculite nanosheet and the nano silicon dioxide particles is about 1 percent), then adding 0.07g of sodium carboxymethylcellulose, 0.08g of sodium hydroxyethyl cellulose and 0.04g of sodium isopropylnaphthalene sulfonate, and stirring for 8 hours to obtain a coating liquid;
2) and (3) coating the coating liquid on one surface of a polyethylene diaphragm with the thickness of 9 mu m (the thickness of the vermiculite nanosheet-nano silicon dioxide particle composite coating is 1.7 mu m), and drying at 70 ℃ for 12h to obtain the battery diaphragm.
Example 4:
a battery separator, the preparation method of which comprises the following steps:
1) adding 26.6mL of vermiculite nanosheet (1-50 μm in flake diameter and 0.5-10 nm in thickness) dispersion liquid with the concentration of 1.5mg/mL and 0.76g of nano silicon dioxide particles with the particle diameter of 50nm into 12.6g of deionized water, stirring for 8 hours, then carrying out ultrasonic treatment for 0.5 hour, wherein the ultrasonic power is 40W, the ultrasonic frequency is 50Hz, and the ultrasonic dispersion time is 2 hours to obtain the vermiculite nanosheet-nano silicon dioxide particle dispersion liquid (the total mass percentage content of the vermiculite nanosheet and the nano silicon dioxide particles is about 1%), then adding 0.088g of sodium carboxymethylcellulose, 0.06g of sodium hydroxyethyl cellulose and 0.04g of sodium dodecyl sulfate, and stirring for 8 hours to obtain a coating liquid;
2) and (3) coating the coating liquid on one surface of a polyethylene diaphragm with the thickness of 9 mu m (the thickness of the vermiculite nano-sheet-nano silicon dioxide particle composite coating is 1.8 mu m), and drying at 70 ℃ for 12h to obtain the battery diaphragm.
Example 5:
a battery separator, the preparation method of which comprises the following steps:
1) adding 70mL of 1.5mg/mL vermiculite nanosheet (1-50 μm in flake diameter and 0.5-10 nm in thickness) dispersion liquid and 2g of 50nm nano zirconium dioxide particles into 927g of deionized water, stirring for 8h, then carrying out ultrasonic treatment for 0.5h, wherein the ultrasonic power is 40W, the ultrasonic frequency is 50Hz, and the ultrasonic dispersion time is 4h to obtain the vermiculite nanosheet-nano zirconium dioxide particle dispersion liquid (the total mass percentage content of the vermiculite nanosheet and the nano zirconium dioxide particles is about 0.2%), adding 0.2g of sodium alginate and 0.5g of sodium dodecyl benzene sulfonate, and stirring for 8h to obtain a coating liquid;
2) and (3) pumping and filtering 1mL of coating solution on one surface of a polyethylene diaphragm with the thickness of 9 mu m (the thickness of the vermiculite nanosheet-nano zirconium dioxide particle composite coating is 1.3 mu m), and drying at 70 ℃ for 12h to obtain the battery diaphragm.
Example 6:
a battery separator, the preparation method of which comprises the following steps:
1) 133mL of 1.5mg/mL vermiculite nanosheet (1-50 μm in sheet diameter and 0.5-10 nm in thickness) dispersion liquid and 0.8g of 50 nm-sized nano alumina particles are added into 865g of deionized water, stirred for 8 hours, subjected to ultrasonic treatment for 0.5 hour, subjected to ultrasonic treatment at the ultrasonic power of 40W and the ultrasonic frequency of 50Hz and subjected to ultrasonic dispersion for 4 hours to obtain a vermiculite nanosheet-nano alumina particle dispersion liquid (the total mass percentage of the vermiculite nanosheet and the nano alumina particles is about 0.1 percent), then 0.1g of polyvinyl alcohol and 0.5g of sodium dodecyl benzene sulfonate are added, and stirred for 8 hours to obtain a coating liquid;
2) and (3) blade-coating the coating liquid on one surface of a polyethylene diaphragm with the thickness of 9 mu m (the thickness of the vermiculite nanosheet-nano alumina particle composite coating is 0.8 mu m), and drying at 70 ℃ for 12h to obtain the battery diaphragm.
Comparative example 1:
a battery separator, the preparation method of which comprises the following steps:
1) adding 0.4g of nano alumina particles with the particle size of 50nm into 39.5g of deionized water, stirring for 8 hours, performing ultrasonic treatment for 0.5 hour, wherein the ultrasonic power is 40W, the ultrasonic frequency is 50Hz, and the ultrasonic dispersion time is 4 hours to obtain nano alumina particle dispersion liquid (the mass percentage of the nano alumina particles is about 1 percent), adding 0.044g of lithium polyacrylate, 0.08g of sodium hydroxyethyl cellulose and 0.04g of sodium alkyl sulfate, and stirring for 8 hours to obtain coating liquid;
2) and (3) coating the coating liquid on one surface of a polyethylene diaphragm with the thickness of 9 mu m (the thickness of the nano alumina particle coating is 1.8 mu m), and drying at 70 ℃ for 12h to obtain the battery diaphragm.
Comparative example 2:
a battery separator, the preparation method of which comprises the following steps:
1) 667mL of 1.5mg/mL vermiculite nanosheet (1-50 μm in flake diameter and 0.5-10 nm in thickness) dispersion liquid is added into 333g of deionized water, stirred for 8h, then subjected to ultrasonic treatment for 0.5h, the ultrasonic power is 40W, the ultrasonic frequency is 50Hz, and the ultrasonic dispersion time is 4h to obtain vermiculite nanosheet dispersion liquid (the mass percentage content of the vermiculite nanosheets is about 0.1%), then 0.1g of lithium polyacrylate and 0.05g of sodium alkyl sulfate are added, and stirred for 8h to obtain a coating liquid;
2) and (3) pumping and filtering 2.5mL of coating solution on one surface of a polyethylene diaphragm with the thickness of 9 microns (the thickness of the vermiculite nanosheet coating is 1.5 microns), and drying at 70 ℃ for 12 hours to obtain the battery diaphragm.
Comparative example 3:
a battery separator, the preparation method of which comprises the following steps:
1) 667mL of 1.5mg/mL vermiculite nanosheet (1-50 μm in flake diameter and 0.5-10 nm in thickness) dispersion liquid is added into 333g of deionized water, stirred for 8h, then subjected to ultrasonic treatment for 0.5h, the ultrasonic power is 40W, the ultrasonic frequency is 50Hz, and the ultrasonic dispersion time is 4h to obtain vermiculite nanosheet dispersion liquid (the mass percentage content of the vermiculite nanosheets is about 0.1%), then 0.1g of lithium polyacrylate and 0.05g of sodium alkyl sulfate are added, and stirred for 8h to obtain a coating liquid;
2) and (3) pumping and filtering 10mL of coating liquid on one surface of a polyethylene diaphragm with the thickness of 9 microns (the thickness of the vermiculite nanosheet coating is 4.1 microns), and drying at 70 ℃ for 12 hours to obtain the battery diaphragm.
And (3) performance testing:
1) a Scanning Electron Microscope (SEM) image of a cross section of the battery separator of example 1 is shown in fig. 1.
As can be seen from fig. 1: the nano alumina particles and the vermiculite nanosheets are stacked in a staggered manner to form a sandwich structure, so that the vermiculite nanosheets are effectively prevented from being tightly stacked.
2) Lithium symmetrical cell assembled by polyethylene separator and cell separator in example 1 (stainless steel/separator/stainless steel cell, electrolyte is LiPF with concentration of 1mol/L6The volume ratio of the ethylene carbonate to the diethyl carbonate is 1:1) at a current density of 0.5mA/cm2The capacity is 0.5mAh/cm2The cycle performance test result under the conditions (2) is shown in FIG. 2.
As can be seen from fig. 2: the cycle life of the lithium symmetrical battery assembled by the battery diaphragm in the example 1 is 2 times that of the lithium symmetrical battery assembled by the polyethylene diaphragm, which shows that the battery assembled by the battery diaphragm in the example 1 has better lithium dendrite resisting effect and higher safety.
3) Respectively adopting the polyethylene diaphragm in the example 1, the battery diaphragms in the examples 1 to 6 and the battery diaphragms in the comparative examples 1 to 3 to assemble a stainless steel/diaphragm/stainless steel battery to test the ionic conductivity, assembling the stainless steel/diaphragm/lithium metal battery to test the lithium ion transference number, wherein the electrolyte is LiPF with the concentration of 1mol/L6The ethylene carbonate-diethyl carbonate solution (volume ratio of ethylene carbonate to diethyl carbonate is 1:1), the results of the test calculation are shown in the following table:
TABLE 1 Performance test results for lithium ion symmetric batteries
As can be seen from Table 1:
a) the battery diaphragm of the embodiment 1-6 can ensure high thermal stability (the thickness is less than 2 μm, and the shrinkage rate at 150 ℃ is less than 8%) of the diaphragm on the premise of low coating thickness;
b) the battery diaphragm of the embodiment 1-6 can ensure that the impedance of the diaphragm is not obviously increased on the premise of ensuring high thermal stability and low thickness, and meets the normal use requirement of the battery;
c) the battery diaphragm of the embodiment 1-6 can improve the transference number of lithium ions and promote the rapid and uniform transmission of the lithium ions, so that the dendritic crystal resistance and the safety of the battery are improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A battery diaphragm is characterized by comprising a diaphragm base material and a vermiculite nanosheet-nano ceramic particle composite coating attached to one side or two sides of the diaphragm base material.
2. The battery separator of claim 1, wherein: the diaphragm base material is selected from one of a polyethylene diaphragm, a polypropylene diaphragm and a polyethylene film-polypropylene film composite diaphragm.
3. The battery separator according to claim 1 or 2, wherein: the thickness of the diaphragm base material is 5-20 μm.
4. The battery separator of claim 1, wherein: the mass ratio of the vermiculite nanosheets to the nano ceramic particles in the vermiculite nanosheet-nano ceramic particle composite coating is 5.3-25: 100.
5. The battery separator of claim 4, wherein: the flake diameter of the vermiculite nanosheet is 1-50 μm, and the thickness is 0.5-10 nm; the particle size of the nano ceramic particles is 20 nm-50 nm.
6. The battery separator according to claim 4 or 5, wherein: the nano ceramic particles are selected from at least one of nano silicon dioxide particles, nano aluminum oxide particles, nano titanium dioxide particles and nano zirconium dioxide particles.
7. The battery separator according to any one of claims 1, 2, 4 and 5, wherein: the thickness of the vermiculite nanosheet-nano ceramic particle composite coating is 0.5-2 microns.
8. The method for preparing a battery separator according to any one of claims 1 to 7, comprising the steps of:
1) dispersing vermiculite nanosheets, nano ceramic particles, a binder and a wetting agent in a solvent to obtain a coating liquid;
2) and coating the coating solution on one side or two sides of the diaphragm substrate, and drying to obtain the battery diaphragm.
9. The method for producing a battery separator according to claim 8, characterized in that: the binder in the step 1) is selected from at least one of lithium polyacrylate, sodium carboxymethyl cellulose, sodium alginate and polyvinyl alcohol; the wetting agent in the step 1) is selected from at least one of alkyl sodium sulfate, butyl sodium naphthalene sulfonate, isopropyl sodium naphthalene sulfonate, aryl sodium naphthalene sulfonate and sodium dodecyl benzene sulfonate.
10. A lithium ion battery comprising the battery separator according to any one of claims 1 to 7.
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| CN111584804A (en) * | 2020-05-08 | 2020-08-25 | 贵州大学 | Preparation method of lithium-sulfur battery diaphragm barrier layer based on two-dimensional nano clay |
| CN113351018A (en) * | 2021-06-29 | 2021-09-07 | 华南理工大学 | vermiculite-MXene composite membrane and preparation method and application thereof |
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| KR20080017110A (en) * | 2006-08-21 | 2008-02-26 | 주식회사 엘지화학 | Sheet-typed separator coated with clay mineral and lithium electrochemical cell employing the same |
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| CN107785522A (en) * | 2016-08-29 | 2018-03-09 | 比亚迪股份有限公司 | A kind of lithium ion battery separator and lithium ion battery and preparation method thereof |
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