CN114824647B - Lithium ion battery diaphragm based on aluminum hydroxide coaxial nanotubes and preparation method thereof - Google Patents
Lithium ion battery diaphragm based on aluminum hydroxide coaxial nanotubes and preparation method thereof Download PDFInfo
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- CN114824647B CN114824647B CN202210553693.1A CN202210553693A CN114824647B CN 114824647 B CN114824647 B CN 114824647B CN 202210553693 A CN202210553693 A CN 202210553693A CN 114824647 B CN114824647 B CN 114824647B
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- lithium ion
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- 239000002071 nanotube Substances 0.000 title claims abstract description 144
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 title claims abstract description 40
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 98
- 239000008103 glucose Substances 0.000 claims abstract description 98
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011230 binding agent Substances 0.000 claims abstract description 34
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002303 glucose derivatives Chemical class 0.000 claims abstract description 23
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003063 flame retardant Substances 0.000 claims abstract description 16
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 14
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 14
- 241001330002 Bambuseae Species 0.000 claims abstract description 14
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 14
- 239000011425 bamboo Substances 0.000 claims abstract description 14
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 14
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 118
- 238000003756 stirring Methods 0.000 claims description 73
- 239000000377 silicon dioxide Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 47
- 238000005406 washing Methods 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 43
- 239000002070 nanowire Substances 0.000 claims description 43
- 238000001914 filtration Methods 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 37
- 235000012239 silicon dioxide Nutrition 0.000 claims description 37
- 238000001816 cooling Methods 0.000 claims description 29
- 239000002270 dispersing agent Substances 0.000 claims description 28
- 239000002562 thickening agent Substances 0.000 claims description 27
- 239000000080 wetting agent Substances 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 24
- 239000012498 ultrapure water Substances 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 19
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000006255 coating slurry Substances 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 16
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000011247 coating layer Substances 0.000 claims description 9
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 8
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000007761 roller coating Methods 0.000 claims description 8
- 125000005372 silanol group Chemical group 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 238000009730 filament winding Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- -1 p-xylylene alcohol Chemical compound 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002090 nanochannel Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007336 electrophilic substitution reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a lithium ion battery diaphragm based on an aluminum hydroxide coaxial nanotube and a preparation method thereof, and glucose derived C@ porous Al (OH) is introduced into the diaphragm 3 The coaxial nano tube improves the mechanical strength and the heat shrinkage performance of the diaphragm, and greatly enhances the liquid absorption and retention capacity of the diaphragm; the COPNA resin is used as the binder to effectively improve the complexity of macromolecular crosslinked network in the diaphragm, and has excellent affinity with the carbon material to effectively improve the glucose derivative C@ porous Al (OH) 3 The affinity of the coaxial nanotube to the diaphragm effectively prolongs the service life of the diaphragm; bamboo tar is selected as a raw material, terephthalyl alcohol is used as a cross-linking agent, and p-toluenesulfonic acid is used as a catalyst to synthesize COPNA resin; the adhesive is modified, so that the heat shrinkage, flame retardance and ionic conductivity of the diaphragm are effectively improved; introducing DOPO and derivatives thereof, octaaminopropyl cage-type silsesquioxane and glucose derived C@ porous Al (OH) 3 The coaxial nano tube is compounded with a plurality of flame-retardant elements to realize synergistic flame retardance, so that the safety of the diaphragm is effectively improved.
Description
Technical Field
The invention relates to the field of battery diaphragms, in particular to a lithium ion battery diaphragm based on aluminum hydroxide coaxial nanotubes and a preparation method thereof.
Background
The lithium battery is a novel secondary battery, has the advantages of high energy density, long cycle life and the like, is widely applied to portable electronic devices, energy storage and power automobiles, and is increasingly applied to the power automobiles along with the development of new energy industries. The diaphragm is an important component of the lithium battery, plays a role in effectively preventing the contact of the positive electrode and the negative electrode from generating short circuit and ensuring the safety of the lithium battery, and therefore, has higher requirements on the performance of the diaphragm.
Polyolefin separators that are currently the most widely used lithium battery separators, but the polyolefin separators on the current market also have the following disadvantages: (1) the ionic conductivity is low, the internal resistance of the battery is increased, and the charge and discharge of the lithium ion battery under the condition of high multiplying power are not facilitated; (2) the problems of poor bonding performance of the polar plate and insufficient performance of the electrophilic solution, such as poor hardness, poor cycle performance, low thermal stability, unstable interface between the polar plate and the diaphragm, and the like of the battery are caused, so that the improvement of the energy density of the battery and the development of the high-performance ultrathin battery are greatly limited; (3) when the battery has thermal runaway, the melting point of the polyolefin material is very low, and the polyolefin diaphragm is easy to break the film to aggravate the thermal runaway, so that the battery burns and even explodes.
Therefore, the development of lithium ion battery separators with high ion conductivity, high electrolyte wettability and high flame retardance is a commonly sought-after goal in the industry.
Disclosure of Invention
The invention aims to solve the problems in the prior art by using a lithium ion battery diaphragm based on an aluminum hydroxide coaxial nanotube and a preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises a base film and a coating layer formed on the surface of the base film; the coating comprises the following components in parts by weight: 0.35 to 0.8 percent of dispersing agent and 9 to 23 percent of glucose derivative C@ porous Al (OH) 3 Coaxial nano tube, 0.2% -0.85% of thickening agent, 0.6% -1.3% of binder, 0.1% -0.4% of wetting agent and the balance of deionized water.
Aiming at the problem that the existing polyolefin diaphragm has poor adhesion to a pole piece and electrolyte wettability, the main solution is to coat a water-based PVDF adhesive layer on one side or two sides of the polyolefin diaphragm, and the adhesive coating layer can effectively improve the adhesion of the diaphragm and has good wettability with the electrolyte, but has the problem of easy falling; aiming at the problems of low ionic conductivity and poor heat resistance of a polyolefin diaphragm, the main solution is to coat a high-temperature resistant ceramic coating on one side or two sides of the polyolefin diaphragm at present, so that the diaphragm can be delayed to be closed to 150 ℃, but the closed-pore temperature of 150 ℃ cannot completely avoid the short circuit of a lithium battery at high temperature and spontaneous combustion caused by the short circuit, so that the heat resistance of the diaphragm needs to be further improved, and the rupture risk of the diaphragm is reduced, thereby improving the safety of the battery.
According to the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube, the glucose-derived C nanotube is selected as a coating material to be added into a slurry component, wherein the glucose-derived C nanotube has good high temperature resistance and heat conduction performance, and is beneficial to improving the heat resistance of a coating, so that the heat resistance of the diaphragm is improved.
Further, the preparation of the glucose-derived C nanotubes comprises the following steps:
adding the silicon dioxide nanowire subjected to hydrophilic treatment into a glucose solution under the condition of continuous stirring, continuing to magnetically stir for 40-50min, then performing ultrasonic dispersion for 6-7h, transferring into a stainless steel autoclave with a PTFE lining, heating for 5-6h at 95-100 ℃, naturally cooling to 18-25 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 70-80 ℃ for 20-24h, and vacuum degree being 0.08Mpa to obtain the carbon-coated silicon dioxide nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, maintaining for 5-6h, filtering, washing, drying at 70-80 ℃ for 10-12h, and drying to obtain the glucose-derived C nanotube.
Further, the mass molar ratio of the silicon dioxide nanowire after hydrophilic treatment to glucose in the glucose solution is 92 mg/101.4 mmol.
The preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring cetyl trimethyl ammonium bromide, absolute ethyl alcohol and deionized water, adding ammonia water solution and 0.1g of tetraethoxysilane, adding (3-mercaptopropyl) trimethoxysilane with the mass fraction of 6%, immersing an indium tin oxide coated substrate, standing for 28h at 55-58 ℃, washing, aging at 100 ℃, washing with 0.15mol/L hydrochloric acid ethanol solution, treating with hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain the silicon dioxide nanowire after hydrophilic treatment.
The sulfonic acid group is loaded on the vertical mesoporous silica pore canal in situ, the pore canal structure is not changed, the selective permeability of the nano channel is mainly caused by a size effect and a charge effect, and when the nano channel is completely occupied by an electric double layer, the selective permeability is optimal.
Further, glucose derived C@ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring glucose derived C nanotube and ultrapure water for 80-90min, then performing ultrasonic dispersion for 190-200min, adding aluminum sulfate and urea, continuously stirring until dissolving, heating to 90-95C for reacting for 12-15h, performing suction filtration, washing with ultrapure water, vacuum drying at 75-80deg.C for 32-36h, drying, heating to 115-120deg.C at a heating rate of 2deg.C/min from 18-25deg.C, maintaining the temperature for 150-155min, and cooling to obtain glucose derived C@ porous Al (OH) 3 Coaxial nanotubes.
Further, the mass ratio of the glucose-derived C nano tube to the aluminum sulfate to the urea is 1.97:13.46:26.59.
Lithium ion battery separator based on aluminium hydroxide coaxial nanotubes, wherein glucose derived C@ porous Al (OH) 3 The introduction of the coaxial nano tube greatly improves the mechanical strength and the heat shrinkage performance of the diaphragm due to the excellent performance of the coaxial nano tube and the cross-linking among different nano tubes; in addition, glucose-derived C nanotubes and porous Al (OH) with flame retardant properties 3 The two can cooperate, which further improves the mechanical properties and heat shrinkage properties of the separator;
the introduction of the glucose derived C nano tube increases the mechanical property of the diaphragm on one hand and enhances the conductive property of the diaphragm on the other hand, thereby being beneficial to enhancing the rapid transmission of lithium ions; in addition, glucose derived C@ porous Al (OH) 3 The coaxial nanotube has a hollow structure as a whole and is coated with Al (OH) 3 The porous structure is presented, so that the lithium ion conductivity is further improved, the specific surface area of the material is greatly increased, and the liquid absorption and retention capacity of the diaphragm is greatly enhanced.
Al (OH) introduced into lithium ion battery diaphragm based on aluminum hydroxide coaxial nano tube 3 Greatly improves the flame retardant capability of the diaphragm, al (OH) 3 Is formed by heating, decomposing and absorbing crystal waterA layer of Al (OH) when the temperature is raised to the decomposition temperature 3 The decomposition releases water vapor, absorbs latent heat, dilutes the concentration of oxygen and combustible gas near the surface of the combustion object, and makes surface combustion difficult to carry out; the charring layer formed on the surface prevents oxygen and heat from entering, and aluminum oxide generated by decomposition of the charring layer is also a good refractory material, has good high temperature resistance and heat conduction performance, and can improve the capability of the material for resisting open fire.
Further, the base film is a polyolefin separator; the dispersing agent is a hydrolyzed polymaleic anhydride dispersing agent, the thickening agent is a hydroxymethyl cellulose sodium dispersing agent, the binder is a COPNA resin binder, and the wetting agent is a silanol nonionic surfactant.
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises the following steps:
s1: dispersing agent, glucose derived C@ porous Al (OH) 3 Premixing the coaxial nanotubes in ultrapure water for 10-90min, wherein the rotating speed is 100-600rpm; adding thickener, stirring for 10-90min at 350-900rpm; adding binder, and stirring for 40-120min at 350-700rpm; adding wetting agent, stirring for 30-90min at 400-900rpm; filtering to remove iron to obtain glucose derivative C@ porous Al (OH) 3 Coating slurry on the coaxial nano tube;
s2: the prepared glucose is derived from C@ porous Al (OH) by adopting a micro-gravure roller coating process 3 The coaxial nanotube coating slurry is coated on two sides of a base film step by step, baked at 65-70 ℃ and then rolled, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained.
The COPNA resin is used as the binder to effectively improve the complexity of macromolecular crosslinked network in the diaphragm, and has excellent affinity with the carbon material to effectively improve the glucose derivative C@ porous Al (OH) 3 The affinity of the coaxial nanotube and the diaphragm effectively prolongs the service life of the diaphragm.
The prior market mostly adopts non-renewable petrochemical raw material COPNA resin, which not only has complex working procedures and large pollution in the processing process, but also has low crosslinking density due to high monomer condensed ring density and large steric hindrance, and has poor carbon residue rate and heat resistance.
According to the invention, bamboo is used as a renewable raw material, bamboo tar is used as a raw material, terephthalyl alcohol is used as a cross-linking agent, and p-toluenesulfonic acid is used as a catalyst to synthesize COPNA resin, so that the pretreatment process is simple, the cost is low, and the emission of waste is reduced.
Further, the preparation of the COPNA resin includes the following steps: under the nitrogen environment, the bamboo tar and the terephthalyl alcohol are weighed according to the mass ratio of 1:1, the p-toluenesulfonic acid with the mass fraction of 5.4-6.8% is added, the reaction is carried out at 130-150 ℃ until the phenomenon of filament winding occurs, the heating is stopped, and the material is discharged and cooled, thus obtaining the COPNA resin.
In an acidic environment, the p-xylylene alcohol can generate active carbon positive ions, and generates electrophilic substitution reaction with a large amount of phenols in bamboo tar and benzene rings in derivatives thereof, alcohol hydroxyl groups in the generated products are dehydrated under the action of acid to generate carbon positive ions again, the carbon positive ions react with aromatic hydrocarbon to generate cross-linked macromolecules, the viscosity of the system is increased along with the deepening of the cross-linking degree, water vapor is not escaped any more, and the cross-linked molecules are cross-linked into a network structure, so that COPNA resin is obtained, and the softening point and heat resistance of the obtained COPNA resin are improved by controlling the addition amount of p-toluenesulfonic acid.
The adhesive is modified, so that the glucose derivative C@ porous Al (OH) is effectively improved 3 The binding force among the coaxial nano tube, the thickener, the binder and the wetting agent effectively improves the thermal shrinkage, the flame retardance and the ionic conductivity of the diaphragm.
Further, the binder is modified COPNA resin, and the preparation method comprises the following steps:
(1) In a nitrogen environment, itaconic acid, deionized water and 1, 6-hexamethylenediamine are reacted for 20-30min at 55-60 ℃ to obtain itaconic acid mixed solution;
(2) Mixing deionized water, absolute ethyl alcohol, acetonitrile, triethylamine and tetraethylammonium hydroxide in a constant-temperature water bath at 52-56 ℃; adding 3-aminopropyl triethoxysilane, refluxing at 52-56 ℃ for 20-22h, distilling under reduced pressure for concentration, adding the concentrated solution into petroleum ether, standing, vacuum filtering, washing with acetone for 2-5 times, and vacuum drying to obtain octaaminopropyl cage-type silsesquioxane;
(3) Mixing and stirring DOPO and itaconic acid mixed solution, heating to 85-88 ℃ and reacting for 2.5-3h; filtering while the mixture is hot, cooling the mixture to 18-25 ℃, transferring the mixture to ice water bath for cooling for 9-11h, and filtering the mixture to obtain the water-soluble flame retardant; adding the octaaminopropyl cage-type silsesquioxane and the COPNA resin, and carrying out ultrasonic stirring for 30-60min to obtain the modified COPNA resin.
Further, the molar volume ratio of itaconic acid, 1, 6-hexamethylenediamine and deionized water is 0.2mol:0.2mol:320mL; the volume ratio of deionized water, absolute ethyl alcohol, acetonitrile, triethylamine and tetraethylammonium hydroxide is 80mL:36mL:9 mL:5mL; the molar ratio of DOPO to itaconic acid was 1.2:1.
DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
the cage type silsesquioxane has high thermal oxidation stability and excellent mechanical properties; in the invention, the porous Al (OH) of C@ is derived from glucose by introducing DOPO and derivatives thereof and octaaminopropyl cage-type silsesquioxane 3 The coaxial nano tube is compounded with a plurality of flame retardant elements to realize synergistic flame retardance;
in Al (OH) 3 On the basis of a charring layer formed by heat decomposition and heat absorption of crystal water, DOPO and derivatives thereof are combined to decompose to generate oxygen-containing phosphoric acid to promote dehydration and charring of the material, and silicon dioxide particles generated by decomposition of cage-type silsesquioxane can cover the surface to generate flame retardant synergistic effect.
The invention uses the three materials to cooperatively flame retardant the diaphragm, uses silicon dioxide particles generated by the decomposition of cage-type silsesquioxane to strengthen DOPO and derivatives thereof, and Al (OH) 3 The quality and strength of the carbon layer formed by catalysis can form a stable ceramic layer containing silicon dioxide and aluminum oxide, the stability of the carbon layer is enhanced, and external heat flow and oxygen are prevented from contacting with internal materials and combustible gases, so that the combustion reaction is prevented, and the flame retardant property of the diaphragm is improved synergistically and greatly.
The COPNA resin is modified, P-H bond is introduced into the COPNA resin, and the modified COPNA resin has very high activity on olefin, epoxy bond and carbonyl in the raw material of the diaphragm, so that the thermal shrinkage of the diaphragm is greatly improved; and the introduction of the active site is beneficial to improving the ion exchange capacity of the diaphragm, effectively preventing the danger of thermal runaway and improving the safety of the diaphragm.
The COPNA resin is condensed polycyclic polynuclear aromatic resin; DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
The invention has the beneficial effects that:
the invention provides a lithium ion battery diaphragm based on an aluminum hydroxide coaxial nanotube and a preparation method thereof, wherein the lithium ion battery diaphragm with high liquid absorption and retention capacity, high flame retardance and high safety is prepared through component definition and process adjustment;
Wherein glucose derived C@ porous Al (OH) 3 The mechanical strength and the heat shrinkage performance of the diaphragm are greatly improved by introducing the coaxial nano tube; the introduction of the glucose-derived C nano tube increases the mechanical property of the diaphragm on one hand, and enhances the conductive property of the diaphragm on the other hand, and the hydrophilic treatment of the silicon dioxide is beneficial to enhancing the rapid transmission of lithium ions; in addition, glucose derived C@ porous Al (OH) 3 The coaxial nanotube has a hollow structure as a whole and is coated with Al (OH) 3 The porous structure is presented, so that the lithium ion conductivity is further improved, the specific surface area of the material is greatly increased, and the liquid absorption and retention capacity of the diaphragm is greatly enhanced;
the COPNA resin is used as the binder to effectively improve the complexity of macromolecular crosslinked network in the diaphragm, and has excellent affinity with the carbon material to effectively improve the glucose derivative C@ porous Al (OH) 3 The affinity of the coaxial nanotube and the diaphragm effectively prolongs the service life of the diaphragm;
according to the invention, bamboo is used as a renewable raw material, bamboo tar is selected as a raw material, terephthalyl alcohol is used as a cross-linking agent, p-toluenesulfonic acid is used as a catalyst to synthesize COPNA resin, the softening point and heat resistance of the obtained COPNA resin are improved by controlling the addition of the p-toluenesulfonic acid, the pretreatment process is simple, the cost is low, and the emission of waste is reduced;
The adhesive is modified, so that the glucose derivative C@ porous Al (OH) is effectively improved 3 Binding force among coaxial nano tube, thickener, binder and wetting agent, and heat recovery of diaphragm is effectively improvedContractility, flame retardance and ionic conductivity;
in the invention, the porous Al (OH) of C@ is derived from glucose by introducing DOPO and derivatives thereof and octaaminopropyl cage-type silsesquioxane 3 The coaxial nano tube is compounded with a plurality of flame retardant elements to realize synergistic flame retardance; the three materials are cooperatively used for flame retardance of the diaphragm, and the silicon dioxide particles generated by the decomposition of cage-type silsesquioxane are utilized to strengthen DOPO and derivatives and Al (OH) thereof 3 The quality and the strength of the carbon layer formed by catalysis can form a stable ceramic layer containing silicon dioxide and aluminum oxide, so that the stability of the carbon layer is enhanced, and the contact of external heat flow and oxygen with internal materials and combustible gas is blocked, so that the combustion reaction is prevented, and the flame retardant property of the diaphragm is improved synergistically and greatly; and the introduction of a large number of active sites is beneficial to improving the ion exchange capacity of the diaphragm, and effectively improving the safety of the diaphragm.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, if directional indications such as up, down, left, right, front, and rear … … are involved in the embodiment of the present invention, the directional indications are merely used to explain a relative positional relationship, a movement condition, and the like between a certain posture such as the respective components, and if the certain posture is changed, the directional indications are changed accordingly. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The following description of the embodiments of the present invention will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present invention and not limiting.
Example 1
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises the following steps:
s1: dispersing agent, glucose derived C@ porous Al (OH) 3 Premixing the coaxial nanotubes in ultrapure water for 10min, wherein the rotating speed is 600rpm; adding the thickener, and continuously stirring for 10min at 900rpm; adding the binder, and continuously stirring for 40min at the rotating speed of 700rpm; adding a wetting agent and stirring for 30min at 900rpm; filtering to remove iron to obtain glucose derivative C@ porous Al (OH) 3 Coating slurry on the coaxial nano tube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises a base film and a formed coating layer coated on the surface of the base film; the coating comprises the following components in parts by weight: 0.35% dispersant, 9% glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes, 0.2% thickener, 0.6% binder, 0.1% wetting agent, balance deionized water;
the base film is a polyethylene diaphragm; the dispersing agent is hydrolyzed polymaleic anhydride, the thickening agent is sodium hydroxymethyl cellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotubes comprises the following steps:
adding 92mg of the hydrophilized silica nanowire into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing to magnetically stir for 40min, then performing ultrasonic dispersion for 7h, transferring into a stainless steel autoclave with a PTFE lining, heating for 6h at 95 ℃, naturally cooling to 18 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 70 ℃ for 24h, and carrying out vacuum degree at 0.08Mpa to obtain the carbon-coated silica nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution and keeping for 5 hours, filtering, washing, drying at 70 ℃ for 10 hours, and obtaining glucose-derived C nanotubes after drying;
Glucose-derived C@ porousAl(OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring 1.97g glucose-derived C nanotube and 215mL ultrapure water for 80min, then performing ultrasonic dispersion for 200min, adding 13.46g aluminum sulfate and 26.59g urea, continuously stirring until the mixture is dissolved, heating to 90C for reaction for 15h, performing suction filtration, washing with ultrapure water, vacuum drying at 75 ℃ for 36h, heating to 115 ℃ from 18 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 155min, and cooling to obtain glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of cetyltrimethylammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 mu L of ammonia water solution and 0.1g of tetraethoxysilane, adding 6% of (3-mercaptopropyl) trimethoxysilane by mass percent, immersing an indium tin oxide coated substrate, standing at 55 ℃ for 28 hours, washing, aging at 100 ℃, washing with 0.15mol/L of ethanol solution of hydrochloric acid, treating with hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire after hydrophilic treatment;
S2: the prepared glucose derivative C@ porous Al (OH) is coated by a micro gravure roller coating process through a coating machine 3 The coaxial nanotube coating slurry is coated on two sides of a 9 mu m base film step by step, the thickness of a single-side coating is 3 mu m, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 65 ℃.
Example 2
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises the following steps:
s1: dispersing agent, glucose derived C@ porous Al (OH) 3 Premixing the coaxial nanotubes in ultrapure water for 60min, wherein the rotating speed is 400rpm; adding the thickener, and continuously stirring for 70min at 500rpm; adding the binder, and continuing stirring for 80min at 600rpm; adding a wetting agent and stirring for 80min at 800rpm; filtering to remove iron to obtain glucose derivative C@ porous Al (OH) 3 Coating slurry on the coaxial nano tube;
based on aluminium hydroxide coaxial nanotubesThe lithium ion battery diaphragm comprises a base film and a formed coating layer coated on the surface of the base film; the coating comprises the following components in parts by weight: 0.6% dispersant, 20% glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes, 0.8% of a thickener, 1% of a binder, 0.3% of a wetting agent, and the balance deionized water;
The base film is a polyethylene diaphragm; the dispersing agent is hydrolyzed polymaleic anhydride, the thickening agent is sodium hydroxymethyl cellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotubes comprises the following steps:
adding 92mg of the hydrophilically treated silica nanowire into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing to magnetically stir for 45min, then performing ultrasonic dispersion for 6.5h, transferring into a stainless steel autoclave with a PTFE lining, heating for 5.5h at 98 ℃, naturally cooling to 20 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 75 ℃ for 22h, and performing vacuum degree of 0.08Mpa to obtain the carbon-coated silica nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, maintaining for 5.5 hours, filtering, washing, drying at 75 ℃ for 11 hours, and drying to obtain glucose-derived C nanotubes;
glucose derived C@ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring 1.97g glucose-derived C nanotube and 215mL ultrapure water for 85min, then performing ultrasonic dispersion for 195min, adding 13.46g aluminum sulfate and 26.59g urea, continuously stirring until the mixture is dissolved, heating to 90-95C for reacting for 12-15h, performing suction filtration, washing with ultrapure water, vacuum drying at 78 ℃ for 34h, heating to 118 ℃ from 20 ℃ at a heating rate of 2 ℃/min after drying, maintaining the temperature for 152min, and cooling to obtain glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of cetyltrimethylammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 mu L of ammonia water solution and 0.1g of tetraethoxysilane, adding 6% of (3-mercaptopropyl) trimethoxysilane by mass percent, immersing an indium tin oxide coated substrate, standing at 56 ℃ for 28 hours, washing, aging at 100 ℃, washing with 0.15mol/L of ethanol solution of hydrochloric acid, treating with hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire after hydrophilic treatment;
s2: the prepared glucose derivative C@ porous Al (OH) is coated by a micro gravure roller coating process through a coating machine 3 The coaxial nanotube coating slurry is coated on two sides of a 9 mu m base film step by step, the thickness of a single-side coating is 3 mu m, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 68 ℃.
Example 3
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises the following steps:
s1: dispersing agent, glucose derived C@ porous Al (OH) 3 Premixing the coaxial nanotubes in ultrapure water for 90min, wherein the rotating speed is 100rpm; adding the thickener, and continuously stirring for 90min at the rotating speed of 350rpm; adding the binder, and continuing stirring for 120min at the rotating speed of 350rpm; adding a wetting agent and stirring for 90min at 400rpm; filtering to remove iron to obtain glucose derivative C@ porous Al (OH) 3 Coating slurry on the coaxial nano tube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises a base film and a formed coating layer coated on the surface of the base film; the coating comprises the following components in parts by weight: 0.8% dispersant, 23% glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes, 0.85% thickener, 1.3% binder, 0.4% wetting agent, the balance deionized water;
the base film is a polyethylene diaphragm; the dispersing agent is hydrolyzed polymaleic anhydride, the thickening agent is sodium hydroxymethyl cellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotubes comprises the following steps:
adding 92mg of the hydrophilized silica nanowire into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing to magnetically stir for 50min, then performing ultrasonic dispersion for 6h, transferring into a stainless steel autoclave with a PTFE lining, heating for 5h at 100 ℃, naturally cooling to 25 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 80 ℃ for 20h, and carrying out vacuum degree of 0.08Mpa to obtain the carbon-coated silica nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, maintaining for 6 hours, filtering, washing, drying at 80 ℃ for 10 hours, and drying to obtain glucose-derived C nanotubes;
Glucose derived C@ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring 1.97g glucose-derived C nanotube and 215mL ultrapure water for 90min, then performing ultrasonic dispersion for 200min, adding 13.46g aluminum sulfate and 26.59g urea, continuously stirring until the mixture is dissolved, heating to 95C for reaction for 12h, performing suction filtration, washing with ultrapure water, vacuum drying at 80 ℃ for 32h, heating to 120 ℃ from 25 ℃ at a heating rate of 2 ℃/min, keeping constant temperature for 155min, and cooling to obtain glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of cetyltrimethylammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 mu L of ammonia water solution and 0.1g of tetraethoxysilane, adding 6% of (3-mercaptopropyl) trimethoxysilane by mass percent, immersing an indium tin oxide coated substrate, standing at 58 ℃ for 28h, washing, aging at 100 ℃, washing with 0.15mol/L of ethanol solution of hydrochloric acid, treating with hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire after hydrophilic treatment;
S2: the prepared glucose derivative C@ porous Al (OH) is coated by a micro gravure roller coating process through a coating machine 3 The coaxial nanotube coating slurry is coated on two sides of a 9 mu m base film step by step, the thickness of a single-side coating is 3 mu m, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 70 ℃ and rolling.
Example 4
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises the following steps:
s1: dispersing agent, glucose derived C@ porous Al (OH) 3 Premixing the coaxial nanotubes in ultrapure water for 10min, wherein the rotating speed is 600rpm; adding the thickener, and continuously stirring for 10min at 900rpm; adding the binder, and continuously stirring for 40min at the rotating speed of 700rpm; adding a wetting agent and stirring for 30min at 900rpm; filtering to remove iron to obtain glucose derivative C@ porous Al (OH) 3 Coating slurry on the coaxial nano tube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises a base film and a formed coating layer coated on the surface of the base film; the coating comprises the following components in parts by weight: 0.35% dispersant, 9% glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes, 0.2% thickener, 0.6% binder, 0.1% wetting agent, balance deionized water;
The base film is a polyethylene diaphragm; the dispersing agent is hydrolyzed polymaleic anhydride, the thickening agent is sodium hydroxymethyl cellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotubes comprises the following steps:
adding 92mg of the hydrophilized silica nanowire into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing to magnetically stir for 40min, then performing ultrasonic dispersion for 7h, transferring into a stainless steel autoclave with a PTFE lining, heating for 6h at 95 ℃, naturally cooling to 18 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 70 ℃ for 24h, and carrying out vacuum degree at 0.08Mpa to obtain the carbon-coated silica nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution and keeping for 5 hours, filtering, washing, drying at 70 ℃ for 10 hours, and obtaining glucose-derived C nanotubes after drying;
glucose derived C@ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: will be1.97g glucose-derived C nanotube, 215mL ultrapure water magnetic stirring for 80min, then performing ultrasonic dispersion for 200min, adding 13.46g aluminum sulfate and 26.59g urea, continuously stirring until dissolving, heating to 90C for reaction for 15h, filtering, washing with ultrapure water, vacuum drying at 75 ℃ for 36h, heating to 115 ℃ from 18 ℃ at a heating rate of 2 ℃/min, keeping constant temperature for 155min, and cooling to obtain glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of cetyltrimethylammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 mu L of ammonia water solution and 0.1g of tetraethoxysilane, adding 6% of (3-mercaptopropyl) trimethoxysilane by mass percent, immersing an indium tin oxide coated substrate, standing at 55 ℃ for 28 hours, washing, aging at 100 ℃, washing with 0.15mol/L of ethanol solution of hydrochloric acid, treating with hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire after hydrophilic treatment;
the adhesive is modified COPNA resin, and the preparation method comprises the following steps:
(1) In a nitrogen environment, 0.2mol of itaconic acid, 320mL of deionized water and 0.2mol of 1, 6-hexamethylenediamine are reacted for 30min at 55 ℃ to obtain an itaconic acid mixed solution;
(2) Mixing 80mL of deionized water, 36mL of absolute ethyl alcohol, 9mL of acetonitrile, 9mL of triethylamine and 5mL of tetraethylammonium hydroxide in a constant temperature water bath at 52 ℃; adding 221mL of 3-aminopropyl triethoxysilane, refluxing at 52 ℃ for 22 hours, concentrating by reduced pressure distillation, adding the concentrated solution into petroleum ether, standing, filtering under reduced pressure, washing with acetone for 2 times, and vacuum drying to obtain octaaminopropyl cage-type silsesquioxane;
(3) Mixing and stirring DOPO0.24mol and itaconic acid 0.2mol, heating to 85 ℃ and reacting for 2.5h; filtering while the mixture is hot, cooling the mixture to 18 ℃, transferring the mixture to ice water bath for cooling for 9 hours, and filtering the mixture to obtain the water-soluble flame retardant; adding 2g of octaaminopropyl cage-type silsesquioxane and 10g of COPNA resin, and carrying out ultrasonic stirring for 30min to obtain modified COPNA resin;
the preparation of the COPNA resin comprises the following steps: under the nitrogen environment, 2g of bamboo tar and 2g of terephthalyl alcohol are added with 5.4 percent of p-toluenesulfonic acid by mass percent, the reaction is carried out at 130 ℃ until the filament winding phenomenon occurs, the heating is stopped, and the discharging and the cooling are carried out, so that COPNA resin is obtained;
s2: the prepared glucose derivative C@ porous Al (OH) is coated by a micro gravure roller coating process through a coating machine 3 The coaxial nanotube coating slurry is coated on two sides of a 9 mu m base film step by step, the thickness of a single-side coating is 3 mu m, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 65 ℃.
Example 5
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises the following steps:
s1: dispersing agent, glucose derived C@ porous Al (OH) 3 Premixing the coaxial nanotubes in ultrapure water for 60min, wherein the rotating speed is 400rpm; adding the thickener, and continuously stirring for 70min at 500rpm; adding the binder, and continuing stirring for 80min at 600rpm; adding a wetting agent and stirring for 80min at 800rpm; filtering to remove iron to obtain glucose derivative C@ porous Al (OH) 3 Coating slurry on the coaxial nano tube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises a base film and a formed coating layer coated on the surface of the base film; the coating comprises the following components in parts by weight: 0.6% dispersant, 20% glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes, 0.8% of a thickener, 1% of a binder, 0.3% of a wetting agent, and the balance deionized water;
the base film is a polyethylene diaphragm; the dispersing agent is hydrolyzed polymaleic anhydride, the thickening agent is sodium hydroxymethyl cellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotubes comprises the following steps:
adding 92mg of the hydrophilically treated silica nanowire into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing to magnetically stir for 45min, then performing ultrasonic dispersion for 6.5h, transferring into a stainless steel autoclave with a PTFE lining, heating for 5.5h at 98 ℃, naturally cooling to 20 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 75 ℃ for 22h, and performing vacuum degree of 0.08Mpa to obtain the carbon-coated silica nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, maintaining for 5.5 hours, filtering, washing, drying at 75 ℃ for 11 hours, and drying to obtain glucose-derived C nanotubes;
Glucose derived C@ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring 1.97g glucose-derived C nanotube and 215mL ultrapure water for 85min, then performing ultrasonic dispersion for 195min, adding 13.46g aluminum sulfate and 26.59g urea, continuously stirring until the mixture is dissolved, heating to 90-95C for reacting for 12-15h, performing suction filtration, washing with ultrapure water, vacuum drying at 78 ℃ for 34h, heating to 118 ℃ from 20 ℃ at a heating rate of 2 ℃/min after drying, maintaining the temperature for 152min, and cooling to obtain glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of cetyltrimethylammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 mu L of ammonia water solution and 0.1g of tetraethoxysilane, adding 6% of (3-mercaptopropyl) trimethoxysilane by mass percent, immersing an indium tin oxide coated substrate, standing at 56 ℃ for 28 hours, washing, aging at 100 ℃, washing with 0.15mol/L of ethanol solution of hydrochloric acid, treating with hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire after hydrophilic treatment;
The adhesive is modified COPNA resin, and the preparation method comprises the following steps:
(1) In a nitrogen environment, 0.2mol of itaconic acid, 320mL of deionized water and 0.2mol of 1, 6-hexamethylenediamine are reacted for 25min at 58 ℃ to obtain an itaconic acid mixed solution;
(2) Mixing 80mL of deionized water, 36mL of absolute ethyl alcohol, 9mL of acetonitrile, 9mL of triethylamine and 5mL of tetraethylammonium hydroxide in a constant temperature water bath at 54 ℃; adding 221mL of 3-aminopropyl triethoxysilane, refluxing at 54 ℃ for 21h, concentrating by reduced pressure distillation, adding the concentrated solution into petroleum ether, standing, filtering under reduced pressure, washing with acetone for 4 times, and vacuum drying to obtain octaaminopropyl cage-type silsesquioxane;
(3) Mixing and stirring DOPO0.24mol and itaconic acid 0.2mol, heating to 87 ℃ and reacting for 2.6h; filtering while the mixture is hot, cooling the mixture to 22 ℃, transferring the mixture to ice water bath for cooling for 10 hours, and filtering the mixture to obtain the water-soluble flame retardant; adding 2g of octaaminopropyl cage-type silsesquioxane and 10g of COPNA resin, and carrying out ultrasonic stirring for 50min to obtain modified COPNA resin;
the preparation of the COPNA resin comprises the following steps: under the nitrogen environment, 2g of bamboo tar and 2g of terephthalyl alcohol are added with 6.2 percent of p-toluenesulfonic acid by mass percent, the reaction is carried out at 140 ℃ until the filament winding phenomenon occurs, the heating is stopped, and the discharging and the cooling are carried out, so that COPNA resin is obtained;
S2: the prepared glucose derivative C@ porous Al (OH) is coated by a micro gravure roller coating process through a coating machine 3 The coaxial nanotube coating slurry is coated on two sides of a 9 mu m base film step by step, the thickness of a single-side coating is 3 mu m, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 68 ℃.
Example 6
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises the following steps:
s1: dispersing agent, glucose derived C@ porous Al (OH) 3 Premixing the coaxial nanotubes in ultrapure water for 90min, wherein the rotating speed is 100rpm; adding the thickener, and continuously stirring for 90min at the rotating speed of 350rpm; adding the binder, and continuing stirring for 120min at the rotating speed of 350rpm; adding a wetting agent and stirring for 90min at 400rpm; filtering to remove iron to obtain glucose derivative C@ porous Al (OH) 3 Coating slurry on the coaxial nano tube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube comprises a base film and a formed coating layer coated on the surface of the base film; the coating comprises the following components in parts by weight: 0.8% dispersant, 23% glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes, 0.85% thickener, 1.3% binder, 0.4% wetting agent, the balance being deionized Sub-water;
the base film is a polyethylene diaphragm; the dispersing agent is hydrolyzed polymaleic anhydride, the thickening agent is sodium hydroxymethyl cellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotubes comprises the following steps:
adding 92mg of the hydrophilized silica nanowire into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing to magnetically stir for 50min, then performing ultrasonic dispersion for 6h, transferring into a stainless steel autoclave with a PTFE lining, heating for 5h at 100 ℃, naturally cooling to 25 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 80 ℃ for 20h, and carrying out vacuum degree of 0.08Mpa to obtain the carbon-coated silica nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, maintaining for 6 hours, filtering, washing, drying at 80 ℃ for 10 hours, and drying to obtain glucose-derived C nanotubes;
glucose derived C@ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring 1.97g glucose-derived C nanotube and 215mL ultrapure water for 90min, then performing ultrasonic dispersion for 200min, adding 13.46g aluminum sulfate and 26.59g urea, continuously stirring until the mixture is dissolved, heating to 95C for reaction for 12h, performing suction filtration, washing with ultrapure water, vacuum drying at 80 ℃ for 32h, heating to 120 ℃ from 25 ℃ at a heating rate of 2 ℃/min, keeping constant temperature for 155min, and cooling to obtain glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of cetyltrimethylammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 mu L of ammonia water solution and 0.1g of tetraethoxysilane, adding 6% of (3-mercaptopropyl) trimethoxysilane by mass percent, immersing an indium tin oxide coated substrate, standing at 58 ℃ for 28h, washing, aging at 100 ℃, washing with 0.15mol/L of ethanol solution of hydrochloric acid, treating with hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire after hydrophilic treatment;
the adhesive is modified COPNA resin, and the preparation method comprises the following steps:
(1) In a nitrogen environment, 0.2mol of itaconic acid, 320mL of deionized water and 0.2mol of 1, 6-hexamethylenediamine are reacted for 20min at 60 ℃ to obtain an itaconic acid mixed solution;
(2) Mixing 80mL of deionized water, 36mL of absolute ethyl alcohol, 9mL of acetonitrile, 9mL of triethylamine and 5mL of tetraethylammonium hydroxide in a constant temperature water bath at 56 ℃; adding 221mL of 3-aminopropyl triethoxysilane, refluxing at 56 ℃ for 20 hours, concentrating by reduced pressure distillation, adding the concentrated solution into petroleum ether, standing, filtering under reduced pressure, washing with acetone for 5 times, and drying in vacuum to obtain octaaminopropyl cage-type silsesquioxane;
(3) Mixing and stirring DOPO0.24mol and itaconic acid 0.2mol, heating to 88 ℃ and reacting for 2.5h; filtering while the mixture is hot, cooling the mixture to 25 ℃, transferring the mixture to ice water bath for cooling for 9 hours, and filtering the mixture to obtain the water-soluble flame retardant; adding 2g of octaaminopropyl cage-type silsesquioxane and 10g of COPNA resin, and carrying out ultrasonic stirring for 60min to obtain modified COPNA resin;
the preparation of the COPNA resin comprises the following steps: under the nitrogen environment, 2g of bamboo tar and 2g of terephthalyl alcohol are added with 6.8 percent of p-toluenesulfonic acid by mass percent, the reaction is carried out at 150 ℃ until the filament winding phenomenon occurs, the heating is stopped, and the discharging and the cooling are carried out to obtain COPNA resin;
s2: the prepared glucose derivative C@ porous Al (OH) is coated by a micro gravure roller coating process through a coating machine 3 The coaxial nanotube coating slurry is coated on two sides of a 9 mu m base film step by step, the thickness of a single-side coating is 3 mu m, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 70 ℃ and rolling.
Comparative example 1
The same polyethylene-based film as in examples 1 to 6 was used, and the other steps were normal.
Comparative example 2
Using example 3 as a control, porous Al (OH) 3 Nanotube replacement glucose derived C@ porous Al (OH) 3 Coaxial nanotubes, other procedures are normal.
Comparative example 3
Using example 3 as a control, glucose-derived C was used in place of glucose-derived C@ porous Al (OH) 3 Coaxial nanotubes, other procedures are normal.
Comparative example 4
Using example 3 as a control, the hydrophilically treated silica was replaced with silica, and the other steps were normal.
Comparative example 5
In the control group of example 6, no octaaminopropyl cage-type silsesquioxane was added, and the other steps were normal.
Comparative example 6
Using example 6 as a control, no glucose-derived C@ porous Al (OH) was added 3 Coaxial nanotubes, other procedures are normal.
Performance test: the separators prepared in examples 1 to 6 and comparative examples 1 to 6 were subjected to performance tests, and the films were tested for thickness, air permeation value, needling strength, ionic conductivity, and heat shrinkage with reference to GB/T36363-2018;
oxygen index measurement: reference IOS4589-2: placing the diaphragm into a transparent combustion cylinder, wherein the temperature of the mixed gas is 24 ℃; when the top surface is ignited, the flame contacts the top surface for 25 seconds, the flame is removed every 5 seconds, whether the membrane burns or not is observed, and the minimum oxygen concentration required by the combustion is just maintained to be the oxygen index;
liquid absorption rate measurement: a 50mm×50mm sample was cut from the prepared membrane, placed in a desiccator for 24 hours, and then taken out, and the sample was weighed and recorded as M (accurate to 0.01 g); immersing the sample in a beaker containing electrolyte, holding for 10min, gently clamping one corner of the sample with plastic forceps, taking out and immediately weighing, and recording as M1 (accurate to 0.01 g); liquid absorption= (M1-M)/M;
And (3) liquid retention rate measurement: a 50mm×50mm sample was cut from the prepared membrane, placed in a desiccator for 24 hours, and then taken out, and the sample was weighed and recorded as M (accurate to 0.01 g); immersing the sample in a beaker filled with electrolyte, slightly clamping one corner of the sample by using plastic forceps after keeping for 10min, taking out and suspending for 3min until part of the electrolyte is naturally dripped off, and weighing, wherein M2 (accurate to 0.01 g) is recorded; retention = (M2-M)/M; i.e. the results are shown in table 1;
TABLE 1
As can be seen by comparing example 3 with comparative example 1, comparative example 2, comparative example 3, wherein glucose derived C@ porous Al (OH) 3 The mechanical strength and the heat shrinkage performance of the diaphragm are greatly improved by introducing the coaxial nano tube; the introduction of the glucose derived C nano tube increases the mechanical property of the diaphragm on one hand and enhances the conductive property of the diaphragm on the other hand, thereby being beneficial to enhancing the rapid transmission of lithium ions; in addition, glucose derived C@ porous Al (OH) 3 The coaxial nanotube has a hollow structure as a whole and is coated with Al (OH) 3 The porous structure is presented, so that the lithium ion conductivity is further improved, the specific surface area of the material is greatly increased, and the liquid absorption and retention capacity of the diaphragm is greatly enhanced;
Comparing example 3 with comparative example 4, it is known that sulfonic acid groups are supported on vertical mesoporous silica pore canal in situ by co-condensation method, and the pore canal structure is not changed, the selective permeability of the nanochannel is mainly caused by size effect and charge effect, when the nanochannel is completely occupied by double electric layers, the selective permeability is optimal, and the preparation and introduction of the hydrophilic treated silica nanowire are limited, so that the ionic conductivity of the membrane is effectively improved;
comparing example 6 with comparative example 5, it is known that synthesizing COPNA resin with bamboo as renewable raw material, bamboo tar as raw material, terephthalyl alcohol as cross-linking agent, p-toluene sulfonic acid as catalyst, and under acidic environment, terephthalyl alcohol can generate active carbon cation, and electrophilic substitution reaction with benzene ring of a large amount of phenols and derivatives thereof in bamboo tar, and alcohol hydroxyl in the product is generated in acid productionThe carbocation is generated again by dehydration, and then reacts with aromatic hydrocarbon to generate cross-linked macromolecules, so that the viscosity of the system is increased along with the deepening of the cross-linking degree, water gas is not escaped any more, and the cross-linked molecules are cross-linked into a network structure, so that COPNA resin is obtained, the softening point and the heat resistance of the COPNA resin are improved by controlling the addition amount of the p-toluenesulfonic acid, the pretreatment process is simple, the cost is low, and the emission of waste is reduced; the complexity of macromolecular crosslinked network in the diaphragm is effectively improved, and the COPNA resin has excellent affinity with the carbon material, so that the glucose derivative C@ porous Al (OH) is effectively improved 3 The affinity of the coaxial nanotube and the diaphragm effectively prolongs the service life of the diaphragm;
the adhesive is modified, so that the glucose derivative C@ porous Al (OH) is effectively improved 3 The binding force among the coaxial nano tube, the thickener, the binder and the wetting agent effectively improves the heat shrinkage, the flame retardance and the ionic conductivity of the diaphragm;
as can be seen by comparing example 6 with example 3, comparative example 5, comparative example 6, the porous Al (OH) of glucose-derived C@ was obtained by introducing DOPO and its derivatives, octaaminopropyl silsesquioxane 3 The coaxial nano tube is compounded with a plurality of flame retardant elements to realize synergistic flame retardance; the three materials are cooperatively used for flame retardance of the diaphragm, and the silicon dioxide particles generated by the decomposition of cage-type silsesquioxane are utilized to strengthen DOPO and derivatives and Al (OH) thereof 3 The quality and the strength of the carbon layer formed by catalysis can form a stable ceramic layer containing silicon dioxide and aluminum oxide, so that the stability of the carbon layer is enhanced, and the contact of external heat flow and oxygen with internal materials and combustible gas is blocked, so that the combustion reaction is prevented, and the flame retardant property of the diaphragm is improved synergistically and greatly; and the introduction of a large number of active sites is beneficial to improving the ion exchange capacity of the diaphragm, and effectively improving the safety of the diaphragm.
In conclusion, the diaphragm prepared by the method has good application prospect in the field of diaphragms.
The foregoing description is only exemplary embodiments of the present invention and is not intended to limit the scope of the invention, but rather, the equivalent structural changes made by the present invention in the light of the inventive concept, or the direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (9)
1. The lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube is characterized by comprising a base film and a coating layer formed on the surface of the base film; the coating comprises the following components in parts by weight: 0.35 to 0.8 percent of dispersing agent and 9 to 23 percent of glucose derivative C@ porous Al (OH) 3 Coaxial nano tube, 0.2% -0.85% of thickener, 0.6% -1.3% of binder, 0.1% -0.4% of wetting agent and the balance of deionized water;
glucose derived C@ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring glucose derived C nanotube and ultrapure water for 80-90min, then performing ultrasonic dispersion for 190-200min, adding aluminum sulfate and urea, continuously stirring until dissolving, heating to 90-95C for reacting for 12-15h, performing suction filtration, washing with ultrapure water, vacuum drying at 75-80deg.C for 32-36h, drying, heating to 115-120deg.C at a heating rate of 2deg.C/min from 18-25deg.C, maintaining the temperature for 150-155min, and cooling to obtain glucose derived C@ porous Al (OH) 3 Coaxial nanotubes.
2. The aluminum hydroxide coaxial nanotube based lithium ion battery separator of claim 1, wherein the base film is a polyolefin separator; the dispersing agent is a hydrolyzed polymaleic anhydride dispersing agent, the thickening agent is a sodium hydroxymethyl cellulose dispersing agent, the binder is a COPNA resin binder, and the wetting agent is a silanol nonionic surfactant.
3. The lithium ion battery separator based on aluminum hydroxide coaxial nanotubes according to claim 1, wherein the preparation of glucose derived C nanotubes comprises the steps of:
1) Mixing and stirring cetyl trimethyl ammonium bromide, absolute ethyl alcohol and deionized water, adding ammonia water solution and tetraethoxysilane, adding (3-mercaptopropyl) trimethoxysilane, immersing an indium tin oxide coated substrate, standing at 55-58 ℃ for 28h, washing, aging at 100 ℃, washing with 0.15mol/L ethanol solution of hydrochloric acid, treating with hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire after hydrophilic treatment;
2) Adding the silicon dioxide nanowire subjected to hydrophilic treatment into a glucose solution under the condition of continuous stirring, continuing to magnetically stir for 40-50min, then performing ultrasonic dispersion for 6-7h, transferring into a stainless steel autoclave with a PTFE lining, heating for 5-6h at 95-100 ℃, naturally cooling to 18-25 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 70-80 ℃ for 20-24h, and vacuum degree being 0.08Mpa to obtain the carbon-coated silicon dioxide nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, maintaining for 5-6h, filtering, washing, drying at 70-80 ℃ for 10-12h, and drying to obtain the glucose-derived C nanotube.
4. The aluminum hydroxide coaxial nanotube based lithium ion battery separator of claim 3 wherein the preparation of the hydrophilically treated silica nanowires comprises the steps of: the mass molar ratio of the silicon dioxide nanowire after hydrophilic treatment to glucose in the glucose solution is 92 mg/101.4 mmol.
5. The aluminum hydroxide coaxial nanotube based lithium ion battery separator of claim 1 wherein the porous Al (OH) is derived from glucose C@ 3 In the preparation of the coaxial nano tube, the mass ratio of the glucose derived C nano tube to the aluminum sulfate to the urea is 1.97:13.46:26.59.
6. The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube is characterized by comprising the following steps:
s1: dispersing agent, glucose derived C@ porous Al (OH) 3 Premixing the coaxial nanotubes in ultrapure water for 10-90min, wherein the rotating speed is 100-600rpm; adding thickener, stirring for 10-90min at 350-900rpm;adding binder, and stirring for 40-120min at 350-700rpm; adding wetting agent, stirring for 30-90min at 400-900rpm; filtering to remove iron to obtain glucose derivative C@ porous Al (OH) 3 Coating slurry on the coaxial nano tube;
S2: the prepared glucose is derived from C@ porous Al (OH) by adopting a micro-gravure roller coating process 3 The coaxial nanotube coating slurry is coated on two sides of a base film step by step, baked at 65-70 ℃ and then rolled, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained.
7. The method for preparing a lithium ion battery separator based on aluminum hydroxide coaxial nanotubes according to claim 6, wherein the binder is modified COPNA resin, and the preparation method comprises the following steps:
(1) In a nitrogen environment, itaconic acid, deionized water and 1, 6-hexamethylenediamine are reacted for 20-30min at 55-60 ℃ to obtain itaconic acid mixed solution;
(2) Mixing deionized water, absolute ethyl alcohol, acetonitrile, triethylamine and tetraethylammonium hydroxide in a constant-temperature water bath at 52-56 ℃; adding 3-aminopropyl triethoxysilane, refluxing at 52-56 ℃ for 20-22h, distilling under reduced pressure for concentration, adding the concentrated solution into petroleum ether, standing, vacuum filtering, washing with acetone for 2-5 times, and vacuum drying to obtain octaaminopropyl cage-type silsesquioxane;
(3) Mixing and stirring DOPO and itaconic acid mixed solution, heating to 85-88 ℃ and reacting for 2.5-3h; filtering while the mixture is hot, cooling the mixture to 18-25 ℃, transferring the mixture to ice water bath for cooling for 9-11h, and filtering the mixture to obtain the water-soluble flame retardant; adding the octaaminopropyl cage-type silsesquioxane and the COPNA resin, and carrying out ultrasonic stirring for 30-60min to obtain the modified COPNA resin.
8. The method for preparing the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nano tube according to claim 7, wherein the molar volume ratio of itaconic acid, 1, 6-hexamethylenediamine and deionized water is 0.2mol:0.2mol:320mL; the volume ratio of deionized water, absolute ethyl alcohol, acetonitrile, triethylamine and tetraethylammonium hydroxide is 80mL:36mL:9 mL:5mL; the molar ratio of DOPO to itaconic acid was 1.2:1.
9. The method for preparing a lithium ion battery separator based on aluminum hydroxide coaxial nanotubes according to claim 7, wherein the preparation of COPNA resin comprises the following steps: under the nitrogen environment, the bamboo tar and the terephthalyl alcohol are weighed according to the mass ratio of 1:1, the p-toluenesulfonic acid with the mass fraction of 5.4-6.8% is added, the reaction is carried out at 130-150 ℃ until the phenomenon of filament winding occurs, the heating is stopped, and the material is discharged and cooled, thus obtaining the COPNA resin.
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| CN113904060A (en) * | 2021-09-30 | 2022-01-07 | 江苏厚生新能源科技有限公司 | Lithium ion battery coating diaphragm and preparation method thereof |
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| CN111403661A (en) * | 2020-03-23 | 2020-07-10 | 南京航空航天大学 | Composite diaphragm for power lithium ion battery and preparation method thereof |
| CN113904060A (en) * | 2021-09-30 | 2022-01-07 | 江苏厚生新能源科技有限公司 | Lithium ion battery coating diaphragm and preparation method thereof |
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