CN116864321A - Titanium-doped hard carbon electrode material and preparation method thereof - Google Patents
Titanium-doped hard carbon electrode material and preparation method thereof Download PDFInfo
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- CN116864321A CN116864321A CN202311126882.1A CN202311126882A CN116864321A CN 116864321 A CN116864321 A CN 116864321A CN 202311126882 A CN202311126882 A CN 202311126882A CN 116864321 A CN116864321 A CN 116864321A
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- deionized water
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- titanium
- hard carbon
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- 239000007772 electrode material Substances 0.000 title claims abstract description 34
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 60
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000001913 cellulose Substances 0.000 claims abstract description 56
- 229920002678 cellulose Polymers 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000002156 mixing Methods 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 235000012431 wafers Nutrition 0.000 claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005406 washing Methods 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000006260 foam Substances 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- 239000000945 filler Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000011159 matrix material Substances 0.000 claims description 27
- 239000000706 filtrate Substances 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 25
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 22
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 20
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 18
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 17
- 239000001263 FEMA 3042 Substances 0.000 claims description 17
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 17
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 17
- 229940033123 tannic acid Drugs 0.000 claims description 17
- 235000015523 tannic acid Nutrition 0.000 claims description 17
- 229920002258 tannic acid Polymers 0.000 claims description 17
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 claims description 14
- 238000010000 carbonizing Methods 0.000 claims description 12
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 12
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 125000004434 sulfur atom Chemical group 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a titanium-doped hard carbon electrode material, which is prepared by cutting foam nickel into wafers, washing the wafers with acetone by ultrasonic, washing the wafers with deionized water, drying the wafers, soaking the wafers in nitric acid solution, and washing the wafers with deionized water until washing solution is neutral; uniformly mixing the reinforcing filler, polytetrafluoroethylene aqueous emulsion and ethanol to obtain an attaching solution, coating the attaching solution on a pretreated nickel sheet, vacuum drying, and then pressing the sheet to obtain the modified substrate, wherein the modified substrate contains sulfur and nitrogen elements, sulfur atom and nitrogen atom doping sites can be formed in the carbonization process, the storage sites are increased, the capacitance value of the electrode can be increased, the modified substrate is carbonized by taking cellulose as a raw material and matched with a metal organic frame on the surface, so that the wettability of the electrode material can be enhanced, the electrolyte can fully permeate and fill the electrode pores, the regularity of the reaction in the electrode is ensured, the stable formation of an interfacial film of solid and electrolyte is ensured, and the cycle life is prolonged.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials, and particularly relates to a titanium-doped hard carbon electrode material and a preparation method thereof.
Background
With the rapid development of new energy electric vehicles and portable electronic products, the human society needs an energy storage device with larger storage capacity as a standby power supply of components. The super capacitor has good development prospect in application, but the self-discharge phenomenon and lower energy density of the super capacitor prevent the super capacitor from rapidly developing, and the carbon material mainly comprises active carbon, carbon nano tubes, graphene, soft carbon, hard carbon and the like. Among all carbon materials, activated carbon is widely used as an electrode material due to the characteristics of low cost, excellent specific surface area, excellent electrochemical performance and the like, and the electrode material at the present stage has poor self wettability, insufficient electrolyte wetting of an electrode, irregular reaction in the electrode and unstable formation of a solid-electrolyte interface film. This may deteriorate battery performance and lead to deterioration of cycle life. Furthermore, incomplete wetting causes lithium metal dendrite formation, which causes serious safety problems.
Disclosure of Invention
The invention aims to provide a titanium-doped hard carbon electrode material and a preparation method thereof, which solve the problems of poor wettability and low capacitance of the electrode material at the present stage.
A titanium doped hard carbon electrode material and a preparation method thereof specifically comprise the following steps:
step S1: cutting foam nickel into wafers with the diameter of 15-20mm, ultrasonically cleaning the wafers with acetone for 30-40min, washing the wafers with deionized water for 3-5min, drying and soaking the wafers in nitric acid solution for 30-40min, and washing the wafers with deionized water until washing solution is neutral to obtain pretreated nickel wafers;
step S2: uniformly mixing the reinforcing filler, polytetrafluoroethylene aqueous emulsion and ethanol to obtain an adhesion liquid, coating the adhesion liquid on a pretreated nickel sheet, vacuum drying at 70-80 ℃, and tabletting at 10-12MPa to obtain the titanium doped hard carbon electrode material.
The mass fraction of the nitric acid solution in the step S1 is 10%.
The dosage ratio of the reinforcing filler to the polytetrafluoroethylene aqueous emulsion to the ethanol in the step S2 is 5g to 1g to 3mL, and the mass fraction of the polytetrafluoroethylene aqueous emulsion is 60%.
Further, the reinforcing filler is prepared by the following steps:
step A1: mixing zinc nitrate hexahydrate and methanol, stirring at a rotating speed of 200-300r/min and a temperature of 20-25 ℃, adding a modified matrix, stirring for 10-15h, standing for 20-25h, centrifuging to remove a supernatant, placing a substrate in a constant temperature tube furnace, carbonizing for 1.5-2h at a temperature of 900-1000 ℃ under a nitrogen atmosphere to obtain a composite filler, dispersing the composite filler in ethanol, adding KH550 and deionized water, stirring at a rotating speed of 150-200r/min and a temperature of 40-50 ℃ for 2-3h to obtain a modified filler;
step A2: mixing deionized water, isopropanol and ammonia water, stirring at a speed of 200-300r/min and a temperature of 20-25 ℃, adding tannic acid, stirring for 25-30 hours, filtering to remove filtrate, dispersing a substrate in deionized water, adding tetrabutyl titanate, acetic acid and n-propanol, reacting at a speed of 60-120r/min and a temperature of 145-150 ℃ for 8-10 hours, carbonizing at a temperature of 800-850 ℃ for 1.5-2 hours in an argon atmosphere, dispersing in ethanol, adding KH570 and deionized water, stirring at a speed of 150-200r/min and a temperature of 40-50 ℃ for 2-3 hours, and obtaining a modified carrier;
step A3: dispersing the modified filler and the modified carrier in deionized water, stirring for 20-30min at the rotation speed of 300-500r/min and the pH value of 8-8.5, filtering to remove filtrate, dispersing a substrate in the deionized water, adding pyrrole and ferric chloride, reacting for 8-10h at the rotation speed of 150-200r/min and the temperature of 3-5 ℃, filtering to remove filtrate, and drying the substrate to obtain the reinforced filler.
Further, the mass ratio of the zinc nitrate hexahydrate to the modified matrix in the step A1 is 3:5, and the dosage of KH550 is 3-5% of the mass of the composite filler.
Further, the dosage ratio of deionized water, isopropanol, ammonia water and tannic acid in the step A2 is 180mL:20mL:1mL:0.6g, the dosage ratio of substrate, tetrabutyl titanate, acetic acid and n-propanol is 2g:1mL:1mL:7mL, and the dosage of KH570 is 3-5% of the mass of the substrate.
Further, the dosage ratio of the modified filler, the modified carrier, the pyrrole and the ferric chloride in the step A3 is 2g to 3g to 0.5mol.
Further, the modified substrate is prepared by the following steps:
step B1: uniformly mixing 4-vinylaniline and ethanol, stirring and dropwise adding glutaraldehyde at the rotation speed of 150-200r/min and the temperature of 40-50 ℃ for reaction for 4-6 hours to obtain an intermediate 1, uniformly mixing the intermediate 1, mercaptoethanol and DMF, and reacting for 1-1.5 hours under the irradiation of ultraviolet light at the rotation speed of 120-150r/min and the wavelength of 365nm to obtain an intermediate 2;
step B2: uniformly mixing the intermediate 2, epoxy chloropropane, benzyl triethyl ammonium chloride and DMF, introducing nitrogen for protection, reacting for 2-4 hours at the temperature of 100-105 ℃ under the condition that the rotating speed is 150-200r/min, cooling to 70-75 ℃, adding sodium hydroxide solution, continuing to react for 15-20 hours to prepare an intermediate 3, mixing cellulose, sodium hydroxide and deionized water, stirring for 3-5 hours at the temperature of 50-60 ℃ under the condition that the rotating speed is 200-300r/min, filtering to remove filtrate, and washing a substrate to be neutral to obtain alkalized cellulose;
step B3: uniformly mixing alkalized cellulose, an intermediate 3 and dioxane, reacting for 7-9 hours at the rotation speed of 120-150r/min and the temperature of 60-80 ℃ to obtain pretreated cellulose, uniformly mixing pretreated cellulose, 4, 5-dicarboxyimidazole, p-toluenesulfonic acid and tetrahydrofuran, refluxing and stirring for 3-5 hours at the rotation speed of 200-300r/min and the temperature of 80-85 ℃, filtering to remove filtrate, and drying a substrate to obtain a modified substrate.
Further, the molar ratio of 4-vinylaniline to glutaraldehyde in the step B1 is 2:1, and the molar ratio of the intermediate 1 to mercaptoethanol is 1:2.
Further, the dosage ratio of the intermediate 2, epichlorohydrin, benzyl triethyl ammonium chloride and sodium hydroxide solution in the step B2 is 40 mmol/80 mmol/0.27 g/14 g, the mass fraction of the sodium hydroxide solution is 30%, and the dosage ratio of cellulose, sodium hydroxide and deionized water is 4 g/3 g/100 mL.
Further, the amount of the intermediate 3 in the step B3 is 3-5% of the mass of the alkalized cellulose, the amount of the 4, 5-dicarboxyimidazole is 10-15% of the mass of the pretreated cellulose, and the amount of the p-toluenesulfonic acid is 5% of the mass of the 4, 5-dicarboxyimidazole.
The beneficial effects of the invention are as follows: the invention prepares a titanium doped hard carbon electrode material, cuts foam nickel into wafers, washes with acetone by ultrasonic, washes with deionized water, dries and soaks in nitric acid solution, soaks and processes, washes with deionized water until washing liquid is neutral, prepares pretreated nickel pieces; uniformly mixing a reinforcing filler, polytetrafluoroethylene aqueous emulsion and ethanol to obtain an attaching solution, coating the attaching solution on a pretreated nickel sheet, vacuum drying, pressing the attaching solution to obtain the modified nickel sheet, mixing the reinforcing filler with zinc nitrate hexahydrate and a modified matrix serving as raw materials, enabling an imidazole structure on the surface of the modified matrix to be matched with zinc ions to form a metal organic framework, carbonizing the modified matrix in a nitrogen atmosphere to form a porous structure to obtain a composite filler, treating the composite filler with KH550 to enable the surface of the composite filler to be grafted with active amino groups to obtain the modified filler, using tannic acid as a raw material to form poly tannic acid under the action of ammonia water, using tetrabutyl titanate as a raw material to form nano titanium dioxide load on the poly tannic acid, carbonizing the poly tannic acid in an argon atmosphere to form titanium doped hard carbon, carrying out surface treatment with KH570 to enable the surface to be grafted with epoxy groups to obtain a modified carrier, mixing modified filler and modified carrier to make amino on modified filler react with epoxy on modified carrier, polymerizing with pyrrole to form polypyrrole cladding structure, making reinforced filler, which enhances electrode material electron transfer effect by inorganic conduction and organic conduction compounding, and simultaneously produces core-shell structure, avoiding surface polypyrrole collapsing in multiple charge and discharge processes by hard core support, modifying matrix to make aldehyde group on glutaraldehyde react with amino on 4-vinylaniline to obtain intermediate 1, mixing intermediate 1 with mercaptoethanol, reacting double bond on intermediate 1 with mercapto ethanol under ultraviolet irradiation to obtain intermediate 2, reacting intermediate 2 with epichlorohydrin to make hydroxy on intermediate 2 react with epichlorohydrin ring-opening reaction, and then ring-closing is carried out under alkaline condition to prepare an intermediate 3, cellulose is treated by sodium hydroxide to form alkalized cellulose, the alkalized cellulose reacts with the intermediate 3 to enable an-ONa group on the alkalized cellulose to react with an epoxy group on the intermediate 3 to form a crosslinked structure, the pretreated cellulose is obtained, carboxyl on the 4, 5-dicarboxylimidazole and hydroxyl on the pretreated cellulose are esterified under the action of p-toluenesulfonic acid to prepare a modified matrix, sulfur and nitrogen elements are contained on the modified matrix, sulfur atom and nitrogen atom doping sites can be formed in the carbonization process, the storage sites are increased, the capacitance value of an electrode can be increased, the modified matrix is carbonized by taking cellulose as a raw material and matched with a metal organic framework on the surface, the wettability of the electrode material can be enhanced, the electrolyte can fully permeate and fill the pores of the electrode, the regularity of the reaction in the electrode is ensured, the stable formation of the boundary between solid and the electrolyte is ensured, and the cycle life is prolonged.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but 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.
Example 1
The preparation method of the titanium doped hard carbon electrode material specifically comprises the following steps:
step S1: cutting foam nickel into wafers with the diameter of 15mm, ultrasonically cleaning the wafers with acetone for 30min, washing the wafers with deionized water for 3min, drying the wafers, soaking the wafers in nitric acid solution for 30min, and washing the wafers with deionized water until washing solution is neutral to obtain pretreated nickel wafers;
step S2: uniformly mixing the reinforcing filler, polytetrafluoroethylene aqueous emulsion and ethanol to obtain an adhesion liquid, coating the adhesion liquid on a pretreated nickel sheet, vacuum drying at 70 ℃, and tabletting at 10MPa to obtain the titanium-doped hard carbon electrode material.
The mass fraction of the nitric acid solution in the step S1 is 10%.
The dosage ratio of the reinforcing filler to the polytetrafluoroethylene aqueous emulsion to the ethanol in the step S2 is 5g to 1g to 3mL, the mass fraction of the polytetrafluoroethylene aqueous emulsion is 60%, and the dosage of the reinforcing filler is 50g.
The reinforced filler is prepared by the following steps:
step A1: mixing zinc nitrate hexahydrate and methanol, stirring at a rotating speed of 200r/min and a temperature of 20 ℃, adding a modified matrix, stirring for 10 hours, standing for 20 hours, centrifuging to remove a supernatant, placing a substrate in a constant-temperature tubular furnace, carbonizing for 1.5 hours at the temperature of 900 ℃ under a nitrogen atmosphere to obtain a composite filler, dispersing the composite filler in ethanol, adding KH550 and deionized water, and stirring for 2 hours at the rotating speed of 150r/min and the temperature of 40 ℃ to obtain a modified filler;
step A2: mixing deionized water, isopropanol and ammonia water, stirring at a rotation speed of 200r/min and a temperature of 20 ℃, adding tannic acid, stirring for 25 hours, filtering to remove filtrate, dispersing a substrate in the deionized water, adding tetrabutyl titanate, acetic acid and n-propanol, reacting for 8 hours at a rotation speed of 60r/min and a temperature of 145 ℃, carbonizing for 1.5 hours at a temperature of 800 ℃ in an argon atmosphere, dispersing in ethanol, adding KH570 and deionized water, stirring at a rotation speed of 150r/min and a temperature of 40 ℃ for 2 hours, and obtaining a modified carrier;
step A3: dispersing the modified filler and the modified carrier in deionized water, stirring for 20min at the rotation speed of 300r/min and the pH value of 8, filtering to remove filtrate, dispersing the substrate in the deionized water, adding pyrrole and ferric chloride, reacting for 8h at the rotation speed of 150r/min and the temperature of 3 ℃, filtering to remove filtrate, and drying the substrate to obtain the reinforced filler.
The mass ratio of the zinc nitrate hexahydrate to the modified matrix in the step A1 is 3:5, the dosage of KH550 is 3-5% of the mass of the composite filler, and the dosage of the modified matrix is 100g.
The dosage ratio of deionized water, isopropanol, ammonia water and tannic acid in the step A2 is 180mL:20mL:1mL:0.6g, the dosage ratio of substrate, tetrabutyl titanate, acetic acid and n-propanol is 2g:1mL:1mL:7mL, the dosage of KH570 is 3% of the mass of the substrate, and the dosage of tannic acid is 120g.
The dosage ratio of the modified filler, the modified carrier, the pyrrole and the ferric chloride in the step A3 is 2g to 3g to 0.5mol, and the dosage of the modified filler is 50g.
The modified matrix is prepared by the following steps:
step B1: uniformly mixing 4-vinylaniline and ethanol, stirring and dropwise adding glutaraldehyde at the rotation speed of 150r/min and the temperature of 40 ℃ for reaction for 4 hours to obtain an intermediate 1, uniformly mixing the intermediate 1, mercaptoethanol and DMF, and reacting for 1 hour under the ultraviolet irradiation condition at the rotation speed of 120r/min and the wavelength of 365nm to obtain an intermediate 2;
step B2: uniformly mixing the intermediate 2, epoxy chloropropane, benzyl triethyl ammonium chloride and DMF, introducing nitrogen for protection, reacting for 2 hours at the rotation speed of 150r/min and the temperature of 100 ℃, cooling to 70 ℃, adding sodium hydroxide solution, continuing to react for 15 hours to obtain an intermediate 3, mixing cellulose, sodium hydroxide and deionized water, stirring for 3 hours at the rotation speed of 200r/min and the temperature of 50 ℃, filtering to remove filtrate, and washing a substrate to be neutral to obtain alkalized cellulose;
step B3: uniformly mixing alkalized cellulose, an intermediate 3 and dioxane, reacting for 7 hours at the temperature of 60 ℃ at the rotating speed of 120r/min to obtain pretreated cellulose, uniformly mixing pretreated cellulose, 4, 5-dicarboxyimidazole, p-toluenesulfonic acid and tetrahydrofuran, refluxing and stirring for 3 hours at the temperature of 80 ℃ at the rotating speed of 200r/min, filtering to remove filtrate, and drying a substrate to obtain a modified matrix.
The molar ratio of the 4-vinylaniline to glutaraldehyde in the step B1 is 2:1, the molar ratio of the intermediate 1 to mercaptoethanol is 1:2, and the dosage of the 4-vinylaniline is 2mol.
The dosage ratio of the intermediate 2, the epichlorohydrin, the benzyl triethyl ammonium chloride and the sodium hydroxide solution in the step B2 is 40 mmol/80 mmol/0.27 g/14 g, the mass fraction of the sodium hydroxide solution is 30%, the dosage ratio of the cellulose, the sodium hydroxide and the deionized water is 4 g/3 g/100 mL, the dosage of the intermediate 2 is 1mol, and the dosage of the cellulose is 150g.
The amount of the intermediate 3 in the step B3 is 3% of the mass of alkalized cellulose, the amount of the 4, 5-dicarboxyimidazole is 10% of the mass of the pretreated cellulose, the amount of the p-toluenesulfonic acid is 5% of the mass of the 4, 5-dicarboxyimidazole, and the amount of the alkalized cellulose is 120g.
Example 2
The preparation method of the titanium doped hard carbon electrode material specifically comprises the following steps:
step S1: cutting foam nickel into wafers with the diameter of 18mm, ultrasonically cleaning the wafers with acetone for 35min, washing the wafers with deionized water for 4min, drying the wafers, soaking the wafers in nitric acid solution for 35min, and washing the wafers with deionized water until washing solution is neutral to obtain pretreated nickel wafers;
step S2: uniformly mixing the reinforcing filler, polytetrafluoroethylene aqueous emulsion and ethanol to obtain an adhesion liquid, coating the adhesion liquid on a pretreated nickel sheet, vacuum drying at 75 ℃, and tabletting at the pressure of 11MPa to obtain the titanium-doped hard carbon electrode material.
The mass fraction of the nitric acid solution in the step S1 is 10%.
The dosage ratio of the reinforcing filler to the polytetrafluoroethylene aqueous emulsion to the ethanol in the step S2 is 5g to 1g to 3mL, the mass fraction of the polytetrafluoroethylene aqueous emulsion is 60%, and the dosage of the reinforcing filler is 50g.
The reinforced filler is prepared by the following steps:
step A1: mixing zinc nitrate hexahydrate and methanol, stirring at a rotating speed of 200r/min and a temperature of 23 ℃, adding a modified matrix, stirring for 13h, standing for 25h, centrifuging to remove a supernatant, placing a substrate in a constant-temperature tubular furnace, carbonizing for 1.8h at a temperature of 950 ℃ under a nitrogen atmosphere to obtain a composite filler, dispersing the composite filler in ethanol, adding KH550 and deionized water, stirring at a rotating speed of 150r/min and a temperature of 45 ℃ for 2.5h to obtain a modified filler;
step A2: mixing deionized water, isopropanol and ammonia water, stirring at a rotation speed of 300r/min and a temperature of 23 ℃, adding tannic acid, stirring for 28 hours, filtering to remove filtrate, dispersing a substrate in the deionized water, adding tetrabutyl titanate, acetic acid and n-propanol, reacting for 9 hours at a rotation speed of 120r/min and a temperature of 148 ℃, carbonizing for 1.8 hours at a temperature of 830 ℃ in an argon atmosphere, dispersing in ethanol, adding KH570 and deionized water, stirring at a rotation speed of 150r/min and a temperature of 45 ℃ for 2.5 hours, and obtaining a modified carrier;
step A3: dispersing the modified filler and the modified carrier in deionized water, stirring for 25min at the rotation speed of 300r/min and the pH value of 8.5, filtering to remove filtrate, dispersing the substrate in the deionized water, adding pyrrole and ferric chloride, reacting for 9h at the rotation speed of 150r/min and the temperature of 4 ℃, filtering to remove filtrate, and drying the substrate to obtain the reinforced filler.
The mass ratio of the zinc nitrate hexahydrate to the modified matrix in the step A1 is 3:5, the KH550 is 4% of the mass of the composite filler, and the modified matrix is 100g.
The dosage ratio of deionized water, isopropanol, ammonia water and tannic acid in the step A2 is 180mL:20mL:1mL:0.6g, the dosage ratio of substrate, tetrabutyl titanate, acetic acid and n-propanol is 2g:1mL:1mL:7mL, the dosage of KH570 is 4% of the mass of the substrate, and the dosage of tannic acid is 120g.
The dosage ratio of the modified filler, the modified carrier, the pyrrole and the ferric chloride in the step A3 is 2g to 3g to 0.5mol, and the dosage of the modified filler is 50g.
The modified matrix is prepared by the following steps:
step B1: uniformly mixing 4-vinylaniline and ethanol, stirring and dropwise adding glutaraldehyde at the rotation speed of 150r/min and the temperature of 40-50 ℃ for reacting for 5 hours to obtain an intermediate 1, uniformly mixing the intermediate 1, mercaptoethanol and DMF, and reacting for 1-1.5 hours under the irradiation of ultraviolet light at the rotation speed of 120r/min and the wavelength of 365nm to obtain an intermediate 2;
step B2: uniformly mixing the intermediate 2, epoxy chloropropane, benzyl triethyl ammonium chloride and DMF, introducing nitrogen for protection, reacting for 3 hours at the rotation speed of 200r/min and the temperature of 103 ℃, cooling to 73 ℃, adding sodium hydroxide solution, continuing to react for 18 hours to prepare an intermediate 3, mixing cellulose, sodium hydroxide and deionized water, stirring for 4 hours at the rotation speed of 200r/min and the temperature of 55 ℃, filtering to remove filtrate, and washing a substrate to be neutral to prepare alkalized cellulose;
step B3: uniformly mixing alkalized cellulose, an intermediate 3 and dioxane, reacting for 8 hours at the temperature of 70 ℃ at the rotating speed of 120r/min to obtain pretreated cellulose, uniformly mixing pretreated cellulose, 4, 5-dicarboxyimidazole, p-toluenesulfonic acid and tetrahydrofuran, refluxing and stirring for 4 hours at the temperature of 83 ℃ at the rotating speed of 200r/min, filtering to remove filtrate, and drying a substrate to obtain a modified matrix.
The molar ratio of the 4-vinylaniline to glutaraldehyde in the step B1 is 2:1, the molar ratio of the intermediate 1 to mercaptoethanol is 1:2, and the dosage of the 4-vinylaniline is 2mol.
The dosage ratio of the intermediate 2, the epichlorohydrin, the benzyl triethyl ammonium chloride and the sodium hydroxide solution in the step B2 is 40 mmol/80 mmol/0.27 g/14 g, the mass fraction of the sodium hydroxide solution is 30%, the dosage ratio of the cellulose, the sodium hydroxide and the deionized water is 4 g/3 g/100 mL, the dosage of the intermediate 2 is 1mol, and the dosage of the cellulose is 150g.
The amount of the intermediate 3 in the step B3 is 4% of the mass of alkalized cellulose, the amount of the 4, 5-dicarboxyimidazole is 15% of the mass of the pretreated cellulose, the amount of the p-toluenesulfonic acid is 5% of the mass of the 4, 5-dicarboxyimidazole, and the amount of the alkalized cellulose is 120g.
Example 3
The preparation method of the titanium doped hard carbon electrode material specifically comprises the following steps:
step S1: cutting foam nickel into wafers with the diameter of 20mm, ultrasonically cleaning the wafers with acetone for 40min, washing the wafers with deionized water for 5min, drying the wafers, soaking the wafers in nitric acid solution for 40min, and washing the wafers with deionized water until washing solution is neutral to obtain pretreated nickel wafers;
step S2: uniformly mixing the reinforcing filler, polytetrafluoroethylene aqueous emulsion and ethanol to obtain an adhesion liquid, coating the adhesion liquid on a pretreated nickel sheet, vacuum drying at 80 ℃, and tabletting at 12MPa to obtain the titanium-doped hard carbon electrode material.
The mass fraction of the nitric acid solution in the step S1 is 10%.
The dosage ratio of the reinforcing filler to the polytetrafluoroethylene aqueous emulsion to the ethanol in the step S2 is 5g to 1g to 3mL, the mass fraction of the polytetrafluoroethylene aqueous emulsion is 60%, and the dosage of the reinforcing filler is 50g.
The reinforced filler is prepared by the following steps:
step A1: mixing zinc nitrate hexahydrate and methanol, stirring at a rotation speed of 300r/min and a temperature of 25 ℃, adding a modified matrix, stirring for 15 hours, standing for 25 hours, centrifuging to remove a supernatant, placing a substrate in a constant-temperature tubular furnace, carbonizing for 2 hours at a temperature of 1000 ℃ under a nitrogen atmosphere to obtain a composite filler, dispersing the composite filler in ethanol, adding KH550 and deionized water, and stirring for 3 hours at a rotation speed of 200r/min and a temperature of 50 ℃ to obtain a modified filler;
step A2: mixing deionized water, isopropanol and ammonia water, stirring at a rotation speed of 300r/min and a temperature of 25 ℃, adding tannic acid, stirring for 30 hours, filtering to remove filtrate, dispersing a substrate in the deionized water, adding tetrabutyl titanate, acetic acid and n-propanol, reacting for 10 hours at a rotation speed of 120r/min and a temperature of 150 ℃, carbonizing for 2 hours at a temperature of 850 ℃ in an argon atmosphere, dispersing in ethanol, adding KH570 and deionized water, stirring for 3 hours at a rotation speed of 200r/min and a temperature of 50 ℃, and obtaining a modified carrier;
step A3: dispersing the modified filler and the modified carrier in deionized water, stirring for 30min at a rotating speed of 500r/min and a pH value of 8.5, filtering to remove filtrate, dispersing a substrate in the deionized water, adding pyrrole and ferric chloride, reacting for 10h at a rotating speed of 200r/min and a temperature of 5 ℃, filtering to remove filtrate, and drying the substrate to obtain the reinforced filler.
The mass ratio of the zinc nitrate hexahydrate to the modified matrix in the step A1 is 3:5, the KH550 is 5% of the mass of the composite filler, and the modified matrix is 100g.
The dosage ratio of deionized water, isopropanol, ammonia water and tannic acid in the step A2 is 180mL:20mL:1mL:0.6g, the dosage ratio of substrate, tetrabutyl titanate, acetic acid and n-propanol is 2g:1mL:1mL:7mL, the dosage of KH570 is 5% of the mass of the substrate, and the dosage of tannic acid is 120g.
The dosage ratio of the modified filler, the modified carrier, the pyrrole and the ferric chloride in the step A3 is 2g to 3g to 0.5mol, and the dosage of the modified filler is 50g.
The modified matrix is prepared by the following steps:
step B1: uniformly mixing 4-vinylaniline and ethanol, stirring and dropwise adding glutaraldehyde at the rotation speed of 200r/min and the temperature of 50 ℃ for reaction for 6 hours to obtain an intermediate 1, uniformly mixing the intermediate 1, mercaptoethanol and DMF, and reacting for 1.5 hours under the ultraviolet irradiation condition with the rotation speed of 150r/min and 365nm to obtain an intermediate 2;
step B2: uniformly mixing the intermediate 2, epoxy chloropropane, benzyl triethyl ammonium chloride and DMF, introducing nitrogen for protection, reacting for 4 hours at the rotation speed of 200r/min and the temperature of 105 ℃, cooling to 75 ℃, adding sodium hydroxide solution, continuing to react for 20 hours to obtain an intermediate 3, mixing cellulose, sodium hydroxide and deionized water, stirring for 5 hours at the rotation speed of 300r/min and the temperature of 60 ℃, filtering to remove filtrate, and washing a substrate to be neutral to obtain alkalized cellulose;
step B3: uniformly mixing alkalized cellulose, an intermediate 3 and dioxane, reacting for 9 hours at the temperature of 80 ℃ at the rotating speed of 150r/min to obtain pretreated cellulose, uniformly mixing pretreated cellulose, 4, 5-dicarboxyimidazole, p-toluenesulfonic acid and tetrahydrofuran, refluxing and stirring for 5 hours at the temperature of 85 ℃ at the rotating speed of 300r/min, filtering to remove filtrate, and drying a substrate to obtain a modified matrix.
The molar ratio of the 4-vinylaniline to glutaraldehyde in the step B1 is 2:1, the molar ratio of the intermediate 1 to mercaptoethanol is 1:2, and the dosage of the 4-vinylaniline is 2mol.
The dosage ratio of the intermediate 2, the epichlorohydrin, the benzyl triethyl ammonium chloride and the sodium hydroxide solution in the step B2 is 40 mmol/80 mmol/0.27 g/14 g, the mass fraction of the sodium hydroxide solution is 30%, the dosage ratio of the cellulose, the sodium hydroxide and the deionized water is 4 g/3 g/100 mL, the dosage of the intermediate 2 is 1mol, and the dosage of the cellulose is 150g.
The amount of the intermediate 3 in the step B3 is 5% of the mass of the alkalized cellulose, the amount of the 4, 5-dicarboxyimidazole is 15% of the mass of the pretreated cellulose, the amount of the p-toluenesulfonic acid is 5% of the mass of the 4, 5-dicarboxyimidazole, and the amount of the alkalized cellulose is 120g.
Comparative example 1
In this comparative example, the pretreated cellulose was placed in a constant temperature tube furnace at 900-1000℃under nitrogen atmosphere, and the modified filler was replaced with the carbonized product for 1.5 hours, and the remaining steps were the same.
Comparative example 2
This comparative example uses cellulose instead of pretreated fibers as compared to example 1, the rest of the procedure being the same.
Comparative example 3
In this comparative example, the modified filler and the modified carrier were dispersed in deionized water at a rotation speed of 300r/min and a pH value of 8, and stirred for 20 minutes, and the filtrate was filtered to remove the resultant, instead of the reinforcing filler, as compared with example 1.
The electrode materials prepared in examples 1 to 3 and comparative examples 1 to 3 were examined for specific capacitance at a current density of 2A/g, and the retention of capacitance after 4000 cycles was calculated, and the results are shown in the following table.
As is clear from the above table, the specific capacities of the electrode materials prepared in examples 1 to 3 were 463.36 to 466.51F/g, the capacity retention rates were 84.33 to 84.45%, and no collapse of the electrodes occurred.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the titanium-doped hard carbon electrode material is characterized by comprising the following steps of:
step S1: cutting foam nickel into wafers, ultrasonically cleaning the wafers by using acetone, washing the wafers by using deionized water, drying the wafers, soaking the wafers in nitric acid solution, and washing the wafers by using deionized water until washing liquid is neutral to obtain pretreated nickel sheets;
step S2: uniformly mixing the reinforcing filler, polytetrafluoroethylene aqueous emulsion and ethanol to obtain an adhesion liquid, coating the adhesion liquid on a pretreated nickel sheet, vacuum drying, and performing sheet pressing treatment to obtain the titanium doped hard carbon electrode material.
2. The method for preparing a titanium-doped hard carbon electrode material according to claim 1, wherein the reinforcing filler is prepared by the steps of:
step A1: mixing zinc nitrate hexahydrate and methanol, stirring, adding a modified matrix, standing, centrifuging to remove supernatant, placing a substrate in a constant-temperature tube furnace, carbonizing to obtain a composite filler, dispersing the composite filler in ethanol, adding KH550 and deionized water, and stirring to obtain a modified filler;
step A2: mixing deionized water, isopropanol and ammonia water, stirring, adding tannic acid, stirring, filtering to remove filtrate, dispersing a substrate in the deionized water, adding tetrabutyl titanate, acetic acid and n-propanol, reacting, carbonizing in an argon atmosphere, dispersing in ethanol, adding KH570 and deionized water, and stirring to obtain a modified carrier;
step A3: dispersing the modified filler and the modified carrier in deionized water, stirring, filtering to remove filtrate, dispersing a substrate in deionized water, adding pyrrole and ferric chloride, reacting, filtering to remove filtrate, and drying the substrate to obtain the reinforced filler.
3. The method for preparing the titanium-doped hard carbon electrode material according to claim 2, wherein the mass ratio of the zinc nitrate hexahydrate to the modified matrix in the step A1 is 3:5, and the KH550 is 3-5% of the mass of the composite filler.
4. The method for preparing the titanium-doped hard carbon electrode material according to claim 2, wherein the dosage ratio of deionized water, isopropanol, ammonia water and tannic acid in the step A2 is 180mL:20mL:1mL:0.6g, the dosage ratio of substrate, tetrabutyl titanate, acetic acid and n-propanol is 2g:1 mL:7mL, and the dosage of KH570 is 3-5% of the mass of the substrate.
5. The method for preparing a titanium-doped hard carbon electrode material according to claim 2, wherein the dosage ratio of the modified filler, the modified carrier, the pyrrole and the ferric chloride in the step A3 is 2 g/3 g/0.5 mol.
6. The method for preparing the titanium-doped hard carbon electrode material according to claim 1, wherein the modified substrate is prepared by the following steps:
step B1: mixing 4-vinylaniline and ethanol, stirring, dropwise adding glutaraldehyde, reacting to obtain an intermediate 1, and mixing and reacting the intermediate 1, mercaptoethanol and DMF to obtain an intermediate 2;
step B2: mixing intermediate 2, epichlorohydrin, benzyl triethyl ammonium chloride and DMF for reaction, cooling, adding sodium hydroxide solution, continuing to react to obtain intermediate 3, mixing and stirring cellulose, sodium hydroxide and deionized water, filtering to remove filtrate, and washing a substrate to be neutral to obtain alkalized cellulose;
step B3: mixing and reacting alkalized cellulose, an intermediate 3 and dioxane to prepare pretreated cellulose, mixing and refluxing pretreated cellulose, 4, 5-dicarboxyimidazole, p-toluenesulfonic acid and tetrahydrofuran, filtering to remove filtrate, and drying a substrate to prepare a modified matrix.
7. The method for preparing a titanium-doped hard carbon electrode material according to claim 6, wherein the molar ratio of 4-vinylaniline to glutaraldehyde in the step B1 is 2:1, and the molar ratio of the intermediate 1 to mercaptoethanol is 1:2.
8. The method for preparing the titanium-doped hard carbon electrode material according to claim 6, wherein the dosage ratio of the intermediate 2, epichlorohydrin, benzyl triethyl ammonium chloride and sodium hydroxide solution in the step B2 is 40 mmol/80 mmol/0.27 g/14 g, the mass fraction of the sodium hydroxide solution is 30%, and the dosage ratio of cellulose, sodium hydroxide and deionized water is 4 g/3 g/100 mL.
9. The method for preparing a titanium-doped hard carbon electrode material according to claim 6, wherein the intermediate 3 in the step B3 is used in an amount of 3-5% by mass of alkalinized cellulose, the amount of 4, 5-dicarboxyimidazole is 10-15% by mass of pretreated cellulose, and the amount of p-toluenesulfonic acid is 5% by mass of 4, 5-dicarboxyimidazole.
10. A titanium-doped hard carbon electrode material, characterized by being prepared according to the preparation method of any one of claims 1 to 9.
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| JP2016192341A (en) * | 2015-03-31 | 2016-11-10 | 大阪瓦斯株式会社 | Titanium-based material for sodium ion secondary battery, manufacturing method thereof, electrode active material using titanium-based material, electrode active material layer, electrode, and sodium ion secondary battery |
| US20190109358A1 (en) * | 2017-10-09 | 2019-04-11 | Nanotek Instruments, Inc. | Sodium ion-based internal hybrid electrochemical energy storage cell |
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| CN115798946A (en) * | 2023-01-30 | 2023-03-14 | 昆山美淼新材料科技有限公司 | Production process of metal graphene multi-element composite electrode |
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| JP2016192341A (en) * | 2015-03-31 | 2016-11-10 | 大阪瓦斯株式会社 | Titanium-based material for sodium ion secondary battery, manufacturing method thereof, electrode active material using titanium-based material, electrode active material layer, electrode, and sodium ion secondary battery |
| US20190109358A1 (en) * | 2017-10-09 | 2019-04-11 | Nanotek Instruments, Inc. | Sodium ion-based internal hybrid electrochemical energy storage cell |
| CN115763088A (en) * | 2022-11-21 | 2023-03-07 | 昆山美淼新材料科技有限公司 | Preparation method of multilayer graphene electrode |
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