CN112151281A - Lithium molybdate composite modified Li2ZnTi3O8Preparation method of nano electrode material - Google Patents
Lithium molybdate composite modified Li2ZnTi3O8Preparation method of nano electrode material Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 46
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 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
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000003990 capacitor Substances 0.000 claims description 9
- 239000005011 phenolic resin Substances 0.000 claims description 9
- 229920001568 phenolic resin Polymers 0.000 claims description 9
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 8
- 229940010552 ammonium molybdate Drugs 0.000 claims description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 Polytetrafluoroethylene Polymers 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 108020001612 μ-opioid receptors Proteins 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BXGJXQJWUCUHJQ-UHFFFAOYSA-N [C].C1(O)=C(C(O)=CC=C1)C=O Chemical compound [C].C1(O)=C(C(O)=CC=C1)C=O BXGJXQJWUCUHJQ-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H01G11/22—Electrodes
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Abstract
Lithium molybdate composite modified Li2ZnTi3O8The preparation method of the nano carbon sphere electrode material comprises the following steps: the method comprises the following steps: preparing a nano polymer ball; step (ii) ofII, secondly: lithium molybdate modified Li2ZnTi3O8(ii) a Step three: preparation of lithium molybdate complex modified Li2ZnTi3O8The nano carbon ball electrode material. The invention discloses a nano carbon sphere electrode material, which overcomes the defect of large resistance of the traditional electrode material, and lithium molybdate modified Li2ZnTi3O8The nano carbon sphere electrode material has higher conductivity and electrochemical stability, can increase the capacitance of the nano carbon sphere electrode material, has larger specific surface area, and is beneficial to the transmission of electron ions. The preparation method disclosed by the invention is simple, the prepared electrode material is low in resistivity, high specific capacitance is provided for the supercapacitor material, the operation is easy, the equipment requirement is low, and the preparation method has a good application prospect.
Description
Technical Field
The invention belongs to the field of electrode material preparation, and particularly relates to composite lithium molybdate modified Li2ZnTi3O8A method for preparing a nano carbon sphere electrode material.
Background
Supercapacitors, also known as electrochemical capacitors, are new types of energy storage devices with properties intermediate between batteries and electrostatic capacitors. The research core of the supercapacitor is mainly focused on the research of electrode materials.
Carbon materials, as an important electrode material, can be used either directly as an electrode material or as a further composite substrate or doped "backbone". The compounded or doped electrode material has higher capacitance value and energy density compared with the original carbon electrode material. The doped carbon material can also keep good cycling stability, which is an important performance index of the electrode material.
The nanometer material attracts the attention of many researchers due to the unique quantum size effect, small size effect, macroscopic quantum tunneling effect and the like. Metal nanomaterials are used in a variety of fields due to their unique photoelectric and chemical properties. Li et al proposed a new structured catalyst in 2017 with platinum nanoparticles partially embedded in resorcinol-formaldehyde carbon spheres (Pt @ RFC) towards MORs. Pt @ RFC has good compatibility and MOR activity, wherein the negative migration of CO electrooxidation peak potential is about 150mv, and the electrocatalytic activity is 2 times that of commercial Pt/C. It is worth noting that the mass activity of Pt @ RFC is well maintained after 3000 times of cyclic voltammetry accelerated degradation, which is 5.8 times that of commercial Pt/C.
Among the materials for preparing the conventional super capacitor, the carbon material is the most widely studied electrode material due to its wide source, low cost and various forms, such as: carbon nanotubes, graphene, activated carbon, and the like. However, most carbon electrode materials are relatively poorly conductive, which can lead to poor rate performance of the device. Therefore, an electrode with good conductivity is a basis for preparing a high-performance supercapacitor. In order to improve the conductivity of the carbon film, the conductive carbon black is added conventionally, but the high proportion of the conductive carbon black reduces the quality and the specific surface area of the carbon film, and the sheet resistance of the carbon film is still relatively high.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a composite Li2ZnTi3O8A method for preparing a nano carbon sphere electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
lithium molybdate composite modified Li2ZnTi3O8The preparation method of the nano carbon sphere electrode material comprises the following steps:
the method comprises the following steps: adding a resorcinol aqueous solution, a low-polymerization-degree paraformaldehyde aqueous solution and a sodium hydroxide solution into a reactor, stirring and mixing, heating to a certain temperature to obtain a low-molecular-weight phenolic resin prepolymer, then adding ammonia water, heating to 100 ℃, polymerizing for 24 hours, washing the obtained resin microspheres with deionized water after the reaction is finished, and drying for 5 hours in a constant-temperature drying oven at 120 ℃ to obtain nano polymer spheres;
step two: dissolving tetrabutyl titanate, zinc nitrate hexahydrate, lithium nitrate and ammonium molybdate in ethanol, adding citric acid at 70 ℃ while stirring until gel is formed, then putting the gel into a vacuum oven at 120 ℃ for drying for 12 hours, transferring the gel into a muffle furnace after drying, presintering the gel for 4 hours at 500-600 ℃, then heating to 600-800 ℃ for calcining for 10 hours, and cooling to obtain the Li modified by lithium molybdate2ZnTi3O8；
Step three: adding the nano polymer spheres into ethanol to form a mixture of 20-50mg/L, and then adding lithium molybdate modified Li accounting for 5-10% of the mass of the nano polymer spheres2ZnTi3O8Performing ultrasonic treatment for 15min at normal temperature, then placing the mixture at 70 ℃ for condensation reflux reaction for 12 hours, transferring the mixture into a muffle furnace after drying, and calcining the mixture for 6 hours at 500-600 DEG CTo obtain the composite lithium molybdate modified Li2ZnTi3O8The electrode material of (1);
preferably, the concentration of the resorcinol aqueous solution in the step one is 0.05-0.10mol/L, the concentration of the sodium hydroxide solution is 0.1mol/L, the concentration of the ammonia water is 0.05-0.1mol/L, and the mass concentration of the paraformaldehyde aqueous solution with low polymerization degree is 280-380 g/L.
Preferably, the heating temperature of the phenolic resin prepolymer with low molecular weight obtained by heating in the step one is 40 ℃.
Further, in the second step, the molar ratio of tetrabutyl titanate: zinc nitrate hexahydrate: lithium nitrate: ammonium molybdate 3-5:1:2-3: 2; tetrabutyl titanate: the mass volume ratio of ethanol is 1 g: 20 mL.
The invention has the following beneficial effects:
the invention discloses a nano carbon sphere electrode material, which overcomes the defect of large resistance of the traditional electrode material and is compounded with lithium molybdate modified Li2ZnTi3O8Into nanocarbon spheres, lithium molybdate modified Li2ZnTi3O8The nano carbon sphere electrode material has good conductivity and electrochemical stability, and the nano carbon sphere electrode material has larger specific surface area due to the increase of the capacitance of the nano carbon sphere electrode material, thereby being beneficial to the transmission of electron ions. The preparation method disclosed by the invention is simple, the prepared electrode material is low in resistivity, high specific capacitance is provided for the supercapacitor material, the operation is easy, the equipment requirement is low, and the preparation method has a good application prospect.
Drawings
FIG. 1 shows modified Li with lithium molybdate complex obtained in example 12ZnTi3O8Scanning electron microscope photos of the nano carbon ball electrode material;
FIG. 2 shows Li modified with lithium molybdate complex obtained in example 12ZnTi3O8Cyclic voltammograms of symmetrical capacitors assembled by the nano carbon sphere electrode material under different voltage windows.
Detailed Description
Example 1
Composite molybdic acidLithium modified Li2ZnTi3O8The preparation method of the nano carbon sphere electrode material comprises the following steps:
the method comprises the following steps: adding 50mL of 0.05mol/L resorcinol aqueous solution and 20mL of 0.1mol/L sodium hydroxide solution into a reactor, stirring and mixing the resorcinol aqueous solution and the sodium hydroxide solution, heating the mixture to 40 ℃ to obtain a low-molecular-weight phenolic resin prepolymer, then adding 20mL of 0.05mol/L ammonia water, heating the mixture to 100 ℃ for polymerization for 24 hours, washing the obtained resin microspheres with deionized water after the reaction is finished, and drying the resin microspheres in a constant-temperature drying oven at 120 ℃ for 5 hours to obtain nano polymer spheres;
step two: dissolving tetrabutyl titanate, zinc nitrate hexahydrate, lithium nitrate and ammonium molybdate in ethanol according to the molar ratio of 3:1:2:2, adding citric acid at 70 ℃ while stirring until gel is formed, then putting the gel into a vacuum oven at 120 ℃ for drying for 12 hours, transferring the gel into a muffle furnace after drying, presintering for 4 hours at 500 ℃, then heating to 600 ℃ for calcining for 10 hours, and cooling to obtain lithium molybdate modified Li2ZnTi3O8；
Step three: adding the nano polymer spheres into ethanol to form a mixture of 20mg/L, and then adding lithium molybdate modified Li accounting for 5 percent of the mass of the nano polymer spheres2ZnTi3O8Carrying out ultrasonic treatment at the ultrasonic power of 150W for 15min at normal temperature, then placing the mixture at 70 ℃ for condensation reflux reaction for 12 hours, carrying out water washing and ethanol leaching for 3 times, carrying out vacuum drying, transferring to a muffle furnace after drying, and calcining for 6 hours at 500 ℃ to obtain the composite lithium molybdate modified Li2ZnTi3O8The electrode material of (1).
Example 2
Lithium molybdate composite modified Li2ZnTi3O8The preparation method of the nano carbon sphere electrode material comprises the following steps:
the method comprises the following steps: adding 50mL of 0.06mol/L resorcinol aqueous solution and 20mL of 0.1mol/L sodium hydroxide solution into a reactor, adding 85g/L low-polymerization-degree paraformaldehyde aqueous solution, stirring and mixing, heating to 40 ℃ to obtain a low-molecular-weight phenolic resin prepolymer, then adding 20mL of 0.06mol/L ammonia water, heating to 100 ℃ for polymerization for 24 hours, washing the obtained resin microspheres with deionized water after the reaction is finished, and drying in a constant-temperature drying oven at 120 ℃ for 5 hours to obtain nano polymer spheres;
step two: dissolving tetrabutyl titanate, zinc nitrate hexahydrate, lithium nitrate and ammonium molybdate in ethanol according to a molar ratio of 4:1:3:2, adding citric acid at 70 ℃ while stirring until gel is formed, then putting the gel into a vacuum oven at 120 ℃ for drying for 12 hours, transferring the dried gel into a muffle furnace, presintering for 4 hours at 530 ℃, then heating to 650 ℃ for calcining for 10 hours, and cooling to obtain lithium molybdate modified Li2ZnTi3O8；
Step three: adding the nano polymer spheres into ethanol to form a mixture of 20mg/L, and then adding lithium molybdate modified Li accounting for 6 percent of the mass of the nano polymer spheres2ZnTi3O8Performing ultrasonic treatment at the ultrasonic power of 160W for 15min at normal temperature, then placing the mixture at 70 ℃ for condensation reflux reaction for 12 hours, performing water washing and ethanol leaching for 3-5 times, performing vacuum drying, transferring to a muffle furnace after drying, and calcining for 6 hours at 540 ℃ to obtain the Li modified by the composite lithium molybdate2ZnTi3O8The electrode material of (1).
Example 3
Lithium molybdate composite modified Li2ZnTi3O8The preparation method of the nano carbon sphere electrode material comprises the following steps:
the method comprises the following steps: adding 50mL of 0.07mol/L resorcinol aqueous solution and 20mL of 0.1mol/L sodium hydroxide solution into a reactor, adding 90g/L low-polymerization-degree paraformaldehyde aqueous solution, stirring, mixing, heating to 40 ℃ to obtain a low-molecular-weight phenolic resin prepolymer, adding 20mL of 0.06mol/L ammonia water, heating to 100 ℃ for polymerization for 24 hours, washing the obtained resin microspheres with deionized water after the reaction is finished, and drying in a constant-temperature drying oven at 120 ℃ for 5 hours to obtain nano polymer spheres;
step two: tetrabutyl titanate, zinc nitrate hexahydrate, lithium nitrate and molybdic acidDissolving ammonium in ethanol according to a molar ratio of 4:1:2:2, adding citric acid at 70 ℃ while stirring until gel is formed, then putting the gel into a vacuum oven at 120 ℃ for drying for 12 hours, transferring the gel into a muffle furnace after drying, presintering the gel for 4 hours at 560 ℃, then heating to 700 ℃ for calcining for 10 hours, and cooling to obtain the lithium molybdate modified Li2ZnTi3O8；
Step three: adding the nano polymer spheres into ethanol to form a mixture of 20mg/L, and then adding lithium molybdate modified Li accounting for 7 percent of the mass of the nano polymer spheres2ZnTi3O8Carrying out ultrasonic treatment at the ultrasonic power of 170W for 15min at normal temperature, then placing the mixture at 70 ℃ for condensation reflux reaction for 12 hours, carrying out water washing and ethanol leaching for 3-5 times, carrying out vacuum drying, transferring to a muffle furnace after drying, and calcining for 6 hours at 560 ℃ to obtain the Li modified by the composite lithium molybdate2ZnTi3O8The electrode material of (1).
Example 4
Lithium molybdate composite modified Li2ZnTi3O8The preparation method of the nano carbon sphere electrode material comprises the following steps:
the method comprises the following steps: adding 50mL of 0.08mol/L resorcinol aqueous solution and 20mL of 0.1mol/L sodium hydroxide solution into a reactor, adding 95g/L low-polymerization-degree paraformaldehyde, stirring, mixing, heating to 40 ℃ to obtain a low-molecular-weight phenolic resin prepolymer, then adding 20mL of 0.08mol/L ammonia water, heating to 100 ℃ for polymerization for 24 hours, washing the obtained resin microspheres with deionized water after the reaction is finished, and drying in a constant-temperature drying oven at 120 ℃ for 5 hours to obtain nano polymer spheres;
step two: dissolving tetrabutyl titanate, zinc nitrate hexahydrate, lithium nitrate and ammonium molybdate in ethanol according to the molar ratio of 5:1:2:2, adding citric acid at 70 ℃ while stirring until gel is formed, then putting the gel into a vacuum oven at 120 ℃ for drying for 12 hours, transferring the gel into a muffle furnace after drying, presintering for 4 hours at 590 ℃, then heating to 750 ℃ for calcining for 10 hours, and cooling to obtain lithium molybdate modified Li2ZnTi3O8；
Step three: adding the nano polymer spheres into ethanol to form a mixture of 20mg/L, and then adding lithium molybdate modified Li accounting for 8 percent of the mass of the nano polymer spheres2ZnTi3O8Ultrasonic power of 180W at normal temperature for 15min, placing the mixture at 70 ℃ for condensation reflux reaction for 12 hours, washing with water and ethanol leaching for 3-5 times, drying in vacuum, transferring to a muffle furnace after drying, and calcining at 580 ℃ for 6 hours to obtain the Li modified by the composite lithium molybdate2ZnTi3O8The electrode material of (1).
Example 5
Lithium molybdate composite modified Li2ZnTi3O8The preparation method of the nano carbon sphere electrode material comprises the following steps:
the method comprises the following steps: adding 50mL of 0.10mol/L resorcinol aqueous solution and 20mL of 0.1mol/L sodium hydroxide solution into a reactor, adding 100g/L low-polymerization-degree paraformaldehyde aqueous solution, stirring, mixing, heating to 40 ℃ to obtain a low-molecular-weight phenolic resin prepolymer, adding 20mL of 0.10mol/L ammonia water, heating to 100 ℃ for polymerization for 24 hours, washing the obtained resin microspheres with deionized water after the reaction is finished, and drying in a constant-temperature drying oven at 120 ℃ for 5 hours to obtain nano polymer spheres;
step two: dissolving tetrabutyl titanate, zinc nitrate hexahydrate, lithium nitrate and ammonium molybdate in ethanol according to the molar ratio of 5:1:3:2, adding citric acid at 70 ℃ while stirring until gel is formed, then putting the gel into a vacuum oven at 120 ℃ for drying for 12 hours, transferring the gel into a muffle furnace after drying, presintering for 4 hours at 600 ℃, then heating to 800 ℃ for calcining for 10 hours, and cooling to obtain lithium molybdate modified Li2ZnTi3O8；
Step three: adding the nano polymer spheres into ethanol to form a mixture of 20mg/L, and then adding lithium molybdate modified Li accounting for 10% of the mass of the nano polymer spheres2ZnTi3O8Ultrasonic treating at normal temperature with ultrasonic power of 200W for 15min, condensing and refluxing the mixture at 70 deg.C for 12 hr, washing with water and ethanol for 3-5 times, vacuum drying, and transferringTransferring the lithium molybdate powder into a muffle furnace, and calcining the lithium molybdate powder for 6 hours at the temperature of 600 ℃ to obtain the lithium molybdate composite modified Li2ZnTi3O8The electrode material of (1).
And (3) electrochemical performance testing:
lithium molybdate complex modified Li obtained in examples 1 to 52ZnTi3O8Weighing the nano carbon ball electrode material, acetylene black and Polytetrafluoroethylene (PTFE) according to the mass ratio of 8:1:1, placing the nano carbon ball electrode material, the acetylene black and the PTFE into an agate mortar, dropwise adding ethanol in a proper amount, and uniformly grinding; coating the nickel-base alloy on foamed nickel, drying the nickel-base alloy for 2 hours at 50 ℃ in a drying oven, taking out a pole piece, rolling the pole piece on a roller press, continuously drying the pole piece for 1 hour at 50 ℃, and using a punching sheet of a button cell punching machine as a button super capacitor electrode; assembling a symmetrical super capacitor by using the obtained pole pieces, wherein a polypropylene microporous membrane is used as a diaphragm, and 6mol/L KOH solution is used as electrolyte; and standing for 24h, and testing the electrochemical performance. The results are shown in Table 1. And the lithium molybdate complex modified Li obtained in example 1 was tested2ZnTi3O8Cyclic voltammetry of a symmetrical capacitor assembled by nano carbon sphere electrode materials under different voltage windows, as shown in fig. 2
Table 1: and (3) testing results:
from the examples, it can be seen that the lithium molybdate complex modified Li prepared by the method2ZnTi3O8The nano carbon ball electrode material capacitor has a larger voltage window, can maintain a large specific capacitance under a large current density, has small specific capacity attenuation after long-term use, and has a good application prospect.
Claims (5)
1. Lithium molybdate composite modified Li2ZnTi3O8Preparation method of nano carbon ball electrode materialThe method is characterized in that the preparation method comprises the following steps:
the method comprises the following steps: adding a resorcinol aqueous solution, a low-polymerization-degree paraformaldehyde aqueous solution and a sodium hydroxide solution into a reactor, stirring and mixing, heating to a certain temperature to obtain a low-molecular-weight phenolic resin prepolymer, then adding ammonia water, heating to 100 ℃, polymerizing for 24 hours, washing the obtained resin microspheres with deionized water after the reaction is finished, and drying for 5 hours in a constant-temperature drying oven at 120 ℃ to obtain nano polymer spheres;
step two: dissolving tetrabutyl titanate, zinc nitrate hexahydrate, lithium nitrate and ammonium molybdate in ethanol, adding citric acid at 70 ℃ while stirring until gel is formed, then putting the gel into a vacuum oven at 120 ℃ for drying for 12 hours, transferring the gel into a muffle furnace after drying, presintering the gel for 4 hours at 500-600 ℃, then heating to 600-800 ℃ for calcining for 10 hours, and cooling to obtain the Li modified by lithium molybdate2ZnTi3O8；
Step three: adding the nano polymer spheres into ethanol to form a mixture of 20-50mg/L, and then adding lithium molybdate modified Li accounting for 5-10% of the mass of the nano polymer spheres2ZnTi3O8Performing ultrasonic treatment at normal temperature for 15min, then placing the mixture at 70 ℃ for condensation reflux reaction for 12 hours, washing with water and ethanol for 3-5 times, and drying in vacuum to obtain the composite lithium molybdate modified Li2ZnTi3O8The nano polymer ball.
2. The method according to claim 1, wherein the concentration of the aqueous resorcinol solution in the first step is 0.05-0.10mol/L, the concentration of the sodium hydroxide solution is 0.1mol/L, the concentration of the ammonia water is 0.05-0.1mol/L, and the mass concentration of the aqueous paraformaldehyde solution with low polymerization degree is 280-380 g/L.
3. The method according to claim 1, wherein the heating temperature of the low molecular weight phenolic resin prepolymer obtained by the heating in the first step is 40 ℃.
4. The process according to claim 1, wherein in the second step, the molar ratio of tetrabutyl titanate: zinc nitrate hexahydrate: lithium nitrate: ammonium molybdate 3-5:1:2-3: 2; tetrabutyl titanate: the mass volume ratio of ethanol is 1 g: 20 mL.
5. The lithium molybdate complex modified Li as claimed in claim 12ZnTi3O8The preparation method of the nanometer carbon sphere electrode material is characterized in that the nanometer carbon sphere electrode material prepared by the preparation method is applied to a super capacitor.
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