CN108611702B - CoNi2S4Preparation method and application of/TiC/C composite porous nanofiber - Google Patents

CoNi2S4Preparation method and application of/TiC/C composite porous nanofiber Download PDF

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CN108611702B
CN108611702B CN201810426544.2A CN201810426544A CN108611702B CN 108611702 B CN108611702 B CN 108611702B CN 201810426544 A CN201810426544 A CN 201810426544A CN 108611702 B CN108611702 B CN 108611702B
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composite porous
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porous nanofiber
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刘瑞来
胡家朋
林皓
徐婕
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Wuyi University
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武夷学院
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Abstract

The invention provides a CoNi2S4The preparation method of the/TiC/C composite porous nanofiber comprises the following steps: TCA/PMMA/TiO2Preparation of composite nanofiber, preparation of TiC/C composite porous nanofiber and CoNi2S4And preparing the/TiC/C composite porous nanofiber. The invention has the following beneficial effects: CoNi prepared by the invention2S4the/TiC/C composite porous nanofiber has the advantages of simple process, low cost and large-scale industrial production, and the obtained composite electrode material has high specific capacitance and excellent recycling stability and is an excellent electrode material of a super capacitor.

Description

CoNi2S4Preparation method and application of/TiC/C composite porous nanofiber
Technical Field
The invention relates to a CoNi2S4A preparation method and application of/TiC/C composite porous nanofiber belong to the field of nano materials and electrochemistry.
Background
The super capacitor is used as a novel energy storage device, has the advantages of rapid charge and discharge process, long service life, high energy density, environmental protection and the like, and is widely applied to hybrid electric vehicles, large-scale electronic equipment, memory storage equipment and renewable energy power stations. How to prepare simple and cheap electrode materials becomes the key of the development of the super capacitor. At present, three main types of materials are used as electrodes of a super capacitor. The first is carbon material and its derivatives, including granular carbon, graphene, carbon nanotubes, etc.; the second kind is metal compound and its derivative, including metal oxide, hydroxide, sulfide and its phosphate, etc.; the third type is conductive polymer and its derivatives, including polyaniline, polypyrrole, phenolic resin, etc. The carbon material has low specific capacitance, and the conductive polymer is easy to be mechanically degraded, so that the use of the conductive polymer as a supercapacitor material is limited. Compared with carbon materials and conductive polymers, metal compounds are poor in conductivity, and can not only realize electrostatic energy storage as with carbon materials, but also realize energy storage through electrochemical faraday reaction. The research of early metallic compounds has mainly focused on RuO2However, RuO2It is expensive and limits its commercial application. Later, inexpensive metal compounds such as Co, Ni, Fe, Mn, etc. were used.
Binary nickel cobalt oxide (NiCo) as compared to single component oxide2O4) Has higher electrochemical activity and excellent conductivity, so researchers prepare NiCo with different morphologies2O4Electrode materials, e.g. nanowires, nanobelts, NiCo2O4-CNT and NiCo2O4Graphene oxide, and the like. With NiCo2O4In contrast, NiCo2S4The material has higher specific capacitance, lower optical forbidden band gap and higher conductivity, namely, more active points are provided for realizing the rapid charge transfer in oxidation and reduction, and the material meets the requirements of rapid charge and discharge in practical application. How to further increase NiCo2S4The specific capacitance and the cycling stability of the capacitor become the key points of research.
Disclosure of Invention
Aiming at the existingTechnical deficiency, it is an object of the present invention to provide a CoNi2S4A preparation method of/TiC/C composite porous nano-fiber and application thereof.
The invention is realized by the following technical scheme:
the invention provides a CoNi2S4The preparation method of the/TiC/C composite porous nanofiber comprises the following steps:
s1, dissolving cellulose triacetate and polymethyl methacrylate in a ternary mixed solvent of N, N' -dimethylformamide/1, 4-dioxane/acetone to obtain a solution A; adding isopropyl titanate into a binary mixed solvent of DMF/glacial acetic acid to obtain a solution B, adding the solution B into the solution A, and blending to obtain a precursor quenching solution;
s2, quenching the precursor quenching solution at-40 to-10 ℃, extracting to remove the ternary mixed solvent and the binary mixed solvent, washing and drying to obtain TCA/PMMA/TiO2Compounding nano fiber;
s3, mixing the TCA/PMMA/TiO2Soaking the composite nano-fiber in an ethanol solution of sodium hydroxide, washing and drying to obtain cellulose/PMMA/TiO2Compounding nano fiber;
s4, mixing the cellulose/PMMA/TiO2Soaking the composite nano-fiber in acetone, removing PMMA, washing and drying to obtain cellulose/TiO2Composite porous nanofibers;
s5, mixing the cellulose/TiO2The composite porous nanofiber is subjected to preoxidation, one-step carbonization, two-step carbonization and carbothermic reduction in sequence to obtain TiC/C composite porous nanofiber;
s6, dissolving nickel nitrate, cobalt acetate and thiourea in deionized water to obtain a solution C, transferring the solution C into a stainless steel tube type autoclave lined with polytetrafluoroethylene, sequentially adding the TiC/C composite porous nanofiber and the deionized water to 80% of the volume of the stainless steel tube type autoclave, heating the temperature from room temperature to 160-180 ℃ at a heating rate of 5 ℃/min, and carrying out heat preservation reaction to obtain the CoNi2S4TiC/C composite porousAnd (3) nano fibers.
Preferably, in the ternary mixed solvent, the mass ratio of the N, N' -dimethylformamide to the 1, 4-dioxane to the acetone is 5: (0.5-1): (0.5 to 1); in the binary mixed solvent, the mass ratio of DMF to glacial acetic acid is 15: 1.
preferably, in the precursor quenching solution, the mass fraction of the cellulose triacetate is 2-5%, the mass fraction of the polymethyl methacrylate is 1-2%, and the mass fraction of the isopropyl titanate is 0.4-1%.
As a preferred scheme, the pre-oxidation, the one-step carbonization and the two-step carbonization specifically comprise the following operations:
in a nitrogen atmosphere with the flow rate of 50-100 mu L/min, heating from room temperature to 300-360 ℃ at the speed of 3-5 ℃/min, keeping the nitrogen flow unchanged after heat preservation for 2h, heating from 300-360 ℃ to 700-800 ℃ at the speed of 3-5 ℃/min, keeping the nitrogen flow unchanged after heat preservation for 1h, heating from 700-800 ℃ to 1000 ℃ at the speed of 3 ℃/min, and keeping the heat preservation for 1 h.
Preferably, the carbothermic reduction is performed by the following steps:
heating the mixture from 1000 ℃ to 1100-1300 ℃ at a speed of 2-3 ℃/min in an argon atmosphere with a flow rate of 50-100 mu L/min, and preserving heat for 2 h.
CoNi obtained by the preparation method2S4The application of the/TiC/C composite porous nanofiber supercapacitor.
The basic principle of the invention is as follows:
1. cellulose triacetate and polymethyl methacrylate are used as polymer precursors, nanofibers are prepared by a thermally induced phase separation method, and the formation of the nanofibers is mainly characterized in that the polymer precursors are crystallized, orderly and regularly arranged in a solution to form a nanofiber structure, so that TCA/PMMA/TiO is obtained2And (3) compounding the nano fibers.
2. Mixing TCA/PMMA/TiO2Soaking the composite nano-fiber in NaOH ethanol solution to convert acetyl on cellulose triacetate into hydroxyl, namely converting TCA into cellulose, converting thermoplastic material into thermosetting material, and preventing the cellulose from being heated too much subsequentlyMelting occurs in the process, the shape of the fiber can not be kept, and the cellulose/PMMA/TiO is obtained2And (3) compounding the nano fibers.
2. Introducing polymethyl methacrylate into the precursor, dissolving and removing the polymethyl methacrylate in an acetone soaking mode to leave a porous structure, and obtaining the cellulose/TiO2The composite porous nanofiber improves the specific surface area of the fiber and is beneficial to the subsequent compounding of nickel and cobalt binary sulfides on the fiber.
3. The cellulose in the porous nano-fiber is converted into carbon fiber through a series of pre-oxidation, one-step carbonization and two-step carbonization, and the distributed carbonization method is mainly used for improving the carbon yield.
4. The carbon thermal reduction is mainly to react part of carbon in the porous carbon fiber with titanium dioxide at high temperature to form TiC/C porous nano fiber.
5. Adding TiC/C porous nano-fiber into a reaction system, and carrying out hydrothermal reaction on Ni2+And Co2+Reacting with thiourea to generate binary sulfide CoNi2S4Formation of binary sulfide CoNi2S4In-situ compounding on porous fiber to obtain CoNi2S4TiC/C porous nanofiber.
Compared with the prior art, the invention has the following beneficial effects:
1. CoNi prepared by the invention2S4the/TiC/C composite porous nanofiber is a nano-scale porous material, so that the specific surface area of the material is greatly improved, and the wettability between electrolyte and an electrode material is improved.
2. PMMA is introduced into the precursor polymer, and then is removed by calcining, a porous structure is left, and the subsequent CoNi is facilitated2S4And TiC/C composite fiber.
3. CoNi prepared by the invention2S4the/TiC/C composite porous nano-fiber is a binary nickel-cobalt sulfide (CoNi) compared with a single-component nickel-cobalt sulfide2S4) Has higher electrochemical activity and excellent conductivity.
4、CoNi2S4And TiCAfter the/C fiber is compounded, the introduction of TiC and C improves the electrical conductivity, chemical stability and mechanical strength of the electrode material. Therefore, the specific capacitance and the recycling times of the material are greatly improved.
5. CoNi prepared by the invention2S4the/TiC/C composite porous nanofiber has the advantages of simple process, low cost and large-scale industrial production, and the obtained composite electrode material has high specific capacitance and excellent recycling stability and is an excellent electrode material of a super capacitor.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows CoNi prepared in example 1 of the present invention2S4And scanning electron microscope photos of the/TiC/C composite porous nano-fibers.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
1)TCA/PMMA/TiO2Preparation of composite nanofibers
S1: 2g of TCA and 1g of PMMA are dissolved in a ternary mixed solvent of 50g of DMF, 5g of 1, 4-dioxane and 5g of acetone, and the solution is dissolved by magnetic stirring for 5 hours at the temperature of 50 ℃ to form a solution A. 0.4g of isopropyl titanate was added to a mixed solution of 30g of DMF and 2g of glacial acetic acid to obtain a solution B. And pouring the solution B into the solution A, and magnetically stirring and blending at normal temperature to obtain a precursor quenching solution.
S2: and (4) pouring the precursor quenching solution obtained in the step (S1) into a culture dish, and putting the culture dish into a refrigerator which is pre-cooled to-10 ℃ in advance for quenching for 3 hours. After quenching, the petri dish was quickly removed and 500mL of ice-water mixture was poured inIn a culture dish, extracting DMF, THF, acetone and glacial acetic acid solvent in the solution, changing distilled water once every 8h, changing for four times totally, washing for 3 times by using absolute ethyl alcohol, drying by blowing air and drying in vacuum to obtain TCA/PMMA/TiO2And (3) compounding the nano fibers.
S3: mixing TCA/PMMA/TiO2Soaking the composite nano-fiber in 0.05mol/LNaOH ethanol solution for 24h, converting TCA into cellulose, washing with distilled water, and drying to obtain cellulose/PMMA/TiO2And (3) compounding the nano fibers.
2) Preparation of TiC/C composite porous nanofiber
S1: mixing cellulose/PMMA/TiO2Soaking the composite nano-fiber in acetone, oscillating in a constant-temperature water bath for 24h to remove a precursor polymer PMMA, washing with acetone for 3 times, and drying to obtain cellulose/TiO2Composite porous nanofibers.
S2: mixing cellulose/TiO2The composite porous nanofiber is placed in an atmosphere furnace under the protection of nitrogen, the flow of nitrogen is 50 mu L/min, the temperature is increased from 25 ℃ to 300 ℃, the temperature increase rate is 3 ℃/min, the temperature is kept for 2h, the temperature is increased from 300 ℃ to 700 ℃, the temperature increase rate is 3 ℃/min, and the temperature is kept for 1 h. The temperature is raised from 700 ℃ to 1000 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 1 h.
S3: and introducing 50 mu L/min argon, heating from 1000 ℃ to 1100 ℃, wherein the heating rate is 2 ℃/min, and keeping the temperature for 2 h. And after the heat preservation is finished, naturally cooling to normal temperature to obtain the TiC/C composite porous nanofiber.
3)CoNi2S4Preparation of/TiC/C composite porous nanofiber
0.04gNi (NO)2)2·6H2O、0.08g Co(Ac)·4H2O and 0.54g thiourea were added to 20mL deionized water and dissolved with magnetic stirring. The solution was poured into a 50mL stainless steel tubular autoclave lined with teflon, and 0.05g of tic/C composite porous nanofiber and deionized water were sequentially added to 80% of the total volume. And (3) placing the high-pressure reaction kettle in a blast box, heating the high-pressure reaction kettle from room temperature to 160 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 12 hours. Naturally cooling to normal temperature after the reaction is finished, and performing suction filtrationWashing and drying to obtain CoNi2S4the/TiC/C composite porous nanofiber.
CoNi prepared in this example2S4The scanning electron microscope of the/TiC/C composite porous nanofiber is shown in figure 1. The diameter of the fiber is 132 +/-46 nm, the porosity is 91.04 percent, and the specific surface area is 215.3m2(ii) in terms of/g. Under the condition that the current density is 1A/g, the specific capacitance is 315F/g, and after 800 times of cyclic use, the capacitance is 89.2 percent of the initial value.
Example 2
1)TCA/PMMA/TiO2Preparation of composite nanofibers
S1: 2g of TCA and 1g of PMMA are dissolved in a ternary mixed solvent of 50g of DMF, 5g of 1, 4-dioxane and 5g of acetone, and the solution is dissolved by magnetic stirring for 5 hours at the temperature of 50 ℃ to form a solution A. 0.4g of isopropyl titanate was added to a mixed solution of 30g of DMF and 2g of glacial acetic acid to obtain a solution B. And pouring the solution B into the solution A, and magnetically stirring and blending at normal temperature to obtain a precursor quenching solution.
S2: and (4) pouring the precursor quenching solution obtained in the step (S1) into a culture dish, and putting the culture dish into a refrigerator which is pre-cooled to-10 ℃ in advance for quenching for 3 hours. After quenching is finished, the culture dish is quickly taken out, 500mL of ice-water mixture is poured into the culture dish, DMF, THF, acetone and glacial acetic acid solvent in the solution are extracted, distilled water is changed once every 8 hours, the solvent is changed for four times totally, absolute ethyl alcohol is used for washing for 3 times, air blast drying and vacuum drying are carried out, and TCA/PMMA/TiO are obtained2And (3) compounding the nano fibers.
S3: mixing TCA/PMMA/TiO2Soaking the composite nano-fiber in 0.05mol/LNaOH ethanol solution for 24h, converting TCA into cellulose, washing with distilled water, and drying to obtain cellulose/PMMA/TiO2And (3) compounding the nano fibers.
2) Preparation of TiC/C composite porous nanofiber
S1: mixing cellulose/PMMA/TiO2Soaking the composite nano-fiber in acetone, oscillating in a constant-temperature water bath for 24h to remove a precursor polymer PMMA, washing with acetone for 3 times, and drying to obtain cellulose/TiO2Composite porous nanofibers.
S2: mixing cellulose/TiO2CompoundingAnd the porous nanofiber is placed in an atmosphere furnace under the nitrogen protection condition, and the nitrogen flow is 50 mu L/min. The temperature is raised from 25 ℃ to 320 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 2 h. The temperature is raised from 320 ℃ to 750 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 1 h. The temperature is raised from 750 ℃ to 1000 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 1 h.
S3: and introducing 50 mu L/min argon, heating from 1000 ℃ to 1200 ℃, wherein the heating rate is 2 ℃/min, and keeping the temperature for 2 h. And after the heat preservation is finished, naturally cooling to normal temperature to obtain the TiC/C composite porous nanofiber.
3)CoNi2S4Preparation of/TiC/C composite porous nanofiber
0.04gNi (NO)3)2·6H2O、0.08g Co(Ac)·4H2O and 0.54g thiourea were added to 20mL deionized water and dissolved with magnetic stirring. The solution was poured into a 50mL stainless steel tubular autoclave lined with teflon, and 0.05g of tic/C composite porous nanofiber and deionized water were sequentially added to 80% of the total volume. And (3) placing the high-pressure reaction kettle in a blast box, heating the high-pressure reaction kettle from room temperature to 160 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 12 hours. Naturally cooling to normal temperature after the reaction is finished, carrying out suction filtration, washing and drying to obtain CoNi2S4the/TiC/C composite porous nanofiber.
CoNi prepared in this example2S4the/TiC/C composite porous nanofiber. The diameter of the fiber is 122 +/-39 nm, the porosity is 93.12 percent, and the specific surface area is 222.9m2(ii) in terms of/g. Under the condition that the current density is 1A/g, the specific capacitance is 330F/g, and after 800 times of cyclic use, the capacitance is 87.2 percent of the initial value.
Example 3
1)TCA/PMMA/TiO2Preparation of composite nanofibers
S1: 3g TCA and 1.5g PMMA were dissolved in a ternary mixed solvent of 50g DMF, 5g 1, 4-dioxane and 5g acetone by magnetic stirring at 50 ℃ for 5h to form solution A. 0.6g of isopropyl titanate was added to a mixed solution of 30g of DMF and 2g of glacial acetic acid to obtain a solution B. And pouring the solution B into the solution A, and magnetically stirring and blending at normal temperature to obtain a precursor quenching solution.
S2: and (4) pouring the precursor quenching solution obtained in the step (S1) into a culture dish, and putting the culture dish into a refrigerator which is pre-cooled to-20 ℃ in advance for quenching for 4 hours. After quenching is finished, the culture dish is quickly taken out, 500mL of ice-water mixture is poured into the culture dish, DMF, THF, acetone and glacial acetic acid solvent in the solution are extracted, distilled water is changed once every 8 hours, the solvent is changed for four times totally, absolute ethyl alcohol is used for washing for 3 times, air blast drying and vacuum drying are carried out, and TCA/PMMA/TiO are obtained2And (3) compounding the nano fibers.
S3: mixing TCA/PMMA/TiO2Soaking the composite nano-fiber in 0.1mol/LNaOH ethanol solution for 24h, converting TCA into cellulose, washing with distilled water, and drying to obtain cellulose/PMMA/TiO2And (3) compounding the nano fibers.
2) Preparation of TiC/C composite porous nanofiber
S1: mixing cellulose/PMMA/TiO2Soaking the composite nano-fiber in acetone, oscillating in a constant-temperature water bath for 24h to remove a precursor polymer PMMA, washing with acetone for 3 times, and drying to obtain cellulose/TiO2Composite porous nanofibers.
S2: mixing cellulose/TiO2The composite porous nanofiber is placed in an atmosphere furnace under the protection of nitrogen, and the flow rate of the nitrogen is 80 mu L/min. The temperature is raised from 25 ℃ to 320 ℃, the heating rate is 4 ℃/min, and the temperature is kept for 2 h. The temperature is raised from 320 ℃ to 750 ℃, the heating rate is 4 ℃/min, and the temperature is kept for 1 h. The temperature is raised from 750 ℃ to 1000 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 1 h.
S3: and (3) introducing 80 mu L/min of argon, heating the mixture from 1000 ℃ to 1200 ℃, wherein the heating rate is 3 ℃/min, and keeping the temperature for 2 h. And after the heat preservation is finished, naturally cooling to normal temperature to obtain the TiC/C composite porous nanofiber.
3)CoNi2S4Preparation of/TiC/C composite porous nanofiber
0.04gNi (NO)3)2·6H2O、0.08g Co(Ac)·4H2O and 0.54g thiourea were added to 20mL deionized water and dissolved with magnetic stirring. The solution was poured into a 50mL stainless steel tube lined with TeflonIn the autoclave, 0.1g of TiC/C composite porous nano-fiber and deionized water are sequentially added to reach 80% of the total volume. And (3) placing the high-pressure reaction kettle in a blast box, heating the high-pressure reaction kettle from room temperature to 170 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 12 hours. Naturally cooling to normal temperature after the reaction is finished, carrying out suction filtration, washing and drying to obtain CoNi2S4the/TiC/C composite porous nanofiber.
CoNi prepared in this example2S4The scanning electron microscope of the/TiC/C composite porous nanofiber is shown in figure 1. The diameter of the fiber is 151 +/-51 nm, the porosity is 88.25 percent, and the specific surface area is 201.4m2(ii) in terms of/g. Under the condition that the current density is 1A/g, the specific capacitance is 310F/g, and after 800 times of cyclic use, the capacitance is 90.1 percent of the initial value.
Example 4
1)TCA/PMMA/TiO2Preparation of composite nanofibers
S1: 4g of TCA and 1.5g of PMMA are dissolved in a ternary mixed solvent of 45g of DMF, 9g of 1, 4-dioxane and 9g of acetone, and the solution is dissolved by magnetic stirring for 5 hours at 50 ℃ to form a solution A. 0.8g of isopropyl titanate was added to a mixed solution of 30g of DMF and 2g of glacial acetic acid to obtain a solution B. And pouring the solution B into the solution A, and magnetically stirring and blending at normal temperature to obtain a precursor quenching solution.
S2: and (4) pouring the precursor quenching solution obtained in the step (S1) into a culture dish, and putting the culture dish into a refrigerator which is pre-cooled to-20 ℃ in advance for quenching for 4 hours. After quenching is finished, the culture dish is quickly taken out, 500mL of ice-water mixture is poured into the culture dish, DMF, THF, acetone and glacial acetic acid solvent in the solution are extracted, distilled water is changed once every 8 hours, the solvent is changed for four times totally, absolute ethyl alcohol is used for washing for 3 times, air blast drying and vacuum drying are carried out, and TCA/PMMA/TiO are obtained2And (3) compounding the nano fibers.
S3: mixing TCA/PMMA/TiO2Soaking the composite nano-fiber in 0.1mol/LNaOH ethanol solution for 24h, converting TCA into cellulose, washing with distilled water, and drying to obtain cellulose/PMMA/TiO2And (3) compounding the nano fibers.
2) Preparation of TiC/C composite porous nanofiber
S1: mixing cellulose/PMMA/TiO2Composite nanoSoaking rice fiber in acetone, shaking in constant temperature water bath for 24 hr to remove precursor polymer PMMA, washing with acetone for 3 times, and drying to obtain cellulose/TiO2Composite porous nanofibers.
S2: mixing cellulose/TiO2The composite porous nanofiber is placed in an atmosphere furnace under the protection of nitrogen, and the flow rate of the nitrogen is 80 mu L/min. The temperature is raised from 25 ℃ to 350 ℃, the heating rate is 4 ℃/min, and the temperature is kept for 2 h. The temperature is raised from 350 ℃ to 800 ℃, the heating rate is 4 ℃/min, and the temperature is kept for 1 h. The temperature is raised from 800 ℃ to 1000 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 1 h.
S3: heating from 1000 deg.C to 1250 deg.C under 100 μ L/min argon gas, heating at 3 deg.C/min, and holding at the temperature for 2 h. And after the heat preservation is finished, naturally cooling to normal temperature to obtain the TiC/C composite porous nanofiber.
3)CoNi2S4Preparation of/TiC/C composite porous nanofiber
0.04gNi (NO)3)2·6H2O、0.08g Co(Ac)·4H2O and 0.54g thiourea were added to 20mL deionized water and dissolved with magnetic stirring. The solution was poured into a 50mL stainless steel tubular autoclave lined with teflon, and 0.1g of tic/C composite porous nanofiber and deionized water were sequentially added to 80% of the total volume. And (3) placing the high-pressure reaction kettle in a blast box, heating the high-pressure reaction kettle from room temperature to 170 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 12 hours. Naturally cooling to normal temperature after the reaction is finished, carrying out suction filtration, washing and drying to obtain CoNi2S4the/TiC/C composite porous nanofiber.
CoNi prepared in this example2S4The scanning electron microscope of the/TiC/C composite porous nanofiber is shown in figure 1. The diameter of the fiber is 148 +/-36 nm, the porosity is 90.18 percent, and the specific surface area is 199.5m2(ii) in terms of/g. Under the condition that the current density is 1A/g, the specific capacitance is 290F/g, and after 800 times of cyclic use, the capacitance is 91.2 percent of the initial value.
Example 5
1)TCA/PMMA/TiO2Preparation of composite nanofibers
S1: 5g of TCA and 2g of PMMA are dissolved in a ternary mixed solvent of 45g of DMF, 9g of 1, 4-dioxane and 9g of acetone, and the solution is dissolved by magnetic stirring for 5 hours at 50 ℃ to form a solution A. 0.8g of isopropyl titanate was added to a mixture of 30g of DMF and 2g of glacial acetic acid to obtain solution B. And pouring the solution B into the solution A, and magnetically stirring and blending at normal temperature to obtain a precursor quenching solution.
S2: and (4) pouring the precursor quenching solution obtained in the step (S1) into a culture dish, and putting the culture dish into a refrigerator which is pre-cooled to-30 ℃ in advance for quenching for 5 hours. After quenching is finished, the culture dish is quickly taken out, 500mL of ice-water mixture is poured into the culture dish, DMF, THF, acetone and glacial acetic acid solvent in the solution are extracted, distilled water is changed once every 8 hours, the solvent is changed for four times totally, absolute ethyl alcohol is used for washing for 3 times, air blast drying and vacuum drying are carried out, and TCA/PMMA/TiO are obtained2And (3) compounding the nano fibers.
S3: mixing TCA/PMMA/TiO2Soaking the composite nano-fiber in 0.15mol/LNaOH ethanol solution for 24h, converting TCA into cellulose, washing with distilled water, and drying to obtain cellulose/PMMA/TiO2And (3) compounding the nano fibers.
2) Preparation of TiC/C composite porous nanofiber
S1: mixing cellulose/PMMA/TiO2Soaking the composite nano-fiber in acetone, oscillating in a constant-temperature water bath for 24h to remove a precursor polymer PMMA, washing with acetone for 3 times, and drying to obtain cellulose/TiO2Composite porous nanofibers.
S2: mixing cellulose/TiO2The composite porous nanofiber is placed in an atmosphere furnace under the nitrogen protection condition, and the nitrogen flow is 100 mu L/min. The temperature is raised from 25 ℃ to 350 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 2 h. The temperature is raised from 350 ℃ to 800 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1 h. The temperature is raised from 800 ℃ to 1000 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 1 h.
S3: heating from 1000 deg.C to 1250 deg.C under 100 μ L/min argon gas, heating at 3 deg.C/min, and holding at the temperature for 2 h. And after the heat preservation is finished, naturally cooling to normal temperature to obtain the TiC/C composite porous nanofiber.
3)CoNi2S4/TPreparation of iC/C composite porous nanofiber
0.04gNi (NO)3)2·6H2O、0.08g Co(Ac)·4H2O and 0.54g thiourea were added to 20mL deionized water and dissolved with magnetic stirring. The solution was poured into a 50mL stainless steel tubular autoclave lined with teflon, and 0.1g of tic/C composite porous nanofiber and deionized water were sequentially added to 80% of the total volume. And (3) placing the high-pressure reaction kettle in a blast box, heating the high-pressure reaction kettle from room temperature to 180 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 12 hours. Naturally cooling to normal temperature after the reaction is finished, carrying out suction filtration, washing and drying to obtain CoNi2S4the/TiC/C composite porous nanofiber.
CoNi prepared in this example2S4The scanning electron microscope of the/TiC/C composite porous nanofiber is shown in figure 1. The diameter of the fiber is 150 +/-39 nm, the porosity is 92.18 percent, and the specific surface area is 210.6m2(ii) in terms of/g. Under the condition that the current density is 1A/g, the specific capacitance is 301F/g, and after the capacitor is recycled for 800 times, the capacitance is 88.7 percent of the initial value.
Comparative example 1
CoNi was obtained in addition to example 1 without PMMA2S4the/TiC/C composite nanofiber. The diameter of the fiber is 165 +/-45 nm, the porosity is 78.22 percent, and the specific surface area is 116.2m2(ii) in terms of/g. Under the condition of current density of 1A/g, the specific capacitance is 189.5F/g, and after 800 times of cyclic use, the capacitance is 85.3 percent of the initial value. The specific surface area and porosity of the material are greatly reduced compared to example 1, thus resulting in a reduction in its specific capacitance.
Comparative example 2
Based on example 1, step 3) CoNi2S4The preparation of the/TiC/C composite porous nano-fiber only adopts the addition of 0.04gNi (NO)3)2·6H2O, 0.08g of Co (Ac). 4H was not added2O, only NiS/TiC/C composite porous nano-fiber can be obtained finally, the diameter of the fiber is 136 +/-66 nm, the porosity is 90.25%, and the specific surface area is 206.1m2(ii) in terms of/g. Under the condition that the current density is 1A/g, the specific capacitance is 206.1F/g, and after the capacitor is recycled for 800 times, the capacitance is 88.4 percent of the initial value.
Comparative example 3
Based on example 1, step 3) CoNi2S4The preparation of the/TiC/C composite porous nano-fiber only adopts the addition of 0.08g Co (Ac). 4H2O, not added 0.04gNi (NO)3)2·6H2O, only CoS/TiC/C composite porous nano-fiber can be obtained finally, the diameter of the fiber is 138 +/-46 nm, the porosity is 89.09%, and the specific surface area is 222.1m2(ii) in terms of/g. Under the condition of current density of 1A/g, the specific capacitance is 189F/g, and after 800 times of cyclic use, the capacitance is 86.2 percent of the initial value.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (2)

1. CoNi2S4The preparation method of the/TiC/C composite porous nanofiber is characterized by comprising the following steps of:
s1, dissolving cellulose triacetate and polymethyl methacrylate inN, N’Dissolving in a ternary mixed solvent of-dimethylformamide/1, 4-dioxane/acetone to obtain a solution A; adding isopropyl titanate into a binary mixed solvent of DMF/glacial acetic acid to obtain a solution B, adding the solution B into the solution A, and blending to obtain a precursor quenching solution;
s2, quenching the precursor quenching solution at-40 to-10 ℃, extracting to remove the ternary mixed solvent and the binary mixed solvent, washing and drying to obtain TCA/PMMA/TiO2Compounding nano fiber;
s3, mixing the TCA/PMMA/TiO2Soaking the composite nano-fiber in an ethanol solution of sodium hydroxide, washing and drying to obtain cellulose/PMMA/TiO2Compounding nano fiber;
s4, mixing the cellulose/PMMA/TiO2Soaking the composite nano-fiber in acetone, removing PMMA, washing and drying to obtain cellulose/TiO2Composite porous nanofiber；
S5, mixing the cellulose/TiO2The composite porous nanofiber is subjected to preoxidation, one-step carbonization, two-step carbonization and carbothermic reduction in sequence to obtain TiC/C composite porous nanofiber;
s6, dissolving nickel nitrate, cobalt acetate and thiourea in deionized water to obtain a solution C, transferring the solution C into a stainless steel tube type autoclave lined with polytetrafluoroethylene, sequentially adding the TiC/C composite porous nanofiber and the deionized water to 80% of the volume of the stainless steel tube type autoclave, heating the temperature from room temperature to 160-180 ℃ at a heating rate of 5 ℃/min, and carrying out heat preservation reaction to obtain the CoNi2S4a/TiC/C composite porous nanofiber;
in the ternary mixed solvent, the solvent is mixed,N, N’-dimethylformamide, 1, 4-dioxane and acetone in a mass ratio of 5: (0.5-1): (0.5 to 1); in the binary mixed solvent, the mass ratio of DMF to glacial acetic acid is 15: 1;
in the precursor quenching solution, the mass fraction of cellulose triacetate is 2-5%, the mass fraction of polymethyl methacrylate is 1-2%, and the mass fraction of isopropyl titanate is 0.4-1%;
the concrete operations of pre-oxidation, one-step carbonization and two-step carbonization are as follows:
in a nitrogen atmosphere with the flow rate of 50-100 mu L/min, heating from room temperature to 300-360 ℃ at the speed of 3-5 ℃/min, keeping the nitrogen flow unchanged after heat preservation for 2h, heating from 300-360 ℃ to 700-800 ℃ at the speed of 3-5 ℃/min, keeping the nitrogen flow unchanged after heat preservation for 1h, heating from 700-800 ℃ to 1000 ℃ at the speed of 3 ℃/min, and keeping the heat preservation for 1 h;
the specific operation of the carbothermic reduction is as follows:
heating the mixture from 1000 ℃ to 1100-1300 ℃ at a speed of 2-3 ℃/min in an argon atmosphere with a flow rate of 50-100 mu L/min, and preserving heat for 2 h.
2. CoNi obtained by the preparation method of claim 12S4The application of the/TiC/C composite porous nanofiber in the super capacitor.
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