CN108611702A - CoNi2S4The preparation method and its usage of the compound porous nanofibers of/TiC/C - Google Patents

CoNi2S4The preparation method and its usage of the compound porous nanofibers of/TiC/C Download PDF

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CN108611702A
CN108611702A CN201810426544.2A CN201810426544A CN108611702A CN 108611702 A CN108611702 A CN 108611702A CN 201810426544 A CN201810426544 A CN 201810426544A CN 108611702 A CN108611702 A CN 108611702A
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tic
compound porous
solution
coni
tio
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CN108611702B (en
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刘瑞来
胡家朋
林皓
徐婕
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Wuyi University
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晋江瑞碧科技有限公司
武夷学院
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    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
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    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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    • 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
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    • 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
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention provides a kind of CoNi2S4The preparation method of the compound porous nanofibers of/TiC/C comprising following steps：TCA/PMMA/TiO2The preparation of composite nano fiber, the preparation of the compound porous nanofibers of TiC/C, CoNi2S4The preparation of the compound porous nanofibers of/TiC/C.The present invention has the advantages that：CoNi prepared by the present invention2S4The compound porous nanofibers of/TiC/C are simple for process, it is of low cost, can a large amount of industrialized productions, the combination electrode material of acquisition has very high specific capacitance and superior recycling stability, is a kind of excellent electrode material for super capacitor.

Description

CoNi2S4The preparation method and its usage of the compound porous nanofibers of/TiC/C
Technical field
The present invention relates to a kind of CoNi2S4The preparation method and its usage of the compound porous nanofibers of/TiC/C, belongs to nanometer Material and electrochemical field.
Background technology
Ultracapacitor is as a kind of novel energy storage device, due to fast charging and discharging process, service life length, energy The advantages that metric density is big, environmental protection is widely used in hybrid-power electric vehicle, large scale electronic equipment, memory storage devices and can Renewable-resource power station.Simple, cheap electrode material how is prepared, the key of ultracapacitor development is become.It is main at present There is electrode of the three classes material as ultracapacitor.The first kind is carbon material and its derivative, including granulated carbon, graphene, carbon Nanotube etc.；Second class is metallic compound and its derivative, including metal oxide, hydroxide, sulfide and its phosphoric acid Salt etc.；Third class is conducting polymer and its derivative, including polyaniline, polypyrrole, phenolic resin etc..The specific capacitance of carbon material Relatively low, conducting polymer is easy to happen mechanical degradation, limits it and is used as super capacitor material.With carbon material and conduction Polymer phase ratio can not only realize electrostatic energy storage as carbon material, can also pass through although metallic compound poorly conductive Electrochemistry faraday's reaction realizes energy storage.The research of early stage metallic compound is concentrated mainly on RuO2, however RuO2It is expensive, Limit its commercial applications.Later people use cheap metallic compound, such as Co, Ni, Fe, Mn compound.
Binary nickel cobalt oxide (the NiCo compared with single component oxide2O4), there is higher electro-chemical activity, excellent Electric conductivity, therefore researcher is prepared for the NiCo of different-shape2O4Electrode material, such as nano wire, nanobelt, NiCo2O4-CNT With NiCo2O4Graphene oxide etc..With NiCo2O4It compares, NiCo2S4With higher specific capacitance, lower photonic band gap energy The fast transfer of charge is realized when gap and higher electric conductivity, i.e. redox with more active sites, in practical application Meet fast charging and discharging demand.How NiCo is further increased2S4Specific capacitance and its cyclical stability, become the key of research.
Invention content
For the defects in the prior art, the object of the present invention is to provide a kind of CoNi2S4The compound porous Nanowires of/TiC/C The preparation method and its usage of dimension.
The present invention is achieved by the following technical solutions：
The present invention provides a kind of CoNi2S4The preparation method of the compound porous nanofibers of/TiC/C comprising following step Suddenly：
S1, Triafol T and polymethyl methacrylate are dissolved in N, N '-dimethyl formamide/1,4- dioxies six In the ternary mixed solvent of ring/acetone, obtain forming solution A after dissolving；Isopropyl titanate is added to the binary of DMF/ glacial acetic acid In the mixed solvent obtains solution B, and the solution B is added in solution A, presoma quenching solution is obtained after blending；
S2, by the presoma quenching solution after -40~-10 DEG C are quenched, extraction remove ternary mixed solvent and Binary mixed solvent, it is washed, be dried to obtain TCA/PMMA/TiO2Composite nano fiber；
S3, by the TCA/PMMA/TiO2After composite nano fiber is soaked in the ethanol solution of sodium hydroxide, through washing It washs, be dried to obtain cellulose/PMMA/TiO2Composite nano fiber；
S4, by the cellulose/PMMA/TiO2Composite nano fiber impregnates in acetone, after removing PMMA, washed, It is dried to obtain cellulose/TiO2Compound porous nanofiber；
S5, by the cellulose/TiO2Compound porous nanofiber is successively by pre-oxidation, step carbonization, the carbonization of two steps And carbon thermal reduction, obtain the compound porous nanofibers of TiC/C；
S6, after nickel nitrate, cobalt acetate and thiocarbamide are dissolved in deionized water, solution C is obtained, the solution C is transferred to interior It is lined in the stainless steel tubular type autoclave of polytetrafluoroethylene (PTFE), sequentially adds the compound porous nanofibers of the TiC/C and deionization Water, until in stainless steel tubular type autoclave volume 80%, with the heating rate of 5 DEG C/min by room temperature to 160~180 DEG C, After insulation reaction, the CoNi is obtained2S4The compound porous nanofibers of/TiC/C.
Preferably, in the ternary mixed solvent, N, N '-dimethyl formamide, Isosorbide-5-Nitrae-dioxane and acetone Mass ratio be 5：(0.5~1)：(0.5~1)；In the binary mixed solvent, the mass ratio of DMF and glacial acetic acid is 15：1.
Preferably, in the presoma quenching solution, the mass fraction of Triafol T is 2~5%, poly- first The mass fraction of base methyl acrylate is 1~2%, and the mass fraction of isopropyl titanate is 0.4~1%.
Preferably, it is described pre-oxidation, a step carbonization, two steps carbonization concrete operations be：
In the nitrogen atmosphere of 50~100 μ L/min flows, with the rate of 3~5 DEG C/min by room temperature to 300~ It 360 DEG C, after keeping the temperature 2h, keeps nitrogen flow constant, 700~800 is warming up to by 300~360 DEG C with the rate of 3~5 DEG C/min DEG C, it after keeping the temperature 1h, keeps nitrogen flow constant, is warming up to 1000 DEG C by 700~800 with the rate of 3 DEG C/min, keeps the temperature 1h.
Preferably, the concrete operations of the carbon thermal reduction are：
In the argon gas atmosphere of 50~100 μ L/min flows, 1100 are warming up to by 1000 DEG C with the rate of 2~3 DEG C/min ~1300 DEG C, keep the temperature 2h.
A kind of CoNi obtained by preparation method above-mentioned2S4In the compound porous nanofiber ultracapacitors of/TiC/C Purposes.
The present invention basic principle be：
1, using Triafol T and polymethyl methacrylate as polymer precursor, pass through Thermal inactive method system Standby nanofiber, the formation of nanofiber is mainly the polymer precursor regular arrangement form Nanowire of crystalline order in the solution Structure is tieed up, TCA/PMMA/TiO is obtained2Composite nano fiber.
2, by TCA/PMMA/TiO2Composite nano fiber is immersed in the ethanol solution of NaOH, will be on Triafol T Acetyl group be changed into hydroxyl, i.e. TCA is changed into cellulose, is changed into thermosets by thermoplastic material, prevents it rear It is melted in continuous heating process, cannot keep fiber morphology, obtain cellulose/PMMA/TiO2Composite nano fiber.
2, the polymethyl methacrylate introduced in presoma, after removal dissolved by acetone soak mode, leave Porous structure obtains cellulose/TiO2Compound porous nanofiber improves pulp freeness, and is conducive to follow-up nickel, cobalt two First sulfide is compound on fiber.
3, the cellulose in porous nano-fibre is made to be changed by a series of pre-oxidation, step carbonization and the carbonization of two steps Carbon fiber, and use distribution carbonizatin method primarily to improving to obtain carbon rate.
4, carbon thermal reduction is mainly reacted the part carbon in porous carbon fiber with titanium dioxide by high temperature, forms TiC/ C porous nano-fibres.
5, TiC/C porous nano-fibres are added in the reaction system, by hydro-thermal reaction by Ni2+And Co2+It is reacted with thiocarbamide Generate binary sulfide CoNi2S4, the binary sulfide CoNi of generation2S4On In-situ reaction to porous fibre, CoNi is obtained2S4/ TiC/C porous nano-fibres.
Compared with prior art, the present invention has following advantageous effect：
1, CoNi prepared by the present invention2S4The compound porous nanofibers of/TiC/C, size are nano level porous material, greatly The big specific surface area for improving material, therefore improve the wellability between electrolyte and electrode material.
2, PMMA is introduced in precursor polymer, it is rear to be removed it using calcining, porous structure is left, is conducive to follow-up CoNi2S4It is compound between TiC/C composite fibres.
3, CoNi prepared by the present invention2S4The compound porous nanofibers of/TiC/C, and one pack system nickel cobalt testing sulphide ratio, two First nickel cobalt sulfide (CoNi2S4), there is higher electro-chemical activity, excellent electric conductivity.
4、CoNi2S4After TiC/C fiber composites, the introducing of TiC and C improve conductivity, the chemical stabilization of electrode material Property and mechanical strength.Therefore it substantially increases the specific capacitance of material and recycles number.
5, CoNi prepared by the present invention2S4The compound porous nanofibers of/TiC/C are simple for process, it is of low cost, can a large amount of works Industry metaplasia is produced, and the combination electrode material of acquisition has very high specific capacitance and superior recycling stability, is a kind of excellent Electrode material for super capacitor.
Description of the drawings
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention, Objects and advantages will become more apparent upon：
Fig. 1 is the CoNi that in the present invention prepared by embodiment 12S4The stereoscan photograph of the compound porous nanofibers of/TiC/C.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention Protection domain.
Embodiment 1
1)TCA/PMMA/TiO2The preparation of composite nano fiber
S1：The ternary mixing that 2g TCA and 1g PMMA are dissolved in 50g DMF, 5g 1,4- dioxane and 5g acetone is molten In agent, 50 DEG C of magnetic agitation 5h dissolvings form solution A.0.4g isopropyl titanates addition 30g DMF, 2g glacial acetic acid are mixed molten In liquid, solution B is obtained.Solution B is poured into solution A, magnetic agitation is blended under room temperature, obtains presoma quenching solution.
S2：The presoma quenching solution that step S1 is obtained is taken and is poured into culture dish, culture dish is put into be cooled in advance in advance- 3h is quenched in 10 DEG C of refrigerators.After quenching, culture dish is quickly removed, 500mL mixture of ice and water is poured into culture dish, is extracted DMF, THF, acetone and the glacial acetic acid solvent in solution are taken, first water is changed every 8h, is changed in total four times, absolute ethyl alcohol washing 3 times, forced air drying, vacuum drying obtain TCA/PMMA/TiO2Composite nano fiber.
S3：By TCA/PMMA/TiO2Composite nano fiber is immersed in 0.05mol/LNaOH alcohol solution dippings for 24 hours, will TCA is converted into cellulose, and distillation water washing, drying obtain cellulose/PMMA/TiO2Composite nano fiber.
2) preparation of the compound porous nanofibers of TiC/C
S1：By cellulose/PMMA/TiO2Composite nano fiber impregnates in acetone, and water bath with thermostatic control is shaken for 24 hours, to remove Precursor polymer PMMA, acetone wash 3 times, drying, obtain cellulose/TiO2Compound porous nanofiber.
S2：By cellulose/TiO2Compound porous nanofiber is placed under the conditions of nitrogen protection in atmosphere furnace, nitrogen stream Amount is 50 μ L/min, and 300 DEG C are warming up to from 25 DEG C, and heating rate is 3 DEG C/min, keeps the temperature 2h at such a temperature, is heated up from 300 DEG C To 700 DEG C, heating rate is 3 DEG C/min, keeps the temperature 1h at such a temperature.It is warming up to 1000 DEG C from 700 DEG C, heating rate is 3 DEG C/ Min keeps the temperature 1h at such a temperature.
S3：Under the conditions of logical 50 μ L/min argon gas, 1100 DEG C are warming up to from 1000 DEG C, heating rate is 2 DEG C/min, in the temperature Degree is lower to keep the temperature 2h.After heat preservation, it is naturally cooling to room temperature, obtains the compound porous nanofibers of TiC/C.
3)CoNi2S4The preparation of the compound porous nanofibers of/TiC/C
By 0.04gNi (NO2)2·6H2O、0.08g Co(Ac)·4H2O and 0.54g thiocarbamides are added in 20mL deionized waters, Magnetic agitation dissolves.Solution is poured into the stainless steel tubular type autoclave that 50mL liners are polytetrafluoroethylene (PTFE), sequentially adds 0.05g The compound porous nanofibers of TiC/C and deionized water are to the 80% of total capacity.Autoclave is placed in bellows, from room Temperature is warming up to 160 DEG C, and heating rate is 5 DEG C/min, keeps the temperature 12h.It is naturally cooling to room temperature after reaction, filters, washing, do It is dry to obtain CoNi2S4The compound porous nanofibers of/TiC/C.
CoNi manufactured in the present embodiment2S4The scanning electron microscope of the compound porous nanofibers of/TiC/C is as shown in Figure 1.Fiber A diameter of 132 ± 46nm, porosity 91.04%, specific surface area 215.3m2/g.Under the conditions of current density is 1A/g, than electricity It is 315F/g to hold, and after recycling 800 times, capacitance is the 89.2% of initial value.
Embodiment 2
1)TCA/PMMA/TiO2The preparation of composite nano fiber
S1：The ternary mixing that 2g TCA and 1g PMMA are dissolved in 50g DMF, 5g 1,4- dioxane and 5g acetone is molten In agent, 50 DEG C of magnetic agitation 5h dissolvings form solution A.0.4g isopropyl titanates addition 30g DMF, 2g glacial acetic acid are mixed molten In liquid, solution B is obtained.Solution B is poured into solution A, magnetic agitation is blended under room temperature, obtains presoma quenching solution.
S2：The presoma quenching solution that step S1 is obtained is taken and is poured into culture dish, culture dish is put into be cooled in advance in advance- 3h is quenched in 10 DEG C of refrigerators.After quenching, culture dish is quickly removed, 500mL mixture of ice and water is poured into culture dish, is extracted DMF, THF, acetone and the glacial acetic acid solvent in solution are taken, first water is changed every 8h, is changed in total four times, absolute ethyl alcohol washing 3 times, forced air drying, vacuum drying obtain TCA/PMMA/TiO2Composite nano fiber.
S3：By TCA/PMMA/TiO2Composite nano fiber is immersed in 0.05mol/LNaOH alcohol solution dippings for 24 hours, will TCA is converted into cellulose, and distillation water washing, drying obtain cellulose/PMMA/TiO2Composite nano fiber.
2) preparation of the compound porous nanofibers of TiC/C
S1：By cellulose/PMMA/TiO2Composite nano fiber impregnates in acetone, and water bath with thermostatic control is shaken for 24 hours, to remove Precursor polymer PMMA, acetone wash 3 times, drying, obtain cellulose/TiO2Compound porous nanofiber.
S2：By cellulose/TiO2Compound porous nanofiber is placed under the conditions of nitrogen protection in atmosphere furnace, nitrogen stream Amount is 50 μ L/min.320 DEG C are warming up to from 25 DEG C, heating rate is 3 DEG C/min, keeps the temperature 2h at such a temperature.It heats up from 320 DEG C To 750 DEG C, heating rate is 3 DEG C/min, keeps the temperature 1h at such a temperature.It is warming up to 1000 DEG C from 750 DEG C, heating rate is 3 DEG C/ Min keeps the temperature 1h at such a temperature.
S3：Under the conditions of logical 50 μ L/min argon gas, 1200 DEG C are warming up to from 1000 DEG C, heating rate is 2 DEG C/min, in the temperature Degree is lower to keep the temperature 2h.After heat preservation, it is naturally cooling to room temperature, obtains the compound porous nanofibers of TiC/C.
3)CoNi2S4The preparation of the compound porous nanofibers of/TiC/C
By 0.04gNi (NO3)2·6H2O、0.08g Co(Ac)·4H2O and 0.54g thiocarbamides are added in 20mL deionized waters, Magnetic agitation dissolves.Solution is poured into the stainless steel tubular type autoclave that 50mL liners are polytetrafluoroethylene (PTFE), sequentially adds 0.05g The compound porous nanofibers of TiC/C and deionized water are to the 80% of total capacity.Autoclave is placed in bellows, from room Temperature is warming up to 160 DEG C, and heating rate is 5 DEG C/min, keeps the temperature 12h.It is naturally cooling to room temperature after reaction, filters, washing, do It is dry to obtain CoNi2S4The compound porous nanofibers of/TiC/C.
CoNi manufactured in the present embodiment2S4The compound porous nanofibers of/TiC/C.A diameter of 122 ± 39nm, the hole of fiber Rate is 93.12%, specific surface area 222.9m2/g.Under the conditions of current density is 1A/g, specific capacitance 330F/g is recycled After 800 times, capacitance is the 87.2% of initial value.
Embodiment 3
1)TCA/PMMA/TiO2The preparation of composite nano fiber
S1：The ternary that 3g TCA and 1.5g PMMA are dissolved in 50g DMF, 5g 1,4- dioxane and 5g acetone mixes In solvent, 50 DEG C of magnetic agitation 5h dissolvings form solution A.30g DMF is added in 0.6g isopropyl titanates, 2g glacial acetic acid mixes In solution, B solution is obtained.B solution is poured into solution A, magnetic agitation is blended under room temperature, obtains presoma quenching solution.
S2：The presoma quenching solution that step S1 is obtained is taken and is poured into culture dish, culture dish is put into be cooled in advance in advance- 4h is quenched in 20 DEG C of refrigerators.After quenching, culture dish is quickly removed, 500mL mixture of ice and water is poured into culture dish, is extracted DMF, THF, acetone and the glacial acetic acid solvent in solution are taken, first water is changed every 8h, is changed in total four times, absolute ethyl alcohol washing 3 times, forced air drying, vacuum drying obtain TCA/PMMA/TiO2Composite nano fiber.
S3：By TCA/PMMA/TiO2Composite nano fiber is immersed in 0.1mol/LNaOH alcohol solution dippings for 24 hours, will TCA is converted into cellulose, and distillation water washing, drying obtain cellulose/PMMA/TiO2Composite nano fiber.
2) preparation of the compound porous nanofibers of TiC/C
S1：By cellulose/PMMA/TiO2Composite nano fiber impregnates in acetone, and water bath with thermostatic control is shaken for 24 hours, to remove Precursor polymer PMMA, acetone wash 3 times, drying, obtain cellulose/TiO2Compound porous nanofiber.
S2：By cellulose/TiO2Compound porous nanofiber is placed under the conditions of nitrogen protection in atmosphere furnace, nitrogen stream Amount is 80 μ L/min.320 DEG C are warming up to from 25 DEG C, heating rate is 4 DEG C/min, keeps the temperature 2h at such a temperature.It heats up from 320 DEG C To 750 DEG C, heating rate is 4 DEG C/min, keeps the temperature 1h at such a temperature.It is warming up to 1000 DEG C from 750 DEG C, heating rate is 3 DEG C/ Min keeps the temperature 1h at such a temperature.
S3：Under the conditions of logical 80 μ L/min argon gas, 1200 DEG C are warming up to from 1000 DEG C, heating rate is 3 DEG C/min, in the temperature Degree is lower to keep the temperature 2h.After heat preservation, it is naturally cooling to room temperature, obtains the compound porous nanofibers of TiC/C.
3)CoNi2S4The preparation of the compound porous nanofibers of/TiC/C
By 0.04gNi (NO3)2·6H2O、0.08g Co(Ac)·4H2O and 0.54g thiocarbamides are added in 20mL deionized waters, Magnetic agitation dissolves.Solution is poured into the stainless steel tubular type autoclave that 50mL liners are polytetrafluoroethylene (PTFE), sequentially adds 0.1g The compound porous nanofibers of TiC/C and deionized water are to the 80% of total capacity.Autoclave is placed in bellows, from room Temperature is warming up to 170 DEG C, and heating rate is 5 DEG C/min, keeps the temperature 12h.It is naturally cooling to room temperature after reaction, filters, washing, do It is dry to obtain CoNi2S4The compound porous nanofibers of/TiC/C.
CoNi manufactured in the present embodiment2S4The scanning electron microscope of the compound porous nanofibers of/TiC/C is as shown in Figure 1.Fiber A diameter of 151 ± 51nm, porosity 88.25%, specific surface area 201.4m2/g.Under the conditions of current density is 1A/g, than electricity It is 310F/g to hold, and after recycling 800 times, capacitance is the 90.1% of initial value.
Embodiment 4
1)TCA/PMMA/TiO2The preparation of composite nano fiber
S1：The ternary that 4g TCA and 1.5g PMMA are dissolved in 45g DMF, 9g 1,4- dioxane and 9g acetone mixes In solvent, 50 DEG C of magnetic agitation 5h dissolvings form solution A.30g DMF is added in 0.8g isopropyl titanates, 2g glacial acetic acid mixes In solution, solution B is obtained.Solution B is poured into solution A, magnetic agitation is blended under room temperature, obtains presoma quenching solution.
S2：The presoma quenching solution that step S1 is obtained is taken and is poured into culture dish, culture dish is put into be cooled in advance in advance- 4h is quenched in 20 DEG C of refrigerators.After quenching, culture dish is quickly removed, 500mL mixture of ice and water is poured into culture dish, is extracted DMF, THF, acetone and the glacial acetic acid solvent in solution are taken, first water is changed every 8h, is changed in total four times, absolute ethyl alcohol washing 3 times, forced air drying, vacuum drying obtain TCA/PMMA/TiO2Composite nano fiber.
S3：By TCA/PMMA/TiO2Composite nano fiber is immersed in 0.1mol/LNaOH alcohol solution dippings for 24 hours, will TCA is converted into cellulose, and distillation water washing, drying obtain cellulose/PMMA/TiO2Composite nano fiber.
2) preparation of the compound porous nanofibers of TiC/C
S1：By cellulose/PMMA/TiO2Composite nano fiber impregnates in acetone, and water bath with thermostatic control is shaken for 24 hours, to remove Precursor polymer PMMA, acetone wash 3 times, drying, obtain cellulose/TiO2Compound porous nanofiber.
S2：By cellulose/TiO2Compound porous nanofiber is placed under the conditions of nitrogen protection in atmosphere furnace, nitrogen stream Amount is 80 μ L/min.350 DEG C are warming up to from 25 DEG C, heating rate is 4 DEG C/min, keeps the temperature 2h at such a temperature.It heats up from 350 DEG C To 800 DEG C, heating rate is 4 DEG C/min, keeps the temperature 1h at such a temperature.It is warming up to 1000 DEG C from 800 DEG C, heating rate is 3 DEG C/ Min keeps the temperature 1h at such a temperature.
S3：Under the conditions of logical 100 μ L/min argon gas, 1250 DEG C are warming up to from 1000 DEG C, heating rate is 3 DEG C/min, at this At a temperature of keep the temperature 2h.After heat preservation, it is naturally cooling to room temperature, obtains the compound porous nanofibers of TiC/C.
3)CoNi2S4The preparation of the compound porous nanofibers of/TiC/C
By 0.04gNi (NO3)2·6H2O、0.08g Co(Ac)·4H2O and 0.54g thiocarbamides are added in 20mL deionized waters, Magnetic agitation dissolves.Solution is poured into the stainless steel tubular type autoclave that 50mL liners are polytetrafluoroethylene (PTFE), sequentially adds 0.1g The compound porous nanofibers of TiC/C and deionized water are to the 80% of total capacity.Autoclave is placed in bellows, from room Temperature is warming up to 170 DEG C, and heating rate is 5 DEG C/min, keeps the temperature 12h.It is naturally cooling to room temperature after reaction, filters, washing, do It is dry to obtain CoNi2S4The compound porous nanofibers of/TiC/C.
CoNi manufactured in the present embodiment2S4The scanning electron microscope of the compound porous nanofibers of/TiC/C is as shown in Figure 1.Fiber A diameter of 148 ± 36nm, porosity 90.18%, specific surface area 199.5m2/g.Under the conditions of current density is 1A/g, than electricity It is 290F/g to hold, and after recycling 800 times, capacitance is the 91.2% of initial value.
Embodiment 5
1)TCA/PMMA/TiO2The preparation of composite nano fiber
S1：The ternary mixing that 5g TCA and 2g PMMA are dissolved in 45g DMF, 9g 1,4- dioxane and 9g acetone is molten In agent, 50 DEG C of magnetic agitation 5h dissolvings form solution A.30g DMF, 2g glacial acetic acid mixed liquors is added in 0.8g isopropyl titanates In, obtain solution B.Solution B is poured into solution A, magnetic agitation is blended under room temperature, obtains presoma quenching solution.
S2：The presoma quenching solution that step S1 is obtained is taken and is poured into culture dish, culture dish is put into be cooled in advance in advance- 5h is quenched in 30 DEG C of refrigerators.After quenching, culture dish is quickly removed, 500mL mixture of ice and water is poured into culture dish, is extracted DMF, THF, acetone and the glacial acetic acid solvent in solution are taken, first water is changed every 8h, is changed in total four times, absolute ethyl alcohol washing 3 times, forced air drying, vacuum drying obtain TCA/PMMA/TiO2Composite nano fiber.
S3：By TCA/PMMA/TiO2Composite nano fiber is immersed in 0.15mol/LNaOH alcohol solution dippings for 24 hours, will TCA is converted into cellulose, and distillation water washing, drying obtain cellulose/PMMA/TiO2Composite nano fiber.
2) preparation of the compound porous nanofibers of TiC/C
S1：By cellulose/PMMA/TiO2Composite nano fiber impregnates in acetone, and water bath with thermostatic control is shaken for 24 hours, to remove Precursor polymer PMMA, acetone wash 3 times, drying, obtain cellulose/TiO2Compound porous nanofiber.
S2：By cellulose/TiO2Compound porous nanofiber is placed under the conditions of nitrogen protection in atmosphere furnace, nitrogen stream Amount is 100 μ L/min.350 DEG C are warming up to from 25 DEG C, heating rate is 5 DEG C/min, keeps the temperature 2h at such a temperature.It is risen from 350 DEG C For temperature to 800 DEG C, heating rate is 5 DEG C/min, keeps the temperature 1h at such a temperature.1000 DEG C are warming up to from 800 DEG C, heating rate 3 DEG C/min, 1h is kept the temperature at such a temperature.
S3：Under the conditions of logical 100 μ L/min argon gas, 1250 DEG C are warming up to from 1000 DEG C, heating rate is 3 DEG C/min, at this At a temperature of keep the temperature 2h.After heat preservation, it is naturally cooling to room temperature, obtains the compound porous nanofibers of TiC/C.
3)CoNi2S4The preparation of the compound porous nanofibers of/TiC/C
By 0.04gNi (NO3)2·6H2O、0.08g Co(Ac)·4H2O and 0.54g thiocarbamides are added in 20mL deionized waters, Magnetic agitation dissolves.Solution is poured into the stainless steel tubular type autoclave that 50mL liners are polytetrafluoroethylene (PTFE), sequentially adds 0.1g The compound porous nanofibers of TiC/C and deionized water are to the 80% of total capacity.Autoclave is placed in bellows, from room Temperature is warming up to 180 DEG C, and heating rate is 5 DEG C/min, keeps the temperature 12h.It is naturally cooling to room temperature after reaction, filters, washing, do It is dry to obtain CoNi2S4The compound porous nanofibers of/TiC/C.
CoNi manufactured in the present embodiment2S4The scanning electron microscope of the compound porous nanofibers of/TiC/C is as shown in Figure 1.Fiber A diameter of 150 ± 39nm, porosity 92.18%, specific surface area 210.6m2/g.Under the conditions of current density is 1A/g, than electricity It is 301F/g to hold, and after recycling 800 times, capacitance is the 88.7% of initial value.
Comparative example 1
On the basis of embodiment 1, it is not added with PMMA, obtains CoNi2S4/ TiC/C composite nano fibers.The diameter of fiber For 165 ± 45nm, porosity 78.22%, specific surface area 116.2m2/g.Under the conditions of current density is 1A/g, specific capacitance is 189.5F/g, after recycling 800 times, capacitance is the 85.3% of initial value.Compared to embodiment 1, the specific surface area of material and Porosity is greatly lowered, therefore leads to the reduction of its specific capacitance.
Comparative example 2
On the basis of embodiment 1, step 3) CoNi2S4The preparation of the compound porous nanofibers of/TiC/C, only with addition 0.04gNi(NO3)2·6H20.08g Co (Ac) 4H is not added by O2O finally can only obtain the compound porous nanometers of NiS/TiC/C Fiber, a diameter of 136 ± 66nm, porosity 90.25%, the specific surface area 206.1m of fiber2/g.Current density is 1A/g Under the conditions of, specific capacitance 206.1F/g, after recycling 800 times, capacitance is the 88.4% of initial value.
Comparative example 3
On the basis of embodiment 1, step 3) CoNi2S4The preparation of the compound porous nanofibers of/TiC/C, only with addition 0.08g Co(Ac)·4H20.04gNi (NO are not added by O3)2·6H2O finally can only obtain the compound porous nanometers of CoS/TiC/C Fiber, a diameter of 138 ± 46nm, porosity 89.09%, the specific surface area 222.1m of fiber2/g.Current density is 1A/g Under the conditions of, specific capacitance 189F/g, after recycling 800 times, capacitance is the 86.2% of initial value.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring the substantive content of the present invention.

Claims (6)

1. a kind of CoNi2S4The preparation method of the compound porous nanofibers of/TiC/C, which is characterized in that include the following steps：
S1, Triafol T and polymethyl methacrylate be dissolved in N, N '-dimethyl formamide/1,4- dioxane/ In the ternary mixed solvent of acetone, obtain forming solution A after dissolving；Isopropyl titanate is added to the two end number mixing of DMF/ glacial acetic acid In solvent, solution B is obtained, the solution B is added in solution A, presoma quenching solution is obtained after blending；
S2, by the presoma quenching solution after -40~-10 DEG C are quenched, extraction removes ternary mixed solvent and binary Mixed solvent, it is washed, be dried to obtain TCA/PMMA/TiO2Composite nano fiber；
S3, by the TCA/PMMA/TiO2It is washed, dry after composite nano fiber is soaked in the ethanol solution of sodium hydroxide Obtain cellulose/PMMA/TiO2Composite nano fiber；
S4, by the cellulose/PMMA/TiO2Composite nano fiber impregnates in acetone, after removing PMMA, washed, dry To cellulose/TiO2Compound porous nanofiber；
S5, by the cellulose/TiO2Compound porous nanofiber is successively by pre-oxidation, step carbonization, the carbonization of two steps and carbon warm Reduction, obtains the compound porous nanofibers of TiC/C；
S6, after nickel nitrate, cobalt acetate and thiocarbamide are dissolved in deionized water, solution C is obtained, the solution C is transferred to and is lined with In the stainless steel tubular type autoclave of polytetrafluoroethylene (PTFE), the compound porous nanofibers of the TiC/C and deionized water are sequentially added, until The 80% of volume in stainless steel tubular type autoclave, with the heating rate of 5 DEG C/min by room temperature to 160~180 DEG C, heat preservation is anti- Ying Hou obtains the CoNi2S4The compound porous nanofibers of/TiC/C.
2. CoNi as described in claim 12S4The preparation method of the compound porous nanofibers of/TiC/C, which is characterized in that described In ternary mixed solvent, the mass ratio of N, N '-dimethyl formamide, Isosorbide-5-Nitrae-dioxane and acetone are 5：(0.5~1)：(0.5 ~1)；In the binary mixed solvent, the mass ratio of DMF and glacial acetic acid is 15：1.
3. CoNi as described in claim 12S4The preparation method of the compound porous nanofibers of/TiC/C, which is characterized in that described In presoma quenching solution, the mass fraction of Triafol T is 2~5%, and the mass fraction of polymethyl methacrylate is 1 ~2%, the mass fraction of isopropyl titanate is 0.4~1%.
4. CoNi as described in claim 12S4The preparation method of the compound porous nanofibers of/TiC/C, which is characterized in that described Pre-oxidation, a step are carbonized, the concrete operations of two steps carbonization are：
In the nitrogen atmosphere of 50~100 μ L/min flows, with the rate of 3~5 DEG C/min by room temperature to 300~360 DEG C, It after keeping the temperature 2h, keeps nitrogen flow constant, is warming up to 700~800 DEG C by 300~360 DEG C with the rate of 3~5 DEG C/min, heat preservation It after 1h, keeps nitrogen flow constant, is warming up to 1000 DEG C by 700~800 DEG C with the rate of 3 DEG C/min, keeps the temperature 1h.
5. CoNi as described in claim 12S4The preparation method of the compound porous nanofibers of/TiC/C, which is characterized in that described The concrete operations of carbon thermal reduction are：
In the argon gas atmosphere of 50~100 μ L/min flows, 1100 are warming up to by 1000 DEG C with the rate of 2~3 DEG C/min~ 1300 DEG C, keep the temperature 2h.
6. a kind of CoNi obtained by preparation method described in claim 12S4The compound porous nanofibers of/TiC/C are in super electricity Purposes in container.
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