CN109244485A - A kind of NiCo/TiO2Cell anode catalyst and preparation method thereof - Google Patents

A kind of NiCo/TiO2Cell anode catalyst and preparation method thereof Download PDF

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CN109244485A
CN109244485A CN201811203111.7A CN201811203111A CN109244485A CN 109244485 A CN109244485 A CN 109244485A CN 201811203111 A CN201811203111 A CN 201811203111A CN 109244485 A CN109244485 A CN 109244485A
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鞠剑峰
吴锦明
王淼
汪洋
姚勇
徐立
查雅君
兰天蓉
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Nantong University Technology Transfer Center Co ltd
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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Abstract

The invention discloses N, the NiCo/TiO of C doping2Anode catalysts for direct methanol fuel cell, product is with the nano-TiO of high-ratio surface2Carrier composite Nano NiCo alloy simultaneously adulterates N, and C is formed.The N of NiCo alloy and doping, C can improve TiO2The electric conductivity of carrier, the doping of NiCo alloy and N, C are to TiO2Synergistic effect improve TiO2To the catalytic oxidation performance of methanol, meanwhile, the intermediate products such as CO that methanol oxidation generates are adsorbed, are transferred to N, the NiCo/TiO of C doping2Catalyst surface, and be final product CO by deep oxidation2, the resisting CO poison ability of catalyst can be improved, since the price of NiCo is far below noble metals such as Pt, Ru, and in N, the NiCo/TiO of C doping2Cost smaller, therefore that catalyst can be substantially reduced is measured in catalyst, and battery performance can be improved.

Description

A kind of NiCo/TiO2Cell anode catalyst and preparation method thereof
Technical field
The present invention relates to a kind of NiCo/TiO2Cell anode catalyst and preparation method thereof, and in particular to a kind of N, C doping NiCo/TiO2Anode catalysts for direct methanol fuel cell and preparation method belong to cell catalyst technical field.
Background technique
Direct methanol fuel cell (Direct Methanol Fuel Cell, DMFC) has less energy consumption, energy density Height, methanol abundance, cheap, system is simple, runs convenient and low noise advantages, it is considered to be future automobile power With the most promising electrochmical power source of other vehicles, cause the extensive concern of people.The material of DMFC most critical first is that electricity Electrode catalyst, it directly affects performance, stability, service life and the manufacturing cost of battery.Precious metals pt is under cryogenic (less than 80 DEG C) have excellent catalytic properties, and the electrode catalyst of DMFC is using Pt as main component at present, and wherein PtRu is urged Agent has stronger CO tolerance catalysts performance and higher catalytic activity than pure Pt, it is considered to be the optimal catalysis of DMFC at present Agent, but due to the defects of it is expensive, Ru is readily soluble, commercialized requirement is also not achieved in the utilization rate in DMFC.
People, which have conducted extensive research, prepares multiplex catalyst to improve its catalytic activity, improves resisting CO poison energy Power.TiO2Doping such as PtRuTiOX/ C and Au/TiO2PtRu catalyst prepares such as PtNi/TiO as carrier2、PdAg/TiO2、 PdNi/TiO2Deng, it is possible to reduce the dosage of precious metals pt or prepare non-platinum catalyst in catalyst, reduce catalyst manufacture at This, improves catalytic performance and resisting CO poison ability, has application prospect.But TiO2For semiconductor, electric conductivity is not satisfactory, makes Used time catalyst need to mix C, influence its performance and application.
Summary of the invention
Goal of the invention: in order to solve the problems in the existing technology, the present invention provides a kind of NiCo/TiO2Battery sun Electrode catalyst and preparation method thereof.
Technical solution: in order to achieve the above-mentioned object of the invention, The technical solution adopted by the invention is as follows:
The present invention provides a kind of NiCo/TiO2Cell anode catalyst, the cell anode catalyst are nano-TiO2It carries Bluk recombination Ni nanoparticle Co alloy simultaneously adulterates N, and C is formed.
Further, the nano-TiO2Carrier is TiO2Nanotube, TiO2Nanofiber, porous hollow TiO2Nanosphere One of or it is a variety of.
Further, the total content of NiCo Nanoalloy is 1~3% in the cell anode catalyst, mole of Ni, Co Than for 7:3~3:7.
Further, the cell anode catalyst is as anode catalysts for direct methanol fuel cell.
The present invention also provides above-mentioned NiCo/TiO2The preparation method of cell anode catalyst, the galvanic anode catalysis Agent is nano-TiO2Carrier composite Nano NiCo alloy simultaneously adulterates N, and C is formed, it is specific the preparation method is as follows:
(1)TiO2The preparation of carrier
The nano-TiO2Carrier is TiO2Nanotube, TiO2Nanofiber, porous hollow TiO2One of nanosphere or It is a variety of；TiO2The preparation of nanotube uses sol-gel method and high pressure hydro-thermal reaction method, TiO2The preparation of nanofiber is using molten Glue-gel method and method of electrostatic spinning, porous hollow TiO2The preparation of nanosphere uses sol-gel method；
(2) solution is prepared
By NiSO4It is dissolved into methanol, is configured to the NiSO that concentration is 10-20mg/mL4/ methanol solution；By CoSO4Dissolution Into methanol, it is configured to the CoSO that concentration is 10-20mg/mL4/ methanol solution；2-methylimidazole is dissolved into methanol, is prepared 2-methylimidazole/the methanol solution for being 50-100mg/mL at concentration；
(3)TiO2Carrier adsorption Ni2+And Co2+
By TiO made from step (1) under stirring2Carrier impregnation is n in the molar ratio of Ni, CoNi:nCo=7:3~3:7's NiSO4/ methanol solution and CoSO4In the mixed solution of/methanol solution, until NiCo/TiO2The content of NiCo reaches 1 in catalyst ~3%, it is washed, is dried with methanol；
(4) Ni is formed2+Co2+Complex-TiO2
Ni has been adsorbed by what step (3) obtained2+And Co2+TiO2It is molten that 2-methylimidazole/methanol is impregnated under carrier stirring In liquid, dip time 4 hours, Ni is formed2+Co2+Complex-TiO2, wherein the molal quantity of 2-methylimidazole is in step (3) NiSO4And CoSO45 times of molal quantity sum, are washed with methanol, drying；
(5) NiCo/TiO is formed2With doping N, C
The Ni that step (4) is obtained2+Co2+Complex-TiO23 hours N to obtain the final product are roasted for 600 DEG C in Ar atmosphere, C doping NiCo/TiO2Anode catalysts for direct methanol fuel cell.Wherein, NiCo alloy is complex ligand (2-methylimidazole) roasting When product of roasting C reduction reaction formed, the source of N, C be ligand (2-methylimidazole) inert gas atmosphere roasting.
It is limited as further, the TiO2The preparation method of nanotube is specific as follows:
The butyl titanate of calculation amount is dissolved in a certain amount of dehydrated alcohol, stir lower dropwise addition dehydrated alcohol, glacial acetic acid and is gone The mixture of ionized water, hydrolyzes to form colloidal sol, then proceedes to stirring to formation gel；Wherein butyl titanate, anhydrous second in colloidal sol Alcohol, glacial acetic acid, deionized water dosage molar ratio are as follows: nButyl titanate: nDehydrated alcohol: nGlacial acetic acid: nDeionized water=1:20~40:1~2.5:2~ 6；
The gel of formation is stood 2~3 days, and 8~10 hours dry in 80 DEG C of vacuum environments, powder will be obtained after grinding Nano-TiO is made in end 500 DEG C air roasting 3 hours in Muffle furnace2Powder；
By TiO obtained2Powder is added in autoclave liner, and the NaOH solution that concentration is 10mol/L is added, It is reacted 24 hours at a temperature of 150 DEG C；Then washed respectively with the HCl solution of deionized water and 0.1mol/L, 80 DEG C drying after 500 DEG C of air atmospheres of Muffle furnace roast 3 hours up to TiO2Nanotube；
It is limited as further, the TiO2The preparation method of nanofiber is specific as follows:
Butyl titanate and polyvinylpyrrolidone PVP are dissolved in dehydrated alcohol, lower dropwise addition dehydrated alcohol, ice vinegar are stirred The mixture of acid, deionized water, forms the colloidal sol of homogeneous transparent, then carries out electrostatic spinning；Wherein butyl titanate, nothing in colloidal sol Water-ethanol, glacial acetic acid, deionized water, the dosage molar ratio of PVP are as follows: nButyl titanate:nDehydrated alcohol:nGlacial acetic acid:nDeionized water:nPVP=1:20~ 40:1~2.5:2~6:0.1~0.2；
When electrostatic spinning, electrostatic spinning apparatus is added in the colloidal sol of formation, the voltage of electrostatic spinning apparatus is adjusted to 25kV, the distance of spinning head to tinfoil paper are 15cm, spray colloidal sol 2mL per hour, obtain PVP/TiO2Fiber；By PVP/TiO2Fiber 500 DEG C air atmosphere roasts 3h, obtains TiO2Nanofiber.
It is limited as further, the porous hollow TiO2The preparation method of nanosphere is specific as follows:
The butyl titanate of calculation amount is dissolved in a certain amount of dehydrated alcohol, a certain amount of Surfactant PEG -400 is added With Vulcan XC-72, the lower mixture that dehydrated alcohol, glacial acetic acid and deionized water is added dropwise is stirred, colloidal sol is hydrolyzed to form；Preparation Butyl titanate when colloidal sol, dehydrated alcohol, glacial acetic acid, deionized water dosage molar ratio are as follows: nButyl titanate: nDehydrated alcohol: nGlacial acetic acid: nDeionized water =1:20~40:1~2.5:2~6；
The colloidal sol hydrolyzed to form is continued into stirring to gel is formed, is then allowed to stand 2-3 days, 80 DEG C of vacuum drying 8~10 are small Shi Hou, by the powder obtained after grinding in Muffle furnace 400~600 DEG C air roasting 3 hours, obtain porous hollow TiO2It receives Rice ball.
It is limited as further, the porous hollow TiO2In the preparation method of nanosphere, PEG-400 dosage is metatitanic acid Butyl ester, dehydrated alcohol, deionized water and glacial acetic acid total volume 1%.
It is limited as further, the porous hollow TiO2In the preparation method of nanosphere, the use of Vulcan XC-72 Amount is that butyl titanate complete hydrolysis ultimately produces TiO2The 30% of theoretical amount.
The utility model has the advantages that the present invention is with the TiO of high-ratio surface2Carrier adsorption Ni2+And Co2+And it reacts to be formed with 2-methylimidazole Ni2+Co2+Complex-TiO2, high-temperature roasting forms N, the NiCo/TiO of C doping under inert gas shielding2.NiCo alloy and doping N, C can improve TiO2The electric conductivity of carrier, the doping of NiCo alloy and N, C are to TiO2Synergistic effect improve TiO2To methanol Catalytic oxidation performance, meanwhile, the intermediate products such as CO that methanol oxidation generates are adsorbed, are transferred to N, the NiCo/TiO of C doping2 Catalyst surface, and be final product CO by deep oxidation2, the resisting CO poison ability of catalyst can be improved, due to NiCo's Price is far below noble metals such as Pt, Ru, and the NiCo/TiO adulterated in N, C2It measures smaller in catalyst, therefore can substantially reduce The cost of catalyst, can be improved battery performance.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, and embodiment is under the premise of the technical scheme of the present invention Implemented, it should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Embodiment 1:
(1)TiO2The preparation of nano-tube support: sol-gel method and high pressure hydro-thermal reaction are used.By the metatitanic acid of calculation amount Butyl ester is dissolved in a certain amount of dehydrated alcohol, stirs the lower mixture that dehydrated alcohol, glacial acetic acid and deionized water is added dropwise, hydrolyzes to form Continue to stir after colloidal sol, stand 2-3 days after gel to be formed, after 80 DEG C of obtained powder mulls after vacuum drying 8-10 hours Nano-TiO is made in 500 DEG C air roasting 3 hours in Muffle furnace2Powder.By TiO obtained2Autoclave liner is added in powder In, the NaOH solution mixing of 10mol/L is added, 150 DEG C are reacted 24 hours.Obtained sample use respectively deionized water and The HCl solution of 0.1mol/L washs, and 500 DEG C of Muffle furnace air roasting 3 hours obtains TiO after 80 DEG C of drying2Nanotube.Prepare colloidal sol When butyl titanate, dehydrated alcohol, glacial acetic acid, deionized water dosage molar ratio are as follows: nButyl titanate: nDehydrated alcohol: nGlacial acetic acid: nDeionized water=1: 20~40:1~2.5:2~6.
(2) by NiSO4It is dissolved into methanol, forms the NiSO of 10-20mg/mL4/ methanol solution；
(3) by CoSO4It is dissolved into methanol, forms the CoSO of 10-20mg/mL4/ methanol solution；
(4) 2-methylimidazole is dissolved into methanol, forms 2-methylimidazole/methanol solution of 50-100mg/mL；
(5) by TiO made from step (1) under stirring2Nano-tube support impregnates molar ratio nNi:nCoThe NiSO of=7:34/ first Alcoholic solution and CoSO4/ methanol solution, until NiCo/TiO2Middle WNiCo=1%, methanol washing, drying；
(6) Ni has been adsorbed by what step (5) obtained2+And Co2+TiO2Stirring is lower to impregnate 2-methylimidazole/methanol solution, Form Ni2+Co2+Complex-TiO2, wherein the molal quantity of 2-methylimidazole is NiSO in step 54And CoSO4The 5 of molal quantity sum Times, dip time 4 hours, methanol washing, drying；
(7) Ni for obtaining step 62+Co2+Complex-TiO2N is obtained within roasting 3 hours for 600 DEG C in Ar atmosphere, C doping NiCo/TiO2Anode catalysts for direct methanol fuel cell.
Embodiment 2
N in step (5)Ni:nCo=1:1, NiCo/TiO2Middle WNiCo=2%, the other the same as in Example 1.
Embodiment 3
N in step (5)Ni:nCo=3:7, NiCo/TiO2Middle WNiCo=3%, the other the same as in Example 1.
Embodiment 4
(1)TiO2The preparation of nano fibre carrier: sol-gel method and method of electrostatic spinning are used.By butyl titanate and gather Vinylpyrrolidone (PVP) is dissolved in dehydrated alcohol, be then added dropwise under stiring dehydrated alcohol, glacial acetic acid, deionized water it is mixed Object is closed, carries out electrostatic spinning after forming the colloidal sol of homogeneous transparent；When electrostatic spinning, electrostatic spinning apparatus is added in the colloidal sol, Adjusting voltage is 25KV, and the distance of spinning head to tinfoil paper is 15cm, sprays colloidal sol 2ml per hour, obtains PVP/TiO2Fiber.By PVP/ TiO2500 DEG C of air atmospheres of fiber roast 3h, and TiO is made2Nanofiber.The dosage molar ratio of above-mentioned each component when preparing colloidal sol are as follows: nButyl titanate:nDehydrated alcohol:nGlacial acetic acid:nDeionized water:nPVP=1:20~40:1~2.5:2~6:0.1~0.2.
(2) by NiSO4It is dissolved into methanol, forms the NiSO of 10-20mg/mL4/ methanol solution；
(3) by CoSO4It is dissolved into methanol, forms the CoSO of 10-20mg/mL4/ methanol solution；
(4) 2-methylimidazole is dissolved into methanol, forms 2-methylimidazole/methanol solution of 50-100mg/mL；
(5) by TiO made from step (1) under stirring2Nanofiber impregnates molar ratio nNi:nCoThe NiSO of=7:34/ methanol Solution and CoSO4/ methanol solution, until NiCo/TiO2Middle WNiCo=1%, methanol washing, drying；
(6) Ni has been adsorbed by what step (5) obtained2+And Co2+TiO2Stirring is lower to impregnate 2-methylimidazole/methanol solution, Form Ni2+Co2+Complex-TiO2, wherein the molal quantity of 2-methylimidazole is NiSO in step (5)4And CoSO4Molal quantity sum 5 times, dip time 4 hours, methanol washing, drying；
(7) Ni for obtaining step (6)2+Co2+Complex-TiO2N is obtained within roasting 3 hours for 600 DEG C in Ar atmosphere, C doping NiCo/TiO2Anode catalysts for direct methanol fuel cell.
Embodiment 5
N in step (5)Ni:nCo=1:1, NiCo/TiO2Middle WNiCo=2%, the other the same as in Example 4.
Embodiment 6
N in step (5)Ni:nCo=3:7, NiCo/TiO2Middle WNiCo=3%, the other the same as in Example 4.
Embodiment 7
(1) porous hollow TiO2The preparation of nanosphere: sol-gel method is used, the butyl titanate of calculation amount is dissolved in one A certain amount of Surfactant PEG -400 and Vulcan XC-72 is added in quantitative dehydrated alcohol, stirs the lower anhydrous second of dropwise addition The mixture of alcohol, glacial acetic acid and deionized water continues to stir after hydrolyzing to form colloidal sol, and 2-3 days, 80 DEG C are stood after gel to be formed After vacuum drying 8-10 hour after obtained powder mull in Muffle furnace 400-600 DEG C air roasting 3 hours, obtained porous air Heart TiO2Nanosphere；Butyl titanate when preparing colloidal sol, dehydrated alcohol, glacial acetic acid, deionized water dosage molar ratio are as follows: nButyl titanate: nDehydrated alcohol: nGlacial acetic acid: nDeionized water=1:20~40:1~2.5:2~6；PEG-400 dosage is butyl titanate, dehydrated alcohol, deionization The 1% of water and glacial acetic acid total volume；The dosage of Vulcan XC-72 is that butyl titanate complete hydrolysis ultimately produces TiO2Theoretical amount 30%.
(2) by NiSO4It is dissolved into methanol, forms the NiSO of 10-20mg/mL4/ methanol solution；
(3) by CoSO4It is dissolved into methanol, forms the CoSO of 10-20mg/mL4/ methanol solution；
(4) 2-methylimidazole is dissolved into methanol, forms 2-methylimidazole/methanol solution of 50-100mg/mL；
(5) by porous hollow TiO made from step (1) under stirring2Nanosphere impregnates molar ratio nNi:nCo=7:3's NiSO4/ methanol solution and CoSO4/ methanol solution, until NiCo/TiO2Middle WNiCo=1%, methanol washing, drying；
(6) Ni has been adsorbed by what step (5) obtained2+And Co2+TiO2Stirring is lower to impregnate 2-methylimidazole/methanol solution, Form Ni2+Co2+Complex-TiO2, wherein the molal quantity of 2-methylimidazole is NiSO in step 54And CoSO4The 5 of molal quantity sum Times, dip time 4 hours, methanol washing, drying；
(7) the formation Ni for obtaining step 62+Co2+Complex-TiO2N, C doping are obtained within roasting 3 hours for 600 DEG C in Ar atmosphere NiCo/TiO2Anode catalysts for direct methanol fuel cell.
Embodiment 8
N in step (5)Ni:nCo=1:1, NiCo/TiO2Middle WNiCo=2%, other same embodiments 7.
Embodiment 9
N in step (5)Ni:nCo=3:7, NiCo/TiO2Middle WNiCo=3%, other same embodiments 7.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of NiCo/TiO2Cell anode catalyst, it is characterised in that: the cell anode catalyst is nano-TiO2Carrier Composite Nano NiCo alloy simultaneously adulterates N, and C is formed.
2. a kind of NiCo/TiO according to claim 12Cell anode catalyst, it is characterised in that: the nano-TiO2It carries Body is TiO2Nanotube, TiO2Nanofiber, porous hollow TiO2One of nanosphere is a variety of.
3. a kind of NiCo/TiO according to claim 12Cell anode catalyst, it is characterised in that: the galvanic anode is urged The total content of NiCo Nanoalloy is 1~3% in agent, and the molar ratio of Ni, Co are 7:3~3:7.
4. a kind of NiCo/TiO according to claim 12Cell anode catalyst, it is characterised in that: the galvanic anode is urged Agent is as anode catalysts for direct methanol fuel cell.
5. a kind of NiCo/TiO2The preparation method of cell anode catalyst, it is characterised in that: the cell anode catalyst is to receive Rice TiO2Carrier composite Nano NiCo alloy simultaneously adulterates N, and C is formed, it is specific the preparation method is as follows:
(1)TiO2The preparation of carrier
The nano-TiO2Carrier is TiO2Nanotube, TiO2Nanofiber, porous hollow TiO2One of nanosphere is a variety of； TiO2The preparation of nanotube uses sol-gel method and high pressure hydro-thermal reaction method, TiO2The preparation of nanofiber is solidifying using colloidal sol- Glue method and method of electrostatic spinning, porous hollow TiO2The preparation of nanosphere uses sol-gel method；
(2) solution is prepared
By NiSO4It is dissolved into methanol, is configured to the NiSO that concentration is 10-20mg/mL4/ methanol solution；By CoSO4It is dissolved into first In alcohol, it is configured to the CoSO that concentration is 10-20mg/mL4/ methanol solution；2-methylimidazole is dissolved into methanol, is configured to dense Degree is 2-methylimidazole/methanol solution of 50-100mg/mL；
(3)TiO2Carrier adsorption Ni2+And Co2+
By TiO made from step (1) under stirring2Carrier impregnation is n in the molar ratio of Ni, CoNi:nCoThe NiSO of=7:3~3:74/ Methanol solution and CoSO4In the mixed solution of/methanol solution, until NiCo/TiO2The content of NiCo reaches 1~3% in catalyst, It is washed, is dried with methanol；
(4) Ni is formed2+Co2+Complex-TiO2
Ni has been adsorbed by what step (3) obtained2+And Co2+TiO2It is impregnated in 2-methylimidazole/methanol solution under carrier stirring, Dip time 4 hours, form Ni2+Co2+Complex-TiO2, wherein the molal quantity of 2-methylimidazole is NiSO in step (3)4With CoSO45 times of molal quantity sum, are washed with methanol, drying；
(5) NiCo/TiO is formed2With doping N, C
The Ni that step (4) is obtained2+Co2+Complex-TiO2600 DEG C of roastings, 3 hours NiCo/ adulterated up to N, C in Ar atmosphere TiO2Anode catalysts for direct methanol fuel cell.
6. a kind of NiCo/TiO according to claim 52The preparation method of cell anode catalyst, it is characterised in that: described TiO2The preparation method of nanotube is specific as follows:
The butyl titanate of calculation amount is dissolved in a certain amount of dehydrated alcohol, stirs lower dropwise addition dehydrated alcohol, glacial acetic acid and deionization The mixture of water, hydrolyzes to form colloidal sol, then proceedes to stirring to formation gel；Wherein butyl titanate, dehydrated alcohol, ice in colloidal sol The dosage molar ratio of acetic acid, deionized water are as follows: nButyl titanate: nDehydrated alcohol: nGlacial acetic acid: nDeionized water=1:20~40:1~2.5:2~6；
The gel of formation is stood 2~3 days, and 8~10 hours dry in 80 DEG C of vacuum environments, the powder that will be obtained after grinding Nano-TiO is made in 500 DEG C air roasting 3 hours in Muffle furnace2Powder；
By TiO obtained2Powder is added in autoclave liner, the NaOH solution that concentration is 10mol/L is added, in 150 DEG C of temperature Degree lower reaction 24 hours；Then it is washed respectively with the HCl solution of deionized water and 0.1mol/L, in Muffle furnace after 80 DEG C of drying 500 DEG C of air atmospheres roast 3 hours up to TiO2Nanotube.
7. a kind of NiCo/TiO according to claim 52The preparation method of cell anode catalyst, it is characterised in that: described TiO2The preparation method of nanofiber is specific as follows:
Butyl titanate and polyvinylpyrrolidone PVP are dissolved in dehydrated alcohol, lower dropwise addition dehydrated alcohol is stirred, glacial acetic acid, goes The mixture of ionized water forms the colloidal sol of homogeneous transparent, then carries out electrostatic spinning；Wherein butyl titanate, anhydrous second in colloidal sol Alcohol, glacial acetic acid, deionized water, the dosage molar ratio of PVP are as follows: nButyl titanate:nDehydrated alcohol:nGlacial acetic acid:nDeionized water:nPVP=1:20~40:1~ 2.5:2~6:0.1~0.2；
When electrostatic spinning, electrostatic spinning apparatus is added in the colloidal sol of formation, the voltage of electrostatic spinning apparatus is adjusted to 25kV, is sprayed The distance of silk head to tinfoil paper is 15cm, sprays colloidal sol 2mL per hour, obtains PVP/TiO2Fiber；By PVP/TiO2500 DEG C of air of fiber Atmosphere roasts 3h, obtains TiO2Nanofiber.
8. a kind of NiCo/TiO according to claim 52The preparation method of cell anode catalyst, it is characterised in that: described Porous hollow TiO2The preparation method of nanosphere is specific as follows:
The butyl titanate of calculation amount is dissolved in a certain amount of dehydrated alcohol, be added a certain amount of Surfactant PEG -400 and Vulcan XC-72 stirs the lower mixture that dehydrated alcohol, glacial acetic acid and deionized water is added dropwise, hydrolyzes to form colloidal sol；It prepares molten Butyl titanate when glue, dehydrated alcohol, glacial acetic acid, deionized water dosage molar ratio are as follows: nButyl titanate: nDehydrated alcohol: nGlacial acetic acid: nDeionized water= 1:20~40:1~2.5:2~6；
The colloidal sol hydrolyzed to form is continued into stirring to gel is formed, is then allowed to stand 2-3 days, after 80 DEG C are dried in vacuo 8~10 hours, By the powder obtained after grinding in Muffle furnace 400~600 DEG C air roasting 3 hours, obtain porous hollow TiO2Nanosphere.
9. a kind of NiCo/TiO according to claim 82The preparation method of cell anode catalyst, it is characterised in that: described Porous hollow TiO2In the preparation method of nanosphere, PEG-400 dosage is butyl titanate, dehydrated alcohol, deionized water and ice vinegar The 1% of sour total volume.
10. a kind of NiCo/TiO according to claim 82The preparation method of cell anode catalyst, it is characterised in that: institute State porous hollow TiO2In the preparation method of nanosphere, the dosage of Vulcan XC-72 is that butyl titanate complete hydrolysis ultimately produces TiO2The 30% of theoretical amount.
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