CN108376614A - A kind of NiCo2O4/ carbon nano-tube combination electrode material and preparation method thereof - Google Patents
A kind of NiCo2O4/ carbon nano-tube combination electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN108376614A CN108376614A CN201810170727.2A CN201810170727A CN108376614A CN 108376614 A CN108376614 A CN 108376614A CN 201810170727 A CN201810170727 A CN 201810170727A CN 108376614 A CN108376614 A CN 108376614A
- Authority
- CN
- China
- Prior art keywords
- nico
- carbon nano
- pipe array
- nano pipe
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 40
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 38
- 229910005949 NiCo2O4 Inorganic materials 0.000 title claims abstract description 33
- 239000007772 electrode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000009415 formwork Methods 0.000 claims abstract description 28
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000004070 electrodeposition Methods 0.000 claims abstract description 24
- 238000000151 deposition Methods 0.000 claims abstract description 23
- 239000012153 distilled water Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000008021 deposition Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 15
- 235000019441 ethanol Nutrition 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002146 bilateral effect Effects 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 8
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002071 nanotube Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 11
- -1 carbon nano tube compound Chemical class 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CZAYMIVAIKGLOR-UHFFFAOYSA-N [Ni].[Co]=O Chemical class [Ni].[Co]=O CZAYMIVAIKGLOR-UHFFFAOYSA-N 0.000 description 1
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of NiCo2O4/ carbon nano-tube combination electrode material and preparation method thereof, it is related to a kind of monomer using carbon nanotube as core, NiCo2O4Nanotube is the nucleocapsid of shell, the generally NiCo of high-sequential nano-tube array2O4/ carbon nano-tube combination electrode material, preparation process include：One, the alumina formwork that aperture is 200nm bilaterals is chosen, the copper film for being 1 μm in its back side magnetron sputtering a layer thickness is dried after trimethylsilyl cyanide, ethyl alcohol, distilled water are cleaned by ultrasonic successively；Two, using the Woelm Alumina handled well as template, nickel-cobalt alloy nano pipe array is prepared using square-wave pulse electrodeposition process in electrolytic cell；Three, using chemical vapour deposition technique in nickel-cobalt alloy nano pipe deposition of carbon nanotubes；Four, alumina formwork is removed with NaOH, NiCo is obtained after calcining2O4/ carbon nano tube compound material.The NiCo that this method obtains2O4/ carbon nano tube compound material is applied to have higher specific capacitance value and good stable electrochemical property when electrode material for super capacitor.
Description
Technical field
The present invention relates to a kind of NiCo2O4/ carbon nano-tube combination electrode material and preparation method thereof belongs to material preparation neck
Domain.
Background technology
In recent years, ultracapacitor because of it with high power density, charge short time and many advantages, such as of having extended cycle life,
It is widely used in communication, aerospace, large scale industry equipment, the fields for requiring abrupt release super-large current such as many such as microelectronic component
It closes, is especially had broad application prospects in new-energy automobile field.Electrode material is the pass for influencing performance of the supercapacitor
Key factor, with RuO2Equal metal oxide containing precious metals have larger specific capacitance value, but expensive price and toxicity because of its fake capacitance principle
Limit its commercial applications.Some cheap metal oxides replace noble metal to become research as electrode material for super capacitor
Hot spot.NiCo2O4It is a kind of typical spinel structure metal composite oxide, there are Co3+/Co2+And Ni3+/Ni2+Oxidation is also
Former electricity is right, can obtain higher operating voltage window and specific capacitance value, while because its non-toxic inexpensive shows as great potential
Electrode material, therefore the NiCo of different structure, form, size2O4Preparation receive the concern of numerous researchers（Such as
CN102259936B; CN102092797B; CN102745752A; CN103107025A; CN103594246A;
CN103318978B; CN104003455B; CN104659358A）.However compared with metal oxide containing precious metals, NiCo2O4Due to it
Electric conductivity is poor, causes specific capacitance relatively low, and cycle impulse electricity is filled under high current density and is not sufficiently stable.Therefore, people's consideration will
NiCo2O4With carbon material or conducting polymer carry out it is compound improve the electric conductivity of material, enhance its chemical property to reach
Purpose（Such as CN103117389B; CN104143450A）.
Carbon nanotube（CNTs）Nanostructure with special one-dimensional hollow, it is mainly by the carbon of hexagonal arrangement original
Son constitute single layer or several layers coaxial pipe constitute, have excellent heat-resisting, corrosion-resistant, impact resistance, and conduct heat and
It conducts electricity very well, it is made to have the potential advantages for preparing large capacity ultracapacitor.But CNTs is separately as electrode of super capacitor
Material specific capacitance is worth too low, generally only 40F/g.In view of the complementarity between transition oxide and carbon nanotube, usually consider
Its is compound, make the combination product that not only there is fake capacitance characteristic, but also there is double layer characteristic, there is high ratio electricity to prepare
The electrode material for super capacitor that appearance, high conductivity, cycle charge-discharge are stablized.Leela etc.（Asymmetric Flexible
Supercapacitor Stack, Nonoscale Research Letters, 2008）Metal is prepared using sol-gal process
Oxide/multi-wall carbon nano-tube combination electrode material shows excellent chemical property, but sol-gal process is added surface and lives
Property agent, is readily incorporated impurity, and cost is higher；Kuan etc.（Electrodeposition of Nickel and Cobalt
Mixed Oxide/Carbon Nanotube Thin Films and Their Charge Storage Properties,
J. Electorchem. soc., 2006）, Fan etc.（Preparation and capacitive properties of
cobalt-nickel oxides/carbon nanotube coposites,Electrochim. Acta. 2007）And Wen
Deng（A three dimensional vertically aligned multiwall carbon nanotube-NiCo2O4
core-shell structure for novel high-performance supercapacitors, J. Mater.
Chem. A, 2014）It is prepared for cobalt-nickel oxide/carbon nano tube compound material, this method reaction using electrochemical deposition method
Time is long, and energy consumption is high；Chinese patent（CN1315139C）Provide a kind of carbon nanotube and the compound approach of transition oxide, profit
With binder that carbon nanotube and transition metal oxide is compound, the addition of binder can increase the internal resistance of material, be unfavorable for this
Composite material is as electrode material for super capacitor.
Invention content
The purpose of the present invention is to provide a kind of NiCo2O4/ carbon nano-tube combination electrode material, while one kind being also provided and is adopted
Nickel-cobalt alloy nano pipe array is prepared with square-wave pulse electrodeposition process, and then by chemical vapour deposition technique in nickel-cobalt alloy nano
Deposition of carbon nanotubes in pipe obtains NiCo by removing alumina formwork and calcining2O4The system of/carbon nano-tube combination electrode material
Preparation Method.
The present invention the specific steps are：
The first step：Porous alumina formwork prepares
The alumina formwork that aperture is 200nm bilaterals is chosen, is 1 μm of copper film in its back side magnetron sputtering a layer thickness, successively
Drying is with spare after trimethylsilyl cyanide, ethyl alcohol, distilled water are cleaned by ultrasonic；
Second step：It is prepared by nickel-cobalt alloy nano pipe array
Nickel-cobalt alloy nano pipe array is prepared using square-wave pulse electrodeposition process in electrolytic cell：It gets out aluminium oxide with the first step
Template is to electrode as working electrode, platinized platinum, and saturated calomel electrode is auxiliary electrode, and square-wave pulse is carried out after deposition liquid is added
Electro-deposition, deposition is after the completion wash with distilled water to neutral；
The deposition liquid ingredient is：1 part of NiSO4•6H2O, 2 parts of CoSO4•7H2O, H3BO3(NH4)2SO4；
The condition of the square-wave pulse electro-deposition is：Continue 30 s in 0 V, then moment add 5 s of potential duration of -2.5 V
Square-wave pulse electro-deposition certain time；
Third walks：It is prepared by nickel cobalt/carbon nano pipe array
Nickel-cobalt alloy nano pipe array is put into tube furnace, air pressure in tube furnace is repeatedly adjusted to 10KPa after displacement Ar, then
500 ~ 800 DEG C are warming up to, the C of 50ml/min is passed through2H2, stop heating after reacting 10 ~ 60min, continue to be passed through Ar and be cooled to room
Temperature；
4th step：NiCo2O4It is prepared by/carbon nano pipe array
Nickel cobalt/carbon nano pipe array is taken out, removal alumina formwork is soaked for a period of time with the NaOH of 1M/L, then uses ethyl alcohol
It cleans to neutrality with distilled water, is placed in Muffle furnace after drying, 300 DEG C of heat preservation 2h are warming up to the heating rate of 1 DEG C/min,
NiCo is obtained after cooling2O4/ carbon nano pipe array.
Advantages of the present invention：One, the NiCo that the present invention obtains2O4/ carbon nano-tube combination electrode material has novel and unique
Structure（Monomer is using carbon nanotube as core, NiCo2O4Nanotube is the nucleocapsid of shell, generally high-sequential nanotube battle array
Row）；Two, the NiCo obtained2O4/ carbon nano-tube combination electrode material is used to have when electrode of super capacitor higher than electricity
Capacitance and good stable electrochemical property.
Specific implementation mode
Here is that the present invention will be described in detail in conjunction with the embodiments, to more fully understand the purpose of the present invention, feature
And advantage.Although the present invention is described in conjunction with the specific embodiment, it is not intended that the invention be limited to described tool
Body embodiment.On the contrary, to may include in the claims in the present invention defined by embodiment in protection domain replace
Generation, improvement and equivalent embodiment, belong to protection scope of the present invention.It can be by normal for the technological parameter not marked especially
Rule technology carries out.
The present invention the specific steps are：
The first step：Porous alumina formwork prepares
The alumina formwork that aperture is 200nm bilaterals is chosen, is 1 μm of copper film in its back side magnetron sputtering a layer thickness, successively
Drying is with spare after trimethylsilyl cyanide, ethyl alcohol, distilled water are cleaned by ultrasonic；
Second step：It is prepared by nickel-cobalt alloy nano pipe array
Nickel-cobalt alloy nano pipe array is prepared using square-wave pulse electrodeposition process in electrolytic cell：It gets out aluminium oxide with the first step
Template is to electrode as working electrode, platinized platinum, and saturated calomel electrode is auxiliary electrode, and square-wave pulse is carried out after deposition liquid is added
Electro-deposition, deposition is after the completion wash with distilled water to neutral；
The deposition liquid ingredient is：1 part of NiSO4•6H2O, 2 parts of CoSO4•7H2O, H3BO3(NH4)2SO4；
The condition of the square-wave pulse electro-deposition is：Continue 30 s in 0 V, then moment add 5 s of potential duration of -2.5 V
Square-wave pulse electro-deposition certain time；
Third walks：It is prepared by nickel cobalt/carbon nano pipe array
Nickel-cobalt alloy nano pipe array is put into tube furnace, air pressure in tube furnace is repeatedly adjusted to 10KPa after displacement Ar, then
500 ~ 800 DEG C are warming up to, the C of 50ml/min is passed through2H2, stop heating after reacting 10 ~ 60min, continue to be passed through Ar and be cooled to room
Temperature；
4th step：NiCo2O4It is prepared by/carbon nano pipe array
Nickel cobalt/carbon nano pipe array is taken out, removal alumina formwork is soaked for a period of time with the NaOH of 1M/L, then uses ethyl alcohol
It cleans to neutrality with distilled water, is placed in Muffle furnace after drying, 300 DEG C of heat preservation 2h are warming up to the heating rate of 1 DEG C/min,
NiCo is obtained after cooling2O4/ carbon nano pipe array.
Embodiment 1：
Step is：
The first step：Porous alumina formwork prepares
The alumina formwork that aperture is 200nm bilaterals is chosen, is 1 μm of copper film in its back side magnetron sputtering a layer thickness, successively
Drying is with spare after trimethylsilyl cyanide, ethyl alcohol, distilled water are cleaned by ultrasonic；
Second step：It is prepared by nickel-cobalt alloy nano pipe array
Nickel-cobalt alloy nano pipe array is prepared using square-wave pulse electrodeposition process in electrolytic cell：Prepare deposition liquid, formula is：
262 g/L NiSO4•6H2O and 562 g/L CoSO4•7H2O, 40 g/L H3BO3With 40 g/L (NH4)2SO4；With first step standard
Alumina formwork is got ready as working electrode, platinized platinum is to electrode, and saturated calomel electrode is auxiliary electrode, is added after depositing liquid
Square wave is that 0 V continues 30 s, and -2.5 V continue to carry out 50 cycles of pulse electrodeposition under 5 s, clear with distilled water after the completion of deposition
It is washed till neutrality；
Third walks：It is prepared by nickel cobalt/carbon nano pipe array
Nickel-cobalt alloy nano pipe array is put into tube furnace, air pressure in tube furnace is repeatedly adjusted to 10KPa after displacement Ar, then
500 DEG C are warming up to, the C of 50ml/min is passed through2H2, stop heating after reacting 10min, continue to be passed through Ar and be cooled to room temperature；
4th step：NiCo2O4It is prepared by/carbon nano pipe array
Nickel cobalt/carbon nano pipe array is taken out, removal alumina formwork is soaked for a period of time with the NaOH of 1M/L, then uses ethyl alcohol
It cleans to neutrality with distilled water, is placed in Muffle furnace after drying, 300 DEG C of heat preservation 2h are warming up to the heating rate of 1 DEG C/min,
NiCo is obtained after cooling2O4/ carbon nano pipe array.
XRD and TEM characterizations are carried out to the sample prepared by embodiment 1, detect NiCo2O4With carbon nanotube object phase,
NiCo2O4/ carbon nano tube compound material is core-shell nano array structure；To NiCo2O4/ carbon nano-tube combination electrode material carries out
Constant current charge-discharge test, the specific capacitance value in the case where current density is 1A/g ask 1046.8F/g respectively.
Embodiment 2：
Step is：
The first step：Porous alumina formwork prepares
The alumina formwork that aperture is 200nm bilaterals is chosen, is 1 μm of copper film in its back side magnetron sputtering a layer thickness, successively
Drying is with spare after trimethylsilyl cyanide, ethyl alcohol, distilled water are cleaned by ultrasonic；
Second step：It is prepared by nickel-cobalt alloy nano pipe array
Nickel-cobalt alloy nano pipe array is prepared using square-wave pulse electrodeposition process in electrolytic cell：Prepare deposition liquid, formula is：
262 g/L NiSO4•6H2O and 562 g/L CoSO4•7H2O, 40 g/L H3BO3With 40 g/L (NH4)2SO4；With first step standard
Alumina formwork is got ready as working electrode, platinized platinum is to electrode, and saturated calomel electrode is auxiliary electrode, is added after depositing liquid
Square wave is that 0 V continues 30 s, and -2.5 V continue to carry out 100 cycles of pulse electrodeposition under 5 s, and distilled water is used after the completion of deposition
It cleans to neutrality；
Third walks：It is prepared by nickel cobalt/carbon nano pipe array
Nickel-cobalt alloy nano pipe array is put into tube furnace, air pressure in tube furnace is repeatedly adjusted to 10KPa after displacement Ar, then
800 DEG C are warming up to, the C of 50ml/min is passed through2H2, stop heating after reacting 10min, continue to be passed through Ar and be cooled to room temperature；
4th step：NiCo2O4It is prepared by/carbon nano pipe array
Nickel cobalt/carbon nano pipe array is taken out, removal alumina formwork is soaked for a period of time with the NaOH of 1M/L, then uses ethyl alcohol
It cleans to neutrality with distilled water, is placed in Muffle furnace after drying, 300 DEG C of heat preservation 2h are warming up to the heating rate of 1 DEG C/min,
NiCo is obtained after cooling2O4/ carbon nano pipe array.
XRD and TEM characterizations are carried out to the sample prepared by embodiment 2, detect NiCo2O4With carbon nanotube object phase,
NiCo2O4/ carbon nano tube compound material is core-shell nano array structure；To NiCo2O4/ carbon nano-tube combination electrode material carries out
Constant current charge-discharge test, the specific capacitance value in the case where current density is 1A/g ask 1153.9F/g respectively.
Embodiment 3：
Step is：
The first step：Porous alumina formwork prepares
The alumina formwork that aperture is 200nm bilaterals is chosen, is 1 μm of copper film in its back side magnetron sputtering a layer thickness, successively
Drying is with spare after trimethylsilyl cyanide, ethyl alcohol, distilled water are cleaned by ultrasonic；
Second step：It is prepared by nickel-cobalt alloy nano pipe array
Nickel-cobalt alloy nano pipe array is prepared using square-wave pulse electrodeposition process in electrolytic cell：Prepare deposition liquid, formula is：
262 g/L NiSO4•6H2O and 562 g/L CoSO4•7H2O, 40 g/L H3BO3With 40 g/L (NH4)2SO4；With first step standard
Alumina formwork is got ready as working electrode, platinized platinum is to electrode, and saturated calomel electrode is auxiliary electrode, is added after depositing liquid
Square wave is that 0 V continues 30 s, and -2.5 V continue to carry out 100 cycles of pulse electrodeposition under 5 s, and distilled water is used after the completion of deposition
It cleans to neutrality；
Third walks：It is prepared by nickel cobalt/carbon nano pipe array
Nickel-cobalt alloy nano pipe array is put into tube furnace, air pressure in tube furnace is repeatedly adjusted to 10KPa after displacement Ar, then
600 DEG C are warming up to, the C of 50ml/min is passed through2H2, stop heating after reacting 60min, continue to be passed through Ar and be cooled to room temperature；
4th step：NiCo2O4It is prepared by/carbon nano pipe array
Nickel cobalt/carbon nano pipe array is taken out, removal alumina formwork is soaked for a period of time with the NaOH of 1M/L, then uses ethyl alcohol
It cleans to neutrality with distilled water, is placed in Muffle furnace after drying, 300 DEG C of heat preservation 2h are warming up to the heating rate of 1 DEG C/min,
NiCo is obtained after cooling2O4/ carbon nano pipe array.
XRD and TEM characterizations are carried out to the sample prepared by embodiment 3, detect NiCo2O4With carbon nanotube object phase,
NiCo2O4/ carbon nano tube compound material is core-shell nano array structure；To NiCo2O4/ carbon nano-tube combination electrode material carries out
Constant current charge-discharge test, the specific capacitance value in the case where current density is 1A/g ask 977.8F/g respectively.
Embodiment 4：
Step is：
The first step：Porous alumina formwork prepares
The alumina formwork that aperture is 200nm bilaterals is chosen, is 1 μm of copper film in its back side magnetron sputtering a layer thickness, successively
Drying is with spare after trimethylsilyl cyanide, ethyl alcohol, distilled water are cleaned by ultrasonic；
Second step：It is prepared by nickel-cobalt alloy nano pipe array
Nickel-cobalt alloy nano pipe array is prepared using square-wave pulse electrodeposition process in electrolytic cell：Prepare deposition liquid, formula is：
262 g/L NiSO4•6H2O and 562 g/L CoSO4•7H2O, 40 g/L H3BO3With 40 g/L (NH4)2SO4；With first step standard
Alumina formwork is got ready as working electrode, platinized platinum is to electrode, and saturated calomel electrode is auxiliary electrode, is added after depositing liquid
Square wave is that 0 V continues 30 s, and -2.5 V continue to carry out 200 cycles of pulse electrodeposition under 5 s, and distilled water is used after the completion of deposition
It cleans to neutrality；
Third walks：It is prepared by nickel cobalt/carbon nano pipe array
Nickel-cobalt alloy nano pipe array is put into tube furnace, air pressure in tube furnace is repeatedly adjusted to 10KPa after displacement Ar, then
700 DEG C are warming up to, the C of 50ml/min is passed through2H2, stop heating after reacting 30min, continue to be passed through Ar and be cooled to room temperature；
4th step：NiCo2O4It is prepared by/carbon nano pipe array
Nickel cobalt/carbon nano pipe array is taken out, removal alumina formwork is soaked for a period of time with the NaOH of 1M/L, then uses ethyl alcohol
It cleans to neutrality with distilled water, is placed in Muffle furnace after drying, 300 DEG C of heat preservation 2h are warming up to the heating rate of 1 DEG C/min,
NiCo is obtained after cooling2O4/ carbon nano pipe array.
XRD and TEM characterizations are carried out to the sample prepared by embodiment 4, detect NiCo2O4With carbon nanotube object phase,
NiCo2O4/ carbon nano tube compound material is core-shell nano array structure；To NiCo2O4/ carbon nano-tube combination electrode material carries out
Constant current charge-discharge test, the specific capacitance value in the case where current density is 1A/g ask 1334.2F/g respectively.
Claims (2)
1. a kind of NiCo2O4/ carbon nano-tube combination electrode material, which is characterized in that NiCo2O4/ carbon nano-tube combination electrode material
Monomer using carbon nanotube as core, NiCo2O4Nanotube is the nucleocapsid of shell, generally high-sequential nano-tube array.
2. a kind of NiCo as described in claim 12O4/ carbon nano-tube combination electrode material, it is characterised in that preparation process is：
The first step：Porous alumina formwork prepares
The alumina formwork that aperture is 200nm bilaterals is chosen, is 1 μm of copper film in its back side magnetron sputtering a layer thickness, successively
Drying is with spare after trimethylsilyl cyanide, ethyl alcohol, distilled water are cleaned by ultrasonic；
Second step：It is prepared by nickel-cobalt alloy nano pipe array
Nickel-cobalt alloy nano pipe array is prepared using square-wave pulse electrodeposition process in electrolytic cell：It gets out aluminium oxide with the first step
Template is to electrode as working electrode, platinized platinum, and saturated calomel electrode is auxiliary electrode, and square-wave pulse is carried out after deposition liquid is added
Electro-deposition, deposition is after the completion wash with distilled water to neutral；
The deposition liquid ingredient is：1 part of NiSO4•6H2O, 2 parts of CoSO4•7H2O, H3BO3(NH4)2SO4；
The condition of the square-wave pulse electro-deposition is：Continue 30 s in 0 V, then moment add 5 s of potential duration of -2.5 V
Square-wave pulse electro-deposition certain time；
Third walks：It is prepared by nickel cobalt/carbon nano pipe array
Nickel-cobalt alloy nano pipe array is put into tube furnace, air pressure in tube furnace is repeatedly adjusted to 10KPa after displacement Ar, then
500 ~ 800 DEG C are warming up to, the C of 50ml/min is passed through2H2, stop heating after reacting 10 ~ 60min, continue to be passed through Ar and be cooled to room
Temperature；
4th step：NiCo2O4It is prepared by/carbon nano pipe array
Nickel cobalt/carbon nano pipe array is taken out, removal alumina formwork is soaked for a period of time with the NaOH of 1M/L, then uses ethyl alcohol
It cleans to neutrality with distilled water, is placed in Muffle furnace after drying, 300 DEG C of heat preservation 2h are warming up to the heating rate of 1 DEG C/min,
NiCo is obtained after cooling2O4/ carbon nano pipe array.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810170727.2A CN108376614B (en) | 2018-03-01 | 2018-03-01 | A kind of NiCo2O4/ carbon nano-tube combination electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810170727.2A CN108376614B (en) | 2018-03-01 | 2018-03-01 | A kind of NiCo2O4/ carbon nano-tube combination electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108376614A true CN108376614A (en) | 2018-08-07 |
| CN108376614B CN108376614B (en) | 2019-09-27 |
Family
ID=63018245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810170727.2A Expired - Fee Related CN108376614B (en) | 2018-03-01 | 2018-03-01 | A kind of NiCo2O4/ carbon nano-tube combination electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108376614B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110828808A (en) * | 2019-11-19 | 2020-02-21 | 肇庆市华师大光电产业研究院 | Preparation method and application of lithium-sulfur battery positive electrode material |
| CN110863226A (en) * | 2019-11-18 | 2020-03-06 | 南通大学 | SERS substrate with composite gold and silver nano array structure and preparation method thereof |
| CN110862078A (en) * | 2019-10-16 | 2020-03-06 | 江苏镭明新材料科技有限公司 | Preparation method of 1D structure carbon nanotube NiCoOOH composite material |
| CN111307897A (en) * | 2020-02-27 | 2020-06-19 | 广州钰芯传感科技有限公司 | NiCo for enzyme-free detection of glucose2O4/Ni-P composite electrode and preparation method and application thereof |
| CN111575761A (en) * | 2020-05-26 | 2020-08-25 | 苏州凌威新能源科技有限公司 | Alumina template, highly vertical ordered antimony nanowire array and preparation method thereof |
| CN113564559A (en) * | 2021-07-28 | 2021-10-29 | 福州大学 | Rapid in-situ preparation method of CNTs @ TC4 composite powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161313A (en) * | 2015-07-14 | 2015-12-16 | 徐靖才 | Method of preparing nickel cobaltite/carbon nanotube composite materials |
| CN106158063A (en) * | 2015-04-23 | 2016-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube paper, its activation method and application for chemical electric power source electrode material |
| CN106449159A (en) * | 2016-11-29 | 2017-02-22 | 大连海洋大学 | Flexible electrode with carbon fiber wrapped metal oxide for capacitor and preparation method |
-
2018
- 2018-03-01 CN CN201810170727.2A patent/CN108376614B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106158063A (en) * | 2015-04-23 | 2016-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube paper, its activation method and application for chemical electric power source electrode material |
| CN105161313A (en) * | 2015-07-14 | 2015-12-16 | 徐靖才 | Method of preparing nickel cobaltite/carbon nanotube composite materials |
| CN106449159A (en) * | 2016-11-29 | 2017-02-22 | 大连海洋大学 | Flexible electrode with carbon fiber wrapped metal oxide for capacitor and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| WEN-WEN LIU ET AL.: "A three dimensional vertically aligned multiwall carbon nanotube/NiCo2O4 core/shell structure for novel high-performance supercapacitors", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862078A (en) * | 2019-10-16 | 2020-03-06 | 江苏镭明新材料科技有限公司 | Preparation method of 1D structure carbon nanotube NiCoOOH composite material |
| CN110863226A (en) * | 2019-11-18 | 2020-03-06 | 南通大学 | SERS substrate with composite gold and silver nano array structure and preparation method thereof |
| CN110828808A (en) * | 2019-11-19 | 2020-02-21 | 肇庆市华师大光电产业研究院 | Preparation method and application of lithium-sulfur battery positive electrode material |
| CN110828808B (en) * | 2019-11-19 | 2022-04-26 | 肇庆市华师大光电产业研究院 | Preparation method and application of lithium-sulfur battery positive electrode material |
| CN111307897A (en) * | 2020-02-27 | 2020-06-19 | 广州钰芯传感科技有限公司 | NiCo for enzyme-free detection of glucose2O4/Ni-P composite electrode and preparation method and application thereof |
| CN111575761A (en) * | 2020-05-26 | 2020-08-25 | 苏州凌威新能源科技有限公司 | Alumina template, highly vertical ordered antimony nanowire array and preparation method thereof |
| CN113564559A (en) * | 2021-07-28 | 2021-10-29 | 福州大学 | Rapid in-situ preparation method of CNTs @ TC4 composite powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108376614B (en) | 2019-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108376614B (en) | A kind of NiCo2O4/ carbon nano-tube combination electrode material and preparation method thereof | |
| Wang et al. | Metal/metal oxide nanoparticles-composited porous carbon for high-performance supercapacitors | |
| Wen et al. | Direct inkjet printing of flexible MXene/graphene composite films for supercapacitor electrodes | |
| Venkatachalam et al. | Double hydroxide mediated synthesis of nanostructured ZnCo2O4 as high performance electrode material for supercapacitor applications | |
| Huang et al. | High performance asymmetric supercapacitor based on hierarchical flower-like NiCo2S4@ polyaniline | |
| Fu et al. | Electrodeposition of nickel hydroxide films on nickel foil and its electrochemical performances for supercapacitor | |
| Li et al. | Hydrous RuO2 nanoparticles coated on Co (OH) 2 nanoflakes as advanced electrode material of supercapacitors | |
| Xu et al. | Design of the seamless integrated C@ NiMn-OH-Ni3S2/Ni foam advanced electrode for supercapacitors | |
| CN105161313B (en) | A kind of preparation method of cobalt acid nickel carbon nanometer tube composite materials | |
| Liu et al. | Sol–gel synthesis of nanoporous NiCo2O4 thin films on ITO glass as high-performance supercapacitor electrodes | |
| Dong et al. | The synthesis of graphene/PVDF composite binder and its application in high performance MnO2 supercapacitors | |
| Zeng et al. | Electrodeposition of hierarchical manganese oxide on metal nanoparticles decorated nanoporous gold with enhanced supercapacitor performance | |
| CN108054019A (en) | Laminated construction NiCo2S4@NixCo(1-x)(OH)2The preparation method and application of composite material | |
| CN105321725B (en) | A kind of ultracapacitor micro-nano structure electrode material and electrode piece preparation method | |
| Wang et al. | Controllable synthesis of NiCo2O4, NiCo2O4/graphene composite and their electrochemical application in supercapacitors | |
| CN105742625B (en) | Nano-electrode material with sandwich and its preparation method and application | |
| CN108172407B (en) | Composite electrode, preparation method and application thereof | |
| CN109786135A (en) | A kind of copper oxide@nickel molybdate/foam copper combination electrode material and preparation method thereof | |
| CN105448536B (en) | Nickel oxide/TiOx nano composite material and preparation method thereof and stored energy application | |
| Song et al. | Preparation of Cu2O/Cu porous granular films by in situ oxidation for electrochemical energy storage | |
| Liu et al. | Hexadecyl trimethyl ammonium bromide assisted growth of NiCo 2 O 4@ reduced graphene oxide/nickel foam nanoneedle arrays with enhanced performance for supercapacitor electrodes | |
| Xue et al. | Design and fabrication of petal-like NiCo2O4@ NiMoO4 core/shell nanosheet arrys electrode for asymmetric supercapacitors | |
| Dhaiveegan et al. | Pulse-reversal deposition of Ni3S2 thin films on carbon fiber cloths for supercapacitors | |
| CN110571067A (en) | Super capacitor electrode material and preparation method thereof | |
| CN102751100B (en) | Preparation method of supercapacitor electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190903 Address after: 310018 School of Material Chemistry, China Metrology University, 258 Xiasha Xueyuan Street, Jianggan District, Hangzhou City, Zhejiang Province Applicant after: CHINA JILIANG UNIVERSITY Address before: Hangzhou City, Zhejiang Province, Jianggan District Xiasha 310018 source Street No. 258 Applicant before: Xu Jingcai |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190927 Termination date: 20210301 |