CN104900416B - A kind of preparation method of nickel@composite carbon electrode materials - Google Patents
A kind of preparation method of nickel@composite carbon electrode materials Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 64
- 239000007772 electrode material Substances 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 27
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 25
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 17
- 239000008103 glucose Substances 0.000 claims abstract description 17
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000003990 capacitor Substances 0.000 description 16
- 239000010405 anode material Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 7
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical class [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 wherein Inorganic materials 0.000 description 1
Classifications
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to combination electrode material preparation field, and in particular to a kind of preparation method of nickel@composite carbon electrode materials.Concretely comprise the following steps：By glucose, NH4Cl and nickel salt, which are uniformly mixed, to be put into crucible and is placed in tube furnace, and using high purity inert gas as protective atmosphere, high-temperature calcination is carried out to mixture, be cooled to room temperature, wash, it is dry after obtain nickel@composite carbon electrode materials.Raw material is cheap and easy to get, and without any solvent, technological operation is easy, has saved production cost, prepared nickel@composite carbon electrode materials show excellent chemical property.
Description
Technical field
The invention belongs to combination electrode material preparation field, and in particular to a kind of preparation side of nickel@composite carbon electrode materials
Method.
Background technology
With the development of modern society, the mankind are to new, inexpensive, environmental-friendly and high performance energy storage device need
Asking also increasingly increases.Ultracapacitor is because having high power density, high energy density, the cycle life of length and low maintenance
Expense, is expected to become a kind of new energy storage equipment.And electrode material plays a part of core in ultracapacitor, because
This electrode material of the research with high energy storage performance is the important directions of ultracapacitor research.
In recent years, metal oxide/hydroxide electrode material obtains pole because it can show higher specific capacitance
Big concern.In numerous metal oxide/hydroxide, nickel oxide/hydroxide is because its is of low cost, environment is friendly
Specific capacitance good, that there is higher and good invertibity and obtain more widely studying and applying.However, nickel oxide/hydrogen
There are the problems such as conductivity is low, cyclical stability is poor for oxide electrode material.Therefore, research is with high electrochemical performance, Gao Wen
Qualitatively new nickel base electrode material has a good application prospect.
In the prior art, also have and reported using metal nickel-base material as electrode material for super capacitor, such as Xing
Nano nickle granules have been made by the reduction of hydrazine hydrate, have obtained specific capacitance (the Nickel nanoparticles of 417F/g
prepared by hydrazine hydrate reduction and their application in
supercapacitor.Powder Technology,2012,224:162-167)；Niu etc., which is reported, passes through hydrazine hydrate reduction
Nickel/graphene combination electrode material has been made in the compound of nickel chloride and graphene oxide, its specific capacitance has reached 560F/g
(Solvothermal synthesis of Ni/reduced graphene oxide composites as electrode
material for supercapacitors.Electrochimica Acta,2014,123:560-568)；However, they
When preparing W metal sill, used solvent is poisonous, and it is also complex and tired to prepare W metal sill method
Difficulty, is unfavorable for its further popularization and application.
The content of the invention
It is an object of the invention to：Nickel@composite carbon electrode materials are prepared using easy method, and this material is provided
Application in ultracapacitor.
Nickel@composite carbon electrode materials are prepared in situ for one-step calcination method in the technical solution adopted by the present invention, it is main include with
Lower step：
(1) by glucose, NH4Cl and nickel salt are uniformly mixed,
Wherein, nickel salt for nickel the water soluble salt, preferably nickel chloride such as chloride, nitrate, sulfate or acetate,
The mass percent of nickel salt and glucose is 20~300%, is preferably 32~250%,
Ammonium chloride not only acts as pore-creating effect, also in preparation process, plays and carries out moulding work to the pattern of carbon material
With；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), using high purity inert gas as protective atmosphere, to the mixture
Carry out high-temperature calcination,
High purity inert gas is more than 99.999% high pure nitrogen, high-purity argon gas, high-purity helium for purity,
High-temperature calcination operation is, with the heating rate of 1~10 DEG C/min, to be warming up to 600~1500 DEG C, and maintains 1~5h,
As preferred：With the heating rate of 5 DEG C/min, 1000 DEG C are warming up to, and maintain 3h；
(4) product after step (3) high temperature is calcined is cooled to room temperature, and is washed with deionized water and absolute ethyl alcohol, is done
Nickel@composite carbon electrode materials are obtained after dry.
The beneficial effects of the present invention are：Nickel@composite carbon electrode materials have been prepared in situ by one-step calcination method.Raw material nickel
Salt and glucose are cheap and easy to get, and without any solvent, technological operation is easy, has saved production cost；Prepare and formed such as the institute of attached drawing 2
The nickel@composite carbon electrode materials of the special construction shown, have loose structure, and its degree of graphitization is higher；Nickel@composite carbons
Electrode material shows more excellent chemical property.The pattern of nickel metal changes mainly by the carbon materials in calcination process
Material determines (and the pattern of carbon material is then mainly determined by ammonium chloride) that carbon material is into graphene conversion process, nickel metal energy
Support frame is enough used as, is entered to a certain extent in the structure of graphene, and in combination electrode material after the completion of reaction,
Since the support frame of nickel metal acts on, be conducive to maintain the special appearance of material, it is easy to overcome simple carbon material pattern
The defects of by destroying.
Brief description of the drawings
Fig. 1 is the XRD diagram of nickel@composite carbon electrode materials obtained by embodiment 1.
Fig. 2 is that the FESEM of nickel@composite carbon electrode materials obtained by embodiment 1 schemes.
Fig. 3 for nickel@composite carbon electrodes material obtained by embodiment 1 in 2M KOH solutions, under the current density of 1A/g
Performance cycle figure.
Fig. 4 is that the UV-Vis of 3 kinds of different materials absorbs spectrogram,
Wherein, curve a represents nickel@composite carbon electrode materials obtained in embodiment 1, (is used successively by abundant pickling
3mol/L hydrochloric acid, deionized water washing, and dry) after UV-Vis absorb spectrogram；
Curve b is represented with being not added with nickel chloride, obtained carbon electrode material, by abundant under 1 equal conditions of embodiment
UV-Vis after pickling (being washed successively with 3mol/L hydrochloric acid, deionized water, and dry) absorbs spectrogram；
Curve c is represented with being not added with ammonium chloride, obtained nickel@composite carbon electrode materials, warp under 1 equal conditions of embodiment
The UV-Vis crossed after abundant pickling (being washed successively with 3mol/L hydrochloric acid, deionized water, and dry) absorbs spectrogram,
Understood through above-mentioned ultraviolet-visible spectrum (UV-Vis) characterization, only with the addition of metal salt and ammonium chloride is calcined
Carbon material, there is obvious graphene-structured characteristic peak for 270nm places in wavelength, show that products therefrom degree of graphitization is high.
Embodiment
Embodiment 1
(1) by 2g glucose, 2g NH4Cl and 1.3010g nickel chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 1000 DEG C are risen to the programming rate of 5 DEG C/min, and maintain this temperature 3h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel@composite carbon electrode materials.
Fig. 1 is the XRD diagram of above-mentioned obtained nickel@carbon composites, is characterized through X-ray powder diffraction (XRD), obtained
Product be nickel@carbon, wherein, nickel corresponds to (JCPDS:04-0850).
Fig. 3 is above-mentioned obtained performance cycle figure of the nickel@carbon composites under 1A/g current densities, from its cycle charge discharge
After electricity 3000 times, it can be seen that its specific capacitance has only decayed about 5%.
The nickel@composite carbon electrodes material being prepared using embodiment 1 is used for super capacitor anode material, obtain compared with
High specific capacitance, test result indicates that：In 2M KOH solutions, under the current density of 1A/g, its specific capacitance has reached 786F/g,
Show excellent chemical property.
Curve a in Fig. 4 represents nickel@composite carbon electrode materials obtained in embodiment 1, by abundant pickling (successively
Washed with 3mol/L hydrochloric acid, deionized water, and dry) after UV-Vis absorb spectrogram, show the stone of carbon material in electrode material
Blackization degree is very high.
Embodiment 2
(1) by 2g glucose, 2g NH4Cl and 1.8281g nickel nitrates be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 1500 DEG C are risen to the programming rate of 10 DEG C/min, and maintain this temperature 0.5h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel@composite carbon electrode materials.
The nickel@composite carbon electrodes material that this method is prepared is used for super capacitor anode material, obtains higher
Specific capacitance, test result indicates that：In 2M KOH solutions, under the current density of 1A/g, its specific capacitance has reached 810F/g, display
Go out excellent chemical property.
Embodiment 3
(1) by 2g glucose, 2g NH4Cl and 1.7686g nickel acetates be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 1400 DEG C are risen to the programming rate of 9 DEG C/min, and maintain this temperature 1h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel@composite carbon electrode materials.
The nickel@composite carbon electrodes material that this method is prepared is used for super capacitor anode material, obtains higher
Specific capacitance, test result indicates that：In 2M KOH solutions, under the current density of 1A/g, its specific capacitance has reached 806F/g, display
Go out excellent chemical property.
Embodiment 4
(1) by 2g glucose, 2g NH4Cl and 1.5884g nickel sulfates be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 1300 DEG C are risen to the programming rate of 8 DEG C/min, and maintain this temperature 1.5h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel@composite carbon electrode materials.
The nickel@carbon composites that this method is prepared are used for super capacitor anode material, obtain higher ratio electricity
Hold, test result indicates that：In 2M KOH solutions, under the current density of 1A/g, its specific capacitance has reached 801F/g, shows excellent
Different chemical property.
Embodiment 5
(1) by 2g glucose, 2g NH4Cl and 1.3010g nickel chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 1200 DEG C are risen to the programming rate of 7 DEG C/min, and maintain this temperature 2h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel@composite carbon electrode materials.
The nickel@composite carbon electrodes material that this method is prepared is used for super capacitor anode material, obtains higher
Specific capacitance, test result indicates that：In 2M KOH solutions, under the current density of 1A/g, its specific capacitance has reached 795F/g, display
Go out excellent chemical property.
Embodiment 6
(1) by 2g glucose, 2g NH4Cl and 1.3010g nickel chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 1100 DEG C are risen to the programming rate of 6 DEG C/min, and maintain this temperature 2.5h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel@composite carbon electrode materials.
The nickel@composite carbon electrodes material that this method is prepared is used for super capacitor anode material, obtains higher
Specific capacitance, test result indicates that：In 2M KOH solutions, under the current density of 1A/g, its specific capacitance has reached 789F/g, display
Go out excellent chemical property.
Embodiment 7
(1) by 2g glucose, 2g NH4Cl and 1.3010g nickel chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 900 DEG C are risen to the programming rate of 4 DEG C/min, and maintain this temperature 3.5h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel@composite carbon electrode materials.
The nickel@composite carbon electrodes material that this method is prepared is used for super capacitor anode material, obtains higher
Specific capacitance, test result indicates that：In 2M KOH solutions, under the current density of 1A/g, its specific capacitance has reached 751F/g, display
Go out excellent chemical property.
Embodiment 8
(1) by 2g glucose, 2g NH4Cl and 1.3010g nickel chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 800 DEG C are risen to the programming rate of 3 DEG C/min, and maintain this temperature 4h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel@composite carbon electrode materials.
The nickel@composite carbon electrodes material that this method is prepared is used for super capacitor anode material, obtains higher
Specific capacitance, test result indicates that：In 2M KOH solutions, under the current density of 1A/g, its specific capacitance has reached 709F/g, display
Preferable chemical property is gone out.
Embodiment 9
(1) by 2g glucose, 2g NH4Cl and 1.3010g nickel chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 700 DEG C are risen to the programming rate of 2 DEG C/min, and maintain this temperature 4.5h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel@composite carbon electrode materials.
The nickel@composite carbon electrodes material that this method is prepared is used for super capacitor anode material, obtains higher
Specific capacitance, test result indicates that：In 2M KOH solutions, under the current density of 1A/g, its specific capacitance has reached 663F/g, display
Go out preferable chemical property.
Embodiment 10
(1) by 2g glucose, 2g NH4Cl and 1.3010g nickel chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 600 DEG C are risen to the programming rate of 1 DEG C/min, and maintain this temperature 5h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel@composite carbon electrode materials.
The nickel@composite carbon electrodes material that this method is prepared is used for super capacitor anode material, obtains very high
Specific capacitance, test result indicates that：In 2M KOH solutions, under the current density of 1A/g, its specific capacitance has reached 605F/g, display
Go out excellent chemical property.
Reference examples 1：
The preparation method of the graphene oxide (RGO) of reduction, comprises the following steps：
(1) 2g GO are put into crucible to be placed in tube furnace；
(2) high pure nitrogen (purity is more than 99.999%)/hydrogen as atmosphere, is risen to the programming rate of 5 DEG C/min
1000 DEG C, and this temperature 3h is maintained, after reaction, products therefrom is washed with deionized water and absolute ethyl alcohol, it is dry, obtain
RGO materials.
The RGO materials being prepared using reference examples 1 are used for super capacitor anode material, in 2M KOH solutions, 1A/
Under the current density of g, its specific capacitance only has 420F/g, shows that its chemical property is wanted relative to the nickel@carbon materials of the present invention
Difference.
Reference examples 2：
The preparation method of nano nickle granules, comprises the following steps：
(1) 1.3010g nickel chlorides are put into crucible to be placed in tube furnace；
(2) high pure nitrogen (purity is more than 99.999%)/hydrogen as atmosphere, is risen to the programming rate of 5 DEG C/min
1000 DEG C, and this temperature 3h is maintained, after reaction, products therefrom is washed with deionized water and absolute ethyl alcohol, it is dry, obtain
Nano nickle granules.
The nano nickle granules material being prepared using reference examples 2 is used for super capacitor anode material, molten in 2M KOH
In liquid, under the current density of 1A/g, its specific capacitance only has 420F/g, shows that its chemical property is very poor.
Reference examples 3：
The preparation method of nano nickel-carbon composite, comprises the following steps：
(1) 2g graphite oxides are placed in ultrasonic disperse 30min in 60mL ethanol；
(2) 0.1301g nickel chloride ultrasonic dissolutions are added dropwise in the mixed liquor of (1) and stirred evenly, then hydrogen is added dropwise in water
Sodium hydroxide solution adjusts pH to 10~11, stirs evenly, is placed in water heating kettle, 120 DEG C, reacts 4h；
(3) product of step (2) is filtered, isolates solid product；
(4) high pure nitrogen (purity is more than 99.999%)/hydrogen as atmosphere, is risen to the programming rate of 5 DEG C/min
1000 DEG C, and this temperature 3h is maintained, after reaction, products therefrom is washed with deionized water and absolute ethyl alcohol, it is dry, obtain
Ni-RGO composite materials.
Nickel-RGO the composite materials being prepared using reference examples 3 are used for super capacitor anode material, molten in 2M KOH
In liquid, under the current density of 1A/g, its specific capacitance only has 550F/g, and stone is only simply carried on by nickel in this present embodiment
On black alkene, this is also to cause a reason of the chemical property relative to the nickel@carbon materials difference of the present invention.
Reference examples 4：
The preparation method (being not added with the conditions of ammonium chloride) of nano nickel-carbon composite, comprises the following steps：
(1) 2g glucose and 1.3010g nickel chlorides be sufficiently mixed uniformly；
(2) mixture in step (1) is put into crucible to be placed in tube furnace；
(3) in the tube furnace described in step (2), protection gas is used as using high pure nitrogen of the purity more than 99.999%
Atmosphere, 1000 DEG C are risen to the programming rate of 5 DEG C/min, and maintain this temperature 3h, and mixture is realized and is calcined；
(4) product after calcining in step (3) is cooled to room temperature, is washed with deionized water and absolute ethyl alcohol, after dry
Obtain nickel-carbon composite.
Nickel-the carbon composite being prepared using reference examples 4 is used for super capacitor anode material, in 2M KOH solutions
In, under the current density of 1A/g, its specific capacitance only has 451F/g, shows that its chemical property is compound relative to the nickel@of the present invention
Wanting for carbon material is poor.
Curve c in above-mentioned experimental data combination attached drawing 4 can be seen that：In the case where lacking ammonium chloride, prepare
Hardly possesses graphene-structured in electrode material.
By the super capacitor of the nickel@composite carbon electrodes material composite material similar with existing literature prepared by embodiment 1
Device performance is contrasted, its result such as table 1：
Table 1
| Composite material | Current density | Electrolyte | Specific capacitance |
| Nickel@carbon | 1A/g | 2M KOH | 786F/g |
| Ni nano particles | 1A/g | 2M KOH | 417F/g |
| Ni@C | 1A/g | 2M KOH | 530F/g |
| Ni-RGO | 1A/g | 2M KOH | 560F/g |
It can be seen from Table 1 that the nickel composite carbon electrode materials application prepared by one-step calcination method is in ultracapacitor
Positive electrode, in 2M KOH electrolyte, Ni nano particle (Nickel of its specific capacitance apparently higher than document report
nanoparticles prepared by hydrazine hydrate reduction and their application
in supercapacitor.Powder Technology,2012,224:162-167), the specific capacitance of Ni@C composites
(Hydrothermal synthesis of Ni@C core–shell composites with high
capacitance.Journal of Alloys and Compounds,2013,575:152-157), Ni-RGO composite materials
(Solvothermal synthesis of Ni/reduced graphene oxide composites as electrode
material for supercapacitors.Electrochimica Acta,2014,123:560-568)。
The excellent electro-chemical activity of nickel@composite carbon electrode materials in the present invention is mainly due to nickel metal as carbon structure
Support frame, advantageously form the nickel@composite carbon electrode materials of special construction.
Claims (6)
- A kind of 1. preparation method of nickel@composite carbon electrode materials, it is characterised in that：The preparation method concretely comprises the following steps,（1）By glucose, NH4Cl and nickel salt are uniformly mixed, without using any solvent；（2）By step（1）In mixture be put into crucible and be placed in tube furnace；（3）In step（2）Described in tube furnace in, using high purity inert gas as protective atmosphere, to the mixture carry out High-temperature calcination；（4）By step（3）Product after high temperature calcining is cooled to room temperature, and washs, nickel@composite carbon electrode materials are obtained after drying Material.
- 2. the preparation method of nickel@composite carbon electrode materials as claimed in claim 1, it is characterised in that：Step（1）Described in Nickel salt is nickel chloride.
- 3. the preparation method of nickel@composite carbon electrode materials as claimed in claim 2, it is characterised in that：Step（1）Described in The mass percent of nickel salt and the glucose is 20 ~ 300%.
- 4. the preparation method of nickel@composite carbon electrode materials as claimed in claim 2, it is characterised in that：Step（3）Described in High purity inert gas is more than 99.999% high pure nitrogen, high-purity argon gas or high-purity helium for purity.
- 5. the preparation method of nickel@composite carbon electrode materials as claimed in claim 2, it is characterised in that：Step（3）Described in High-temperature calcination operation is, with the heating rate of 1 ~ 10 °C/min, to be warming up to 600 ~ 1500 °C, and maintain 1 ~ 5h.
- 6. the preparation method of nickel@composite carbon electrode materials as claimed in claim 2, it is characterised in that：Step（4）Described in Washing operation is to be washed with deionized water and absolute ethyl alcohol.
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