CN104900416A - Preparation method of novel nickel @combined carbon electrode material - Google Patents
Preparation method of novel nickel @combined carbon electrode material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 129
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000007772 electrode material Substances 0.000 title claims abstract description 63
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 22
- 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
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 60
- 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 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 14
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 14
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 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
- 239000007789 gas Substances 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
- 238000001354 calcination Methods 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 17
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 239000010405 anode material Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 8
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 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
- 230000000694 effects Effects 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 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 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 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
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-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
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 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
- 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
- 238000011835 investigation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [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
- 150000003839 salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
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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 the field of preparation of combined electrode materials, and concretely relates to a preparation method of novel nickel @combined carbon electrode materials. The method includes the steps: evenly mixing glucose, NH4C1 and nickel salt, placing the mixture into a crucible, placing the crucible in a tubular furnace, taking high purity inert gas as a protective atmosphere to perform high temperature calcining on the mixture, cooling the mixture to a normal temperature, washing and drying the mixture, and finally obtaining a nickel @combined carbon electrode material. Raw materials are low in cost and easily available, no solvent is needed, processes are easy to operate, and the production cost is saved. The prepared novel nickel @combined carbon electrode material exhibits excellent electrochemistrical performance.
Description
Technical field
The invention belongs to combination electrode material preparation field, be specifically related to a kind of preparation method of nickel composite carbon electrode material.
Background technology
Along with the development of modern society, the demand of the mankind to novel, low cost, environmental friendliness and high performance energy memory device also increases day by day.Ultracapacitor, because having high power density, high energy density, long cycle life and low maintenance cost, is expected to become a kind of novel energy storage equipment.And electrode material plays a part core in ultracapacitor, therefore research has the important directions that the electrode material of high energy storage performance is ultracapacitor research.
In recent years, metal oxide/hydroxide electrode material is paid close attention to greatly because it can show higher ratio capacitance.In numerous metal oxide/hydroxide, nickel oxide/hydroxide because it is with low cost, environmental friendliness, there is higher ratio capacitance and good invertibity and obtain investigation and application more widely.But there is the problems such as conductance is low, cyclical stability is poor in nickel oxide/hydroxide electrode material.Therefore, research has high electrochemical performance, the New Nickel base electrode material of high stability has a good application prospect.
In prior art, also have and adopt metallic nickel sill as electrode material for super capacitor, nano nickle granules has been obtained by the reduction of hydrazine hydrate as Xing etc. reports, obtain ratio capacitance (the Nickel nanoparticles prepared by hydrazine hydrate reduction and their application in supercapacitor.Powder Technology of 417F/g, 2012,224:162-167); Niu etc. report and have obtained nickel/graphene combination electrode material by the compound of hydrazine hydrate reduction nickel chloride and graphene oxide, its ratio capacitance reaches 560F/g (Solvothermal synthesis of Ni/reduced graphene oxide composites as electrode material for supercapacitors.Electrochimica Acta, 2014,123:560-568); But the solvent that they use when preparing W metal sill being poisonous, preparing W metal sill method also comparatively complicated and difficult, being unfavorable for that it is further applied.
Summary of the invention
The object of the invention is to: adopt easy method to prepare New Nickel composite carbon electrode material, and the application of this material in ultracapacitor is provided.
The technical solution used in the present invention is that one-step calcination method original position prepares New Nickel composite carbon electrode material, mainly comprises the following steps:
(1) by glucose, NH
4cl and nickel salt mix,
Wherein, nickel salt is chloride, nitrate, the water soluble salt such as sulfate or acetate of nickel, preferred nickel chloride,
The mass percent of nickel salt and glucose is 20 ~ 300%, is preferably 32 ~ 250%,
Ammonium chloride not only plays pore-creating effect, also in preparation process, plays and carries out moulding effect to the pattern of material with carbon element;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), using high purity inert gas as protective atmosphere, high-temperature calcination is carried out to described mixture,
High purity inert gas is high pure nitrogen, high-purity argon gas, the high-purity helium that purity is greater than 99.999%,
High-temperature calcination is operating as, and with the heating rate of 1 ~ 10 DEG C/min, is warming up to 600 ~ 1500 DEG C, and maintains 1 ~ 5h,
As preferably: with the heating rate of 5 DEG C/min, be warming up to 1000 DEG C, and maintain 3h;
(4) product after high-temperature calcination in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
Beneficial effect of the present invention is: prepared nickel composite carbon electrode material by one-step calcination method original position.Raw material nickel salt and glucose cheap and easy to get, without the need to any solvent, technological operation is easy, has saved production cost; Preparation forms the New Nickel composite carbon electrode material of special construction as shown in Figure 2, have loose structure, and its degree of graphitization is higher; This New Nickel composite carbon electrode material shows more excellent chemical property.The pattern of nickel metal changes and is mainly determined (pattern of material with carbon element is then primarily of ammonium chloride decision) by the institute of the material with carbon element in calcination process, material with carbon element is in Graphene conversion process, nickel metal can as support frame, enter into the structure of Graphene to a certain extent, and in combination electrode material after the completion of reaction, due to the support frame effect of nickel metal, be conducive to the special appearance maintaining material, overcome the defect that simple material with carbon element pattern is easily destroyed.
Accompanying drawing explanation
The XRD figure of Fig. 1 New Nickel composite carbon electrode material obtained by embodiment 1.
The FESEM figure of Fig. 2 New Nickel composite carbon electrode material obtained by embodiment 1.
Fig. 3 obtained by embodiment 1 New Nickel composite carbon electrode material in 2M KOH solution, the performance cycle figure under the current density of 1A/g.
Fig. 4 is that the UV-Vis of 3 kinds of different materials absorbs spectrogram,
Wherein, curve a represents nickel composite carbon electrode material obtained in embodiment 1, and the UV-Vis after abundant pickling (use 3mol/L hydrochloric acid, deionized water wash successively, and dry) absorbs spectrogram;
Curve b represent with embodiment 1 equal conditions under do not add nickel chloride, obtained carbon electrode material, the UV-Vis after abundant pickling (successively with 3mol/L hydrochloric acid, deionized water washing, and dry) absorbs spectrogram;
Curve c represent with embodiment 1 equal conditions under do not add ammonium chloride, obtained nickel composite carbon electrode material, the UV-Vis after abundant pickling (successively with 3mol/L hydrochloric acid, deionized water washing, and dry) absorbs spectrogram,
Characterize known through above-mentioned ultraviolet-visible spectrum (UV-Vis), only with the addition of the material with carbon element that slaine and ammonium chloride carry out calcining, be that obvious graphene-structured characteristic peak appears in 270nm place at wavelength, show that products therefrom degree of graphitization is high.
Embodiment
Embodiment 1
(1) by 2g glucose, 2g NH
4cl and 1.3010g nickel chloride fully mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 1000 DEG C with the programming rate of 5 DEG C/min, and maintain this temperature 3h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
Fig. 1 is the XRD figure of above-mentioned obtained New Nickel carbon composite, and characterize through X-ray powder diffraction (XRD), obtained product is nickel carbon, and wherein, nickel corresponds to (JCPDS:04-0850).
Fig. 3 is the above-mentioned obtained performance cycle figure of New Nickel carbon composite under 1A/g current density, after its cycle charge-discharge 3000 times, can see that its ratio capacitance has only decayed about 5%.
The New Nickel composite carbon electrode material that employing embodiment 1 prepares is for super capacitor anode material, obtain higher ratio capacitance, experimental result shows: in 2M KOH solution, under the current density of 1A/g, its ratio capacitance reaches 786F/g, demonstrates excellent chemical property.
Curve a in Fig. 4 represents nickel composite carbon electrode material obtained in embodiment 1, through abundant pickling (successively with 3mol/L hydrochloric acid, deionized water washing, and dry) after UV-Vis absorb spectrogram, show that the degree of graphitization of material with carbon element in electrode material is very high.
Embodiment 2
(1) by 2g glucose, 2g NH
4cl and 1.8281g nickel nitrate fully mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 1500 DEG C with the programming rate of 10 DEG C/min, and maintain this temperature 0.5h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
The nickel composite carbon electrode material that the method prepares is for super capacitor anode material, obtain higher ratio capacitance, experimental result shows: in 2M KOH solution, under the current density of 1A/g, its ratio capacitance reaches 810F/g, demonstrates excellent chemical property.
Embodiment 3
(1) by 2g glucose, 2g NH
4cl and 1.7686g nickel acetate fully mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 1400 DEG C with the programming rate of 9 DEG C/min, and maintain this temperature 1h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
The nickel composite carbon electrode material that the method prepares is for super capacitor anode material, obtain higher ratio capacitance, experimental result shows: in 2M KOH solution, under the current density of 1A/g, its ratio capacitance reaches 806F/g, demonstrates excellent chemical property.
Embodiment 4
(1) by 2g glucose, 2g NH
4cl and 1.5884g nickelous sulfate fully mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 1300 DEG C with the programming rate of 8 DEG C/min, and maintain this temperature 1.5h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
The nickel carbon composite that the method prepares is for super capacitor anode material, obtain higher ratio capacitance, experimental result shows: in 2M KOH solution, under the current density of 1A/g, its ratio capacitance reaches 801F/g, demonstrates excellent chemical property.
Embodiment 5
(1) by 2g glucose, 2g NH
4cl and 1.3010g nickel chloride fully mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 1200 DEG C with the programming rate of 7 DEG C/min, and maintain this temperature 2h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
The nickel composite carbon electrode material that the method prepares is for super capacitor anode material, obtain higher ratio capacitance, experimental result shows: in 2M KOH solution, under the current density of 1A/g, its ratio capacitance reaches 795F/g, demonstrates excellent chemical property.
Embodiment 6
(1) by 2g glucose, 2g NH
4cl and 1.3010g nickel chloride fully mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 1100 DEG C with the programming rate of 6 DEG C/min, and maintain this temperature 2.5h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
The nickel composite carbon electrode material that the method prepares is for super capacitor anode material, obtain higher ratio capacitance, experimental result shows: in 2M KOH solution, under the current density of 1A/g, its ratio capacitance reaches 789F/g, demonstrates excellent chemical property.
Embodiment 7
(1) by 2g glucose, 2g NH
4cl and 1.3010g nickel chloride fully mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 900 DEG C with the programming rate of 4 DEG C/min, and maintain this temperature 3.5h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
The nickel composite carbon electrode material that the method prepares is for super capacitor anode material, obtain higher ratio capacitance, experimental result shows: in 2M KOH solution, under the current density of 1A/g, its ratio capacitance reaches 751F/g, demonstrates excellent chemical property.
Embodiment 8
(1) by 2g glucose, 2g NH
4cl and 1.3010g nickel chloride fully mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 800 DEG C with the programming rate of 3 DEG C/min, and maintain this temperature 4h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
The New Nickel composite carbon electrode material that the method prepares is for super capacitor anode material, obtain higher ratio capacitance, experimental result shows: in 2M KOH solution, under the current density of 1A/g, its ratio capacitance reaches 709F/g, shows good chemical property.
Embodiment 9
(1) by 2g glucose, 2g NH
4cl and 1.3010g nickel chloride fully mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 700 DEG C with the programming rate of 2 DEG C/min, and maintain this temperature 4.5h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
The New Nickel composite carbon electrode material that the method prepares is for super capacitor anode material, obtain higher ratio capacitance, experimental result shows: in 2M KOH solution, under the current density of 1A/g, its ratio capacitance reaches 663F/g, demonstrates good chemical property.
Embodiment 10
(1) by 2g glucose, 2g NH
4cl and 1.3010g nickel chloride fully mixes;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 600 DEG C with the programming rate of 1 DEG C/min, and maintain this temperature 5h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after dry, obtains nickel composite carbon electrode material.
The nickel composite carbon electrode material that the method prepares is for super capacitor anode material, obtain very high ratio capacitance, experimental result shows: in 2M KOH solution, under the current density of 1A/g, its ratio capacitance reaches 605F/g, demonstrates excellent chemical property.
Reference examples 1:
The preparation method of the graphene oxide (RGO) of reduction, comprises the following steps:
(1) 2g GO put into crucible and be placed in tube furnace;
(2) using high pure nitrogen (purity is greater than 99.999%)/hydrogen as atmosphere, rise to 1000 DEG C with the programming rate of 5 DEG C/min, and maintain this temperature 3h, after reaction terminates, by products therefrom deionized water and absolute ethanol washing, dry, obtain RGO material.
Adopt the RGO material for preparing of reference examples 1 for super capacitor anode material, in 2M KOH solution, under the current density of 1A/g, its ratio capacitance only has 420F/g, shows poor relative to New Nickel material with carbon element of the present invention of its chemical property.
Reference examples 2:
The preparation method of nano nickle granules, comprises the following steps:
(1) 1.3010g nickel chloride put into crucible and be placed in tube furnace;
(2) using high pure nitrogen (purity is greater than 99.999%)/hydrogen as atmosphere, rise to 1000 DEG C with the programming rate of 5 DEG C/min, and maintain this temperature 3h, after reaction terminates, by products therefrom deionized water and absolute ethanol washing, dry, obtain nano nickle granules.
The nano nickle granules material that employing reference examples 2 prepares is for super capacitor anode material, and in 2M KOH solution, under the current density of 1A/g, its ratio 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 oxide is placed in 60mL ethanol ultrasonic disperse 30min;
(2) by 0.1301g nickel chloride ultrasonic dissolution in water, drop in the mixed liquor of (1) and stir, then drip sodium hydroxide solution regulate pH to 10 ~ 11, stir, be placed in water heating kettle, 120 DEG C, reaction 4h;
(3) product of step (2) is filtered, isolate solid product;
(4) using high pure nitrogen (purity is greater than 99.999%)/hydrogen as atmosphere, rise to 1000 DEG C with the programming rate of 5 DEG C/min, and maintain this temperature 3h, after reaction terminates, by products therefrom deionized water and absolute ethanol washing, dry, obtain Ni-RGO composite material.
Nickel-RGO the composite material that employing reference examples 3 prepares is for super capacitor anode material, in 2M KOH solution, under the current density of 1A/g, its ratio capacitance only has 550F/g, because the nickel in the present embodiment is only simply be carried on Graphene, this is also the reason causing chemical property poor relative to New Nickel material with carbon element of the present invention.
Reference examples 4:
Preparation method's (under not adding ammonium chloride condition) of nano nickel-carbon composite, comprises the following steps:
(1) 2g glucose and 1.3010g nickel chloride are fully mixed;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), be greater than the high pure nitrogen of 99.999% as protective atmosphere using purity, rise to 1000 DEG C with the programming rate of 5 DEG C/min, and maintain this temperature 3h, calcining is realized to mixture;
(4) product after calcining in step (3) is cooled to normal temperature, with deionized water and absolute ethanol washing, after drying, obtains nickel-carbon composite.
Nickel-carbon composite that employing reference examples 4 prepares is for super capacitor anode material, in 2M KOH solution, under the current density of 1A/g, its ratio capacitance only has 451F/g, shows poor relative to New Nickel complex carbon material of the present invention of its chemical property.
The curve c of above-mentioned experimental data by reference to the accompanying drawings in 4 can find out: when lacking ammonium chloride, possess graphene-structured hardly in the electrode material prepared.
The ultracapacitor performance of similar composite material in nickel composite carbon electrode material prepared by embodiment 1 and existing document contrasted, its result is as table 1:
Table 1
| Composite material | Current density | Electrolyte | Ratio capacitance |
| New Nickel carbon | 1A/g | 2M KOH | 786F/g |
| Ni nano particle | 1A/g | 2M KOH | 417F/g |
| NiC | 1A/g | 2M KOH | 530F/g |
| Ni-RGO | 1A/g | 2M KOH | 560F/g |
Can be found out by table 1, by the standby New Nickel composite carbon electrode materials application of one-step calcination legal system in super capacitor anode material, in 2M KOH electrolyte, its ratio capacitance is apparently higher than Ni nano particle (the Nickel nanoparticles prepared by hydrazine hydrate reduction and their application in supercapacitor.Powder Technology of bibliographical information, 2012, 224:162-167), ratio capacitance (the Hydrothermal synthesis of NiC core – shell composites with high capacitance.Journal of Alloys and Compounds of NiC composite material, 2013, 575:152-157), Ni-RGO composite material (Solvothermal synthesis of Ni/reduced graphene oxide composites as electrode material for supercapacitors.Electrochimica Acta, 2014, 123:560-568).
The electro-chemical activity of the New Nickel composite carbon electrode material excellence in the present invention, mainly owing to the support frame of nickel metal as carbon structure, is conducive to the nickel composite carbon electrode material forming special construction.
Claims (6)
1. a preparation method for nickel composite carbon electrode material, is characterized in that: the concrete steps of described preparation method are,
(1) by glucose, NH
4cl and nickel salt mix;
(2) mixture in step (1) is put into crucible and is placed in tube furnace;
(3) in the tube furnace described in step (2), using high purity inert gas as protective atmosphere, high-temperature calcination is carried out to described mixture;
(4) product after high-temperature calcination in step (3) is cooled to normal temperature, washing, dry rear acquisition nickel composite carbon electrode material.
2. the preparation method of nickel composite carbon electrode material as claimed in claim 2, is characterized in that: the nickel salt described in step (1) is nickel chloride.
3. the preparation method of nickel composite carbon electrode material as claimed in claim 2, is characterized in that: the mass percent of the nickel salt described in step (1) and described glucose is 20 ~ 300%.
4. the preparation method of nickel composite carbon electrode material as claimed in claim 2, is characterized in that: the high purity inert gas described in step (3) is high pure nitrogen, high-purity argon gas, the high-purity helium that purity is greater than 99.999%.
5. the preparation method of nickel composite carbon electrode material as claimed in claim 2, is characterized in that: the high-temperature calcination described in step (3) is operating as, with the heating rate of 1 ~ 10 DEG C/min, is warming up to 600 ~ 1500 DEG C, and maintains 1 ~ 5h.
6. the preparation method of nickel composite carbon electrode material as claimed in claim 2, is characterized in that: the washing operation described in step (4) is for using deionized water and absolute ethanol washing.
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| CN108682564A (en) * | 2018-05-23 | 2018-10-19 | 济南大学 | A kind of Ni-C composite material and preparation methods for ultracapacitor |
| CN111764155A (en) * | 2020-06-17 | 2020-10-13 | 武汉纺织大学 | Two-dimensional transition metal carbide/conductive carbon fiber composite material and preparation method and application thereof |
| CN111764155B (en) * | 2020-06-17 | 2022-11-04 | 武汉纺织大学 | Two-dimensional transition metal carbide/conductive carbon fiber composite material and preparation method and application thereof |
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Application publication date: 20150909 Assignee: JIANGSU RONGSHENG ELECTRONIC CO.,LTD. Assignor: CHANGZHOU University|NANTONG JIANGHAI CAPACITOR Co.,Ltd. Contract record no.: X2024980000484 Denomination of invention: A preparation method of nickel @ composite carbon electrode material Granted publication date: 20180511 License type: Common License Record date: 20240110 |