CN108075128A - A kind of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material - Google Patents
A kind of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material Download PDFInfo
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- CN108075128A CN108075128A CN201810012852.0A CN201810012852A CN108075128A CN 108075128 A CN108075128 A CN 108075128A CN 201810012852 A CN201810012852 A CN 201810012852A CN 108075128 A CN108075128 A CN 108075128A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000007772 electrode material Substances 0.000 title claims abstract description 45
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000011248 coating agent Substances 0.000 title claims abstract description 23
- 238000000576 coating method Methods 0.000 title claims abstract description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000036571 hydration Effects 0.000 claims abstract description 11
- 238000006703 hydration reaction Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 6
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000013110 organic ligand Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005486 sulfidation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- VBNWKIADIBAREY-UHFFFAOYSA-N acetic acid nickel Chemical compound [Ni].CC(O)=O.CC(O)=O.CC(O)=O VBNWKIADIBAREY-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- -1 cobalt acetates Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical class CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material and preparation method thereof, belong to the preparation field of electrode for super capacitor material.The preparation method includes procedure below:By graphene oxide(GO)It is added in ethylene glycol solution, ultrasonic disperse, GO is made to be uniformly dispersed in ethylene glycol solution;By polyvinylpyrrolidone(PVP), four hydration cobalt acetates, four hydration nickel acetates be added in the GO dispersion liquids of above-mentioned configuration, ultrasonic disperse dissolving after be transferred to round-bottomed flask carry out oil bath reaction and centrifuge washing drying;The product that centrifuge washing after oil bath is dried and thiocarbamide are calcined to obtain N doping carbon coating cobalt nickel sulfide/graphene combination electrode material.Uniform cobalt nickel sulfide particle is coated with nitrogen-doped carbon on the electrode material microscopic appearance of preparation, and is uniformly supported on graphene-based bottom, while has higher specific capacitance, excellent high rate performance and cyclical stability.
Description
Technical field
The invention belongs to the preparation fields of electrode for super capacitor material, and in particular to a kind of N doping carbon coating cobalt nickel
Sulfide/graphene combination electrode material and preparation method thereof.
Background technology
Ultracapacitor due to its have higher power density, excellent high rate performance, fast charge/discharge rate,
The characteristics of cycle life of overlength, quick charge transport rate and low-maintenance cost etc. are excellent, can be applicable to energy storage device,
On dynamic power system and many electronic equipments, the extensive concern from industrial quarters and academia is attracted.Super electricity
The performance of container with its used in electrode material it is closely related, currently used three kinds of electrode materials(Carbon material, metal oxidation
Object/hydroxide, conducting polymer)Respectively there are advantage and disadvantage:Carbon material simple production process, cheap, good cycle, but compare
Capacity is relatively low;Metal oxide/hydroxide and conducting polymer specific capacity are high but of high cost, cyclical stability is bad.Research
Show to carry out above-mentioned different types of electrode material compound the shortcomings that can not only making up homogenous material, while can also be real
The mutual supplement with each other's advantages of existing material property, obtains the super capacitor for having high power capacity, excellent cycling and high rate performance concurrently.
Carbon material has large specific surface area, and conductive and excellent thermal conductivity, chemical stability is good, it is at low cost the features such as, be
The electrode material that ultracapacitor is studied earliest, technology are the most ripe.Mainly have for the carbon material of ultracapacitor:Activity
Charcoal, carbon black, carbon fiber, carbon nanotubes, carbon aerogels, graphene etc..Transient metal sulfide has very high theoretical specific capacity
And good cyclical stability, while electric conductivity is hundred times of oxide, is a kind of ultracapacitor with bright prospects
Electrode material.By the use of graphene as the compound base material of transient metal sulfide the synergistic effect of the two can be utilized to prepare
Go out the electrode material of high performance ultracapacitor.
The content of the invention
It is an object of the invention to provide a kind of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material and its
Preparation method.In order to further improve the chemical property of cobalt nickel sulfide/graphene, in step carbonization and sulfidation,
Organic ligand is carbonized to form carbon, in the carbon for forming nitrogen-doping to organic ligand in vulcanization, it is conductive to promote electrode material
Property and defect, so as to improve chemical property.Uniform cobalt nickel sulfide particle on the electrode material microscopic appearance of preparation
Nitrogen-doped carbon is coated with, and is uniformly supported on graphene-based bottom, while there is higher specific capacitance, excellent multiplying power
Performance and cyclical stability.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of preparation method of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material, includes the following steps:
(1)By quantitative graphene oxide(GO)It is added in ethylene glycol solution, ultrasonic disperse so that graphene oxide(GO)
It is uniformly dispersed in ethylene glycol solution;
(2)By quantitative polyvinylpyrrolidone(PVP), four hydration cobalt acetates(Co(CH3COO)2·4H2O), four hydration acetic acid
Nickel(Ni(CH3COO)2·4H2O)It is added to step(1)In solution, liquid mixed above is transferred to round bottom after ultrasound fully dissolving
The reaction of oil bath pan finish application bath is placed in flask, it is multiple with absolute ethyl alcohol centrifuge washing then after it naturally cools to room temperature,
The product after washing is finally placed in drying;
(3)By quantitative step(2)The product of centrifugal drying and the mixing of quantitative thiocarbamide are laid in porcelain boat, are then put porcelain boat
Calcining carries out carbonization and the vulcanizing treatment of a step in the tube furnace of argon gas protection, is finally made after it naturally cools to room temperature
It is standby to obtain N doping carbon coating cobalt nickel sulfide/graphene combination electrode material.
Electrode material obtained by the present invention, cobalt nickel sulfide particle are coated with nitrogen-doped carbon, and size is homogeneous, uniformly
It is supported on graphene-based bottom.
One-step method is carbonized simultaneously and vulcanization, organic ligand are carbonized to form carbon, the nitrogen-doping in sulfidation in thiocarbamide
In the carbon formed to organic ligand, N doping carbon coating cobalt nickel sulfide/graphene combination electrode material is formed, improves electrode
The chemical property of material.
The remarkable advantage of the present invention is:
(1)The present invention is vulcanized using thiocarbamide as sulphur source by the way of calcining, and organic ligand occurs simultaneously in sulfidation
Carburizing reagent, whole process vulcanization and carbonization be carried out at the same time, preparation process is simple, and operation controllability is strong.
(2)Organic ligand is carbonized to form carbon, improves the electric conductivity of electrode material.
(3)In sulfidation, the nitrogen in thiocarbamide can be doped in the carbon of organic ligand formation, be conducive to improve electricity
The chemical property of pole material.
(4)Electrode material prepared by the present invention specific capacitance under 1 A/g current density charge and discharge is 1028 F/g, 10 A/g
Specific capacitance conservation rate under current density charge and discharge(It is forthright again)For 89.3%, 6 A/g current densities charge and discharge cycles 1500 times, than
Capacity retention(Cyclical stability)For 93.6%, show that prepared electrode material has higher specific capacitance, excellent multiplying power
Performance and cyclical stability.
Description of the drawings
Fig. 1 is the XRD diffraction of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material made from embodiment 1
Collection of illustrative plates.
Fig. 2 is the scanning electron microscope of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material made from embodiment 1
Figure;As can be seen from the figure the carbon-coated nanocrystalline size of cobalt nickel sulfide of N doping is homogeneous, grain size in 80 ~ 100 nm,
It is uniformly supported on graphene-based bottom.
Fig. 3 is that the EDS of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material made from embodiment 1 schemes;From
Electrode material prepared by it can be seen from the figure that mainly contains the elements such as Co, Ni, S, C, N, and wherein N content shows to pass through this up to 25%
N element is successfully doped in electrode material by method.
Fig. 4 is the high-resolution of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material made from embodiment 1
TEM schemes;As can be seen from the figure prepared cobalt nickel sulfide is wrapped in carbon(Carbon)In.
Fig. 5 is that the GCD of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material made from embodiment 1 schemes;From
The charge and discharge under different current densities of electrode material prepared by it can be seen from the figure that all show higher coulombic efficiency.
Specific embodiment
The present invention is further illustrated the present invention with the following example, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
A kind of preparation method of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material, concretely comprises the following steps:
(1)Weigh 10 mg graphene oxides(GO, self-control)It is added in 50 mL ethylene glycol, ultrasonic disperse 30 minutes makes GO exist
It is uniformly dispersed in ethylene glycol;
(2)Weigh the polyvinylpyrrolidone of 0.3 g(PVP), the four hydration cobalt acetates of 125 mg(Co(CH3COO)2·4H2O)
Nickel acetate is hydrated with the four of 124 mg(Ni(CH3COO)2·4H2O)It is added to step(1)In solution, ultrasound fully dissolving, then
Liquid mixed above is transferred in round-bottomed flask be placed on oil bath pan 150 DEG C of oil baths reactions 5 it is small when.Finally, treat that it is naturally cold
But to after room temperature, with absolute ethyl alcohol centrifuge washing 4-5 times, the product after washing is placed in electric drying oven with forced convection and is dried;
(3)Weigh 15 mg steps(2)The product of centrifugal drying and 35 mg thiocarbamides are uniformly laid in after mixing in porcelain boat by hand,
Then porcelain boat is placed in the carbonization of one step of calcining progress and vulcanizing treatment, calcining heat 250 in the tube furnace of argon gas protection
DEG C, heating rate is per minute for 1 DEG C, when heat preservation 5 is small.Finally product is can obtain after it naturally cools to room temperature.
Embodiment 2
A kind of preparation method of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material, concretely comprises the following steps:
(1)Weigh 5 mg graphene oxides(GO, self-control)It is added in 30 mL ethylene glycol, ultrasonic disperse 30 minutes makes GO in second
It is uniformly dispersed in glycol;
(2)Weigh the polyvinylpyrrolidone of 0.5 g(PVP), the four hydration cobalt acetates of 250 mg(Co(CH3COO)2·4H2O)
Nickel acetate is hydrated with the four of 250 mg(Ni(CH3COO)2·4H2O)It is added to step(1)In solution, ultrasound fully dissolving, then
Liquid mixed above is transferred in round-bottomed flask be placed on oil bath pan 250 DEG C of oil baths reactions 1 it is small when.Finally, treat that it is naturally cold
But to after room temperature, with absolute ethyl alcohol centrifuge washing 4-5 times, the product after washing is placed in electric drying oven with forced convection and is dried;
(3)Weigh 30 mg steps(2)The product of centrifugal drying and 50 mg thiocarbamides are uniformly laid in after mixing in porcelain boat by hand,
Then porcelain boat is placed in the carbonization of one step of calcining progress and vulcanizing treatment, calcining heat 300 in the tube furnace of argon gas protection
DEG C, heating rate is per minute for 1 DEG C, when heat preservation 4 is small.Finally product is can obtain after it naturally cools to room temperature.
Embodiment 3
A kind of preparation method of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material, concretely comprises the following steps:
(1)Weigh 20 mg graphene oxides(GO, self-control)It is added in 100 mL ethylene glycol, ultrasonic disperse 30 minutes makes GO exist
It is uniformly dispersed in ethylene glycol;
(2)Weigh the polyvinylpyrrolidone of 0.1 g(PVP), the four hydration cobalt acetates of 60 mg(Co(CH3COO)2·4H2O)With
The four hydration nickel acetates of 70 mg(Ni(CH3COO)2·4H2O)It is added to step(1)In solution, ultrasound fully dissolving then will
Liquid mixed above be transferred in round-bottomed flask be placed on oil bath pan 200 DEG C of oil baths reactions 1 it is small when.Finally, its natural cooling is treated
To after room temperature, with absolute ethyl alcohol centrifuge washing 4-5 times, the product after washing is placed in electric drying oven with forced convection and is dried;
(3)Weigh 5 mg steps(2)The product of centrifugal drying and 10 mg thiocarbamides are uniformly laid in after mixing in porcelain boat, so by hand
It is 500 DEG C that porcelain boat is placed in the carbonization of one step of calcining progress and vulcanizing treatment, calcining heat in the tube furnace of argon gas protection afterwards,
Heating rate is per minute for 1 DEG C, when heat preservation 1 is small.Finally product is can obtain after it naturally cools to room temperature.
Electrochemical property test
By N doping carbon coating cobalt nickel sulfide/graphene combination electrode material of above method preparation, acetylene black(Conductive agent)
And Kynoar(PVDF, binding agent)By 8:1:1(Mass ratio)Ratio addition mixing after be evenly coated in conduct in nickel foam
Working electrode, using platinum filament as to electrode, using mercury oxidation mercury electrode as reference electrode, using 3 mol/L KOH solutions as electricity
Liquid is solved, measures under electrode material three-electrode system made from embodiment 1,2,3 that specific capacitance is respectively under 1 A/g current densities
1028th, 987,968 F/g, specific capacitance conservation rate under 10 A/g current densities(It is forthright again)Respectively 89.3,87.5,88.4%, 6
A/g current densities charge and discharge cycles 2000 times, specific capacitance conservation rate(Cyclical stability)Respectively 93.6,91.5,90.3%.
Show that electrode material chemical property prepared by embodiment 1 is optimal.
Comparative example 1
The method for preparing cobalt nickel sulfide/graphene combination electrode material:
Weigh step in 40 mg embodiments 1(2)The product of centrifugal drying and 120 mg thioacetamides, are added to 30 mL ethyl alcohol
In solution, it is transferred to after ultrasound fully dissolving in the stainless steel cauldron of 50 mL, it is small is placed in 170 DEG C of hydro-thermal reactions 6 in baking oven
When.Finally after it naturally cools to room temperature, with absolute ethyl alcohol centrifuge washing 4-5 times, the product after washing is placed in electric heating drum
It is dried in wind drying box.
Cobalt nickel sulfide/graphene combination electrode material prepared by above method is subjected to electricity according to above-mentioned same method
Chemical property is tested, and measures under electrode material three-electrode system made from comparative example 1 that specific capacitance is under 1 A/g current densities
952 F/g, specific capacitance conservation rate under 10 A/g current densities(It is forthright again)Only 73.7%, 6 A/g current density charge and discharge cycles
2000 times, specific capacitance conservation rate(Cyclical stability)Only 53.8%.
Due to the present invention preparation method introduce nitrogen-doped carbon be coated on cobalt nickel sulfide surface, introduce the defects of more and
Increase electrode material electric conductivity, compared to comparative example 1, N doping carbon coating cobalt nickel sulfide/graphene prepared by the present invention is multiple
Composite electrode material has better high rate performance and cyclical stability.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (2)
1. a kind of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material, which is characterized in that its preparation method includes
Following steps:
(1)It adds graphene oxide into ethylene glycol solution, ultrasonic disperse so that graphene oxide is equal in ethylene glycol solution
It is even scattered;
(2)Polyvinylpyrrolidone, four hydration cobalt acetates, four hydration nickel acetates are added to step(1)In solution, ultrasound is fully
Liquid mixed above is transferred in round-bottomed flask after dissolving and is placed in the reaction of oil bath pan finish application bath, then treats that it naturally cools to room
Wen Hou, it is multiple with absolute ethyl alcohol centrifuge washing, finally the product after washing is dried;
(3)By step(2)Product and the thiocarbamide mixing of centrifugal drying are laid in porcelain boat, and porcelain boat then is placed in argon gas protection
Calcining carries out carbonization and the vulcanizing treatment of a step in tube furnace, and N doping is finally prepared after it naturally cools to room temperature
Carbon coating cobalt nickel sulfide/graphene combination electrode material.
2. N doping carbon coating cobalt nickel sulfide/graphene combination electrode material according to claim 1, feature exist
In:Its preparation method comprises the following specific steps that:
(1)It weighs 5 ~ 30 mg graphene oxides to be added in 30 ~ 100 mL ethylene glycol solutions, ultrasonic disperse 30 minutes makes oxidation
Graphene is uniformly dispersed in ethylene glycol solution;
(2)Weigh the polyvinylpyrrolidone of 0.1 ~ 0.5 g, the four hydration cobalt acetates of 60 ~ 250 mg and four water of 60 ~ 250 mg
It closes nickel acetate and is added to step(1)In solution, liquid mixed above is then transferred in round-bottomed flask and is placed in oil by ultrasonic dissolution
When 100 ~ 300 DEG C of oil bath reactions 1 ~ 5 are small on bath, finally, after it naturally cools to room temperature, with absolute ethyl alcohol centrifuge washing
4-5 times, the product after washing is dried;
(3)Weigh 5 ~ 30 mg steps(2)The product of centrifugal drying and 10 ~ 60 mg thiocarbamides, are laid in porcelain boat after mixing,
Then porcelain boat is placed in carbonization and the vulcanizing treatment that calcining in the tube furnace of argon gas protection carries out a step, calcining heat for 200 ~
500 DEG C, heating rate is 1 DEG C/min, when heat preservation 1 ~ 5 is small, finally treats that it naturally cools to room temperature, is prepared N doping
Carbon coating cobalt nickel sulfide/graphene combination electrode material.
Priority Applications (1)
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