CN110136980A - Hydrolyze vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation method of regulation - Google Patents
Hydrolyze vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation method of regulation Download PDFInfo
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- CN110136980A CN110136980A CN201910514837.0A CN201910514837A CN110136980A CN 110136980 A CN110136980 A CN 110136980A CN 201910514837 A CN201910514837 A CN 201910514837A CN 110136980 A CN110136980 A CN 110136980A
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- 239000004744 fabric Substances 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 82
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000004073 vulcanization Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000007772 electrode material Substances 0.000 title claims abstract description 34
- 230000033228 biological regulation Effects 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 230000007062 hydrolysis Effects 0.000 claims abstract description 25
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 235000019441 ethanol Nutrition 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 14
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 9
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 11
- 238000005342 ion exchange Methods 0.000 abstract description 5
- 238000005530 etching Methods 0.000 abstract description 4
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 229910017709 Ni Co Inorganic materials 0.000 description 10
- 229910003267 Ni-Co Inorganic materials 0.000 description 10
- 229910003262 Ni‐Co Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation methods of hydrolysis regulation, including the preparation of cobalt-based metal organic frame/carbon cloth composite material, the preparation of porous nickel cobalt layered double hydroxide/carbon cloth composite material and porous vulcanization nickel cobalt/carbon cloth composite material preparation, in porous nickel cobalt layered double hydroxide/carbon cloth composite material preparation process, through cobalt-based metal-organic framework material Co-MOFs and nickel nitrate solution ion exchange and Ni occur for the present invention2+Hydrolysis generates hole to the etching of Co-MOFs, synthesize the nickel cobalt layered double hydroxide for the hollow porous structure being grown on carbon cloth, on the basis of keeping MOFs parent shape, the hollow porous appearance structure with multiple valence state, bigger serface and high electroactive binary metal sulfide based on carbon cloth is prepared, improves composite material as the capacitive properties of electrode, high rate performance and electrochemistry cycle life.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, and in particular to the vulcanization nickel cobalt/carbon cloth for hydrolyzing regulation is porous super
The preparation method of grade capacitance electrode material.
Background technique
In recent years, huge resource consumption and problem of environmental pollution became increasingly conspicuous, with Industry Structure transition and upgrade,
The high speed development of New Energy Industry and technology is pushed.Supercapacitor is due to having both quick, safe charge-discharge characteristic, superelevation
Power density and the physical properties such as light, small in size, vital impetus is played to the development of new energy technology.And
The performance of supercapacitor and the property of its electrode material are closely related, compared to traditional carbon material, transition metal vulcanization
Object especially vulcanizes nickel cobalt, is widely studied due to energy-storage property with higher.However, it is existing studies have reported that nickel sulfide
That there are specific surface areas is low for cobalt nanostructure, and active site is uneven, causes the energy-storage property of electrode material poor, cycle life is short
Defect is not able to satisfy demand of the supercapacitor to electrode material.Metal-organic framework material (MOFs) has cellular structure
With great specific surface area, the potential ability that MOFs generates electric double layer capacitance in supercapacitor applications is imparted.However,
Both at home and abroad in research, preparing electrode material as matrix using MOFs is mainly that the method for utilizing high-temperature heat treatment decomposes MOFs structure,
Making the specific surface area of material seriously reduces, and the energy storage property of electrode material is caused sharply to decline.
Summary of the invention
To solve the above problems, the present invention provides vulcanization nickel cobalt/porous super capacitance electrode material of carbon cloth of hydrolysis regulation
Preparation method, avoid under the conditions of high-temperature heat treatment decompose cobalt-based metal-organic framework material caused by material precursor structure
It collapses, can be improved capacitive properties, high rate performance and cycle life of the composite material as electrode.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
Hydrolyze vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation method of regulation, it is characterised in that: specific steps
Are as follows:
Step 1: the preparation of cobalt-based metal organic frame/carbon cloth composite material: preparing the reaction of cobalt-based metal-organic framework material
Carbon cloth is immersed in cobalt-based metal-organic framework material reaction solution and reacts 2-20h, after reaction taken out sample, then use by liquid
Distilled water and ethyl alcohol cleaning, it is dry, obtain cobalt-based metal organic frame/carbon cloth composite material；
Step 2: the preparation of porous nickel cobalt layered double hydroxide/carbon cloth composite material: the cobalt-based gold that step 1 is obtained
Belong to organic frame/carbon cloth composite material and immerse in nickel nitrate solution and react, be stirred to react 3-40min, after reaction with water and
Ethyl alcohol cleaning, obtains porous nickel cobalt layered double hydroxide/carbon cloth composite material；
Step 3: porous vulcanization nickel cobalt/carbon cloth composite material preparation: thioacetamide is as sulphur source, much with step 2 institute
Hole nickel cobalt layered double hydroxide/carbon cloth composite material is collectively disposed in reaction kettle and carries out hydro-thermal reaction, by sample after reaction
Product take out, and are washed and dried with distilled water and ethyl alcohol, obtain the porous vulcanization nickel cobalt/carbon cloth composite with hollow structure
Material.
Further, in step 1, the carbon cloth is before immersing cobalt-based metal-organic framework material reaction solution also in nitre
9-24h is impregnated in acid, is cleaned after immersion with distilled water.
Further, in step 1, cobalt-based metal-organic framework material reaction solution includes the water as metal ion center
The 2-methylimidazole of cobalt nitrate and the predecessor as organic ligand is closed, nitric hydrate cobalt and 2-methylimidazole are also respectively in solvent
Middle dissolution simultaneously mixes.
Further, the solvent of nitric hydrate cobalt and 2-methylimidazole is water, methanol, ethyl alcohol and n,N-Dimethylformamide
One of.
Further, the molar ratio of nitric hydrate cobalt and 2-methylimidazole is 1:5-1:12.
Further, the molar ratio of nitric hydrate nickel and nitric hydrate cobalt is 1:2-2:1.
Further, in step 2, the solvent of nickel nitrate solution is one of methanol and ethyl alcohol.
Further, in step 3, thioacetamide and porous nickel cobalt layered double hydroxide/carbon cloth composite material
Reaction temperature be 90-200 DEG C, reaction time 1-10h, thioacetamide and nitric hydrate cobalt and nitric hydrate nickel always rub
The ratio of your number is 2:1-6:1.
The present invention passes through cobalt-based in porous nickel cobalt layered double hydroxide/carbon cloth composite material preparation process
Ion exchange and etching process occur for metal organic frame/carbon cloth composite material Co-MOFs/CC and nickel nitrate solution, in synthesis
The porous nickel cobalt layered double hydroxide (Ni-Co LDH) of hollow structure, detailed process is as follows:
Ni2+Hydrolytic process: Ni occurs2++2H2O=Ni(OH)2+2H+
The H generated by hydrolysis+It etches Co-MOFs structure and generates hole configurations, and ion occurs with Co-MOFs/CC simultaneously
Exchange, the Ni-Co LDH of formation are deposited on surface, obtain porous nickel cobalt layered double hydroxide/carbon cloth of hollow structure
Composite material Ni-Co LDH/CC.
The invention has the benefit that
1, vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation method of hydrolysis regulation of the invention, overcome with
Toward the harsh conditions for decomposing cobalt-based metal organic frame MOFs structure using high-temperature heat treatment and chemically treated method, avoid
The collapsing for leading to MOFs precursor structure at high temperature, is able to maintain that the porosity of resulting materials, so that it is big to have composite material
Specific surface area；
2, the present invention utilizes second yuan of metal ion Ni2+Hydrolysis, on the one hand make its generate hydrogen ion enter MOFs mother
It performs etching generation hole in body, on the other hand carries out ion exchange and obtain binary metal structure, and be further made and have
Electrode of the composite material of empty porous appearance structure as supercapacitor；
3, ion exchange process is controlled by simple hydrolysis and prepares base on the basis of keeping MOFs parent shape
In the hollow porous flexible material with multiple valence state, bigger serface and high electroactive binary metal sulfide of carbon cloth
Material plays a crucial role in the performance for improving energy accumulating device, provides more channels for electrolyte ion,
Make more sufficiently, efficiently contact between electroactive point and electrolyte ion, while also shortening ion diffusion and electronics turn
Path is moved, to improve capacitive properties and high rate performance of the composite material as electrode.
Detailed description of the invention
Fig. 1 is preparation route schematic diagram of the invention；
Fig. 2 is vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material scanning electron microscope (SEM) photograph of hydrolysis regulation；
Fig. 3 is vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material high power transmission electron microscope picture of hydrolysis regulation；
Fig. 4 is the X-ray diffraction pattern for the porous super capacitance electrode material of vulcanization nickel cobalt removed from carbon cloth；
Fig. 5 is vulcanization nickel cobalt/porous super capacitance electrode material of carbon cloth of hydrolysis regulation in different scanning rates (20 mV s-1-
100mV s-1) under cyclic voltammetry curve figure；
Fig. 6 is vulcanization nickel cobalt/charge and discharge of the porous super capacitance electrode material of carbon cloth under different current densities of hydrolysis regulation
Curve；
Fig. 7 is vulcanization nickel cobalt/porous super capacitance electrode material of carbon cloth of hydrolysis regulation in 10 A g-1What Shi Xunhuan 20000 was enclosed
Cycle characteristics curve.
Specific embodiment
In order to which those skilled in the art better understood when technical solution provided by the present invention, below with reference to specific
Embodiment is illustrated.
Fig. 1 is preparation route schematic diagram of the invention, and the present invention passes through the cobalt-based metal organic frame that is grown on carbon cloth
(Co-MOFs) preparation of composite material, porous nickel cobalt layered double hydroxide/carbon cloth (Ni-Co LDH/CC) composite material
Preparation and the preparation of porous vulcanization nickel cobalt/carbon cloth (Ni-Co-S/CC) composite material realize, be prepared based on carbon cloth
The hollow porous appearance structure with multiple valence state, bigger serface and high electroactive binary metal sulfide, mentioning
It is played a crucial role in the performance of high energy storage device.
Step 1: the preparation for the Co-MOFs composite material being grown on carbon cloth:
Carbon cloth is impregnated into 9-24h in nitric acid, after cleaned with distilled water.It is with nitric hydrate cobalt and 2-methylimidazole respectively
After dissolving and mix in a solvent, carbon cloth is immersed in mixed liquor, reacts 2- for the predecessor of metal ion center and organic ligand
After 20h, sample is taken out, is washed and dried respectively with distilled water and ethyl alcohol, the cobalt-based metal for obtaining being grown on carbon cloth is organic
Frame material Co-MOFs(Co-MOFs/CC) composite material；
Wherein: the molar ratio of nitric hydrate cobalt and 2-methylimidazole is 1:5-1:12, and solvent is water, methanol, ethyl alcohol and N, N- bis-
One of methylformamide.
Step 2: the preparation of porous Ni-Co LDH/CC composite material
The resulting Co-MOFs/CC of step 1 is immersed in the solution containing nickel nitrate, 3-40 min is stirred to react, uses water respectively
It is cleaned with ethyl alcohol；
Wherein: the molar ratio of nitric hydrate cobalt is 1:2-2:1, the solution solvent for use containing nickel nitrate in nickel nitrate and step 1
For methanol or ethyl alcohol.
In this step, pass through Co-MOFs/CC and metal ion Ni2+Ion exchange and etching process are carried out, is synthesized hollow
The Ni-Co layered double-hydroxide (Ni-Co LDH) of structure, detailed process is as follows:
Ni2+Hydrolytic process: Ni occurs2++2H2O=Ni(OH)2+2H+
The H generated by hydrolysis+It etches Co-MOFs structure and generates hole configurations, and ion occurs with Co-MOFs/CC simultaneously
Exchange forms Ni-Co LDH and is deposited on surface, obtains the Ni-Co LDH/CC of hollow structure.
Step 3: the preparation of porous Ni-Co-S/CC composite material
Using thioacetamide (TAA) as sulphur source, it is anti-that progress hydro-thermal in reaction kettle is placed in Ni-Co LDH/CC obtained by step 2
Answer, take out sample after reaction, washed and dried with distilled water and ethyl alcohol, products obtained therefrom be grown in it is hollow on carbon cloth
The Ni-Co-S composite material of structure；
Wherein: reaction temperature are as follows: 90-200 DEG C, the reaction time are as follows: 1-10 h, thioacetamide and nitric hydrate cobalt and hydration
The ratio of the total mole number of nickel nitrate is 2:1-6:1.
Embodiment 1
(1), carbon cloth is impregnated to 10 h in nitric acid, is cleaned with distilled water.By 1 mmol nitric hydrate cobalt and 8 mmol
2-methylimidazole is dissolved in respectively in 30 ml methanol, and after being stirred, processed carbon cloth (2 cm*5 cm) is immersed mixed liquor
In, after being stirred to react 5 h, sample is taken out, wash with distilled water, is placed in 60 DEG C of thermostatic drying chambers and dries.
(2), 2 mmol nitric hydrate nickel are dissolved in 30 ml methanol, gained sample in step (1) is immersed nickel nitrate
In solution, 10 min are stirred to react, sample is taken out, is cleaned respectively with distilled water and ethyl alcohol.
(3), it takes 6 mmol thioacetamides to be dissolved in 30 ml ethanol solutions, thioacetyl amine aqueous solution is placed in 50 ml water
In hot kettle, and sample obtained by step (2) is immersed in solution, 3 h are reacted at 120 DEG C, take out sample after reaction, are used respectively
Distilled water and ethyl alcohol are cleaned, and are placed in 70 DEG C of thermostatic drying chambers and are dried.
Fig. 2 is vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material scanning electron microscope (SEM) photograph of hydrolysis regulation, the sulphur of preparation
Change nickel cobalt/carbon cloth electrode material and shows the hollow porous structure to interpenetrate.
Fig. 3 is vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material projection electron microscope of hydrolysis regulation, nickel sulfide
Nano-pore structure is dispersed on cobalt/carbon cloth material, pore size is in 2-5 nm.
Fig. 4 is the X-ray diffraction pattern for the porous super capacitance electrode material of vulcanization nickel cobalt removed from carbon cloth, is divided on carbon cloth
The vulcanization nickel cobalt of cloth shows crystalline structure, in 2 θ=16.3o、26.7 o、31.5 o、38.2 o、50.3 o、55 oDiffraction maximum point
Not and CoNi2S4(111), (220), (311), (400), (511) it is consistent with (440) crystal face.
Fig. 5 is vulcanization nickel cobalt/porous super capacitance electrode material of carbon cloth of hydrolysis regulation in different scanning rates (20 mV
s-1-100mV s-1) under cyclic voltammetry curve figure, under different sweep speeds, the vulcanization nickel cobalt/carbon cloth for hydrolyzing regulation is more
Porous materials all show apparent redox characteristic, while having good chemical invertibity.
Fig. 6 is the vulcanization nickel cobalt/porous super capacitance electrode material of carbon cloth filling under different current densities of hydrolysis regulation
Discharge curve, in 1 A g-1Current density under, hydrolyze regulation vulcanization nickel cobalt/carbon cloth porous material discharge time be 520
S, specific capacitance are 942 F g-1。
Fig. 7 is vulcanization nickel cobalt/porous super capacitance electrode material of carbon cloth of hydrolysis regulation in 10 A g-1Shi Xunhuan 20000
The cycle characteristics curve of circle hydrolyzes vulcanization nickel cobalt/carbon cloth porous material of regulation in higher 10 A g of current density-1, pass through
After 20000 circle charge and discharge cycles, specific capacitance remains to be maintained at 85% or so, has excellent cyclical stability, considerably beyond height
The cycle life of the porous electrode material of temperature processing MOFs.
Embodiment 2
(1), carbon cloth is impregnated to 10 h in nitric acid, is cleaned with distilled water.By 1 mmol nitric hydrate cobalt and 8 mmol
2-methylimidazole is dissolved in respectively in 30 ml methanol, and after being stirred, processed carbon cloth (2 cm*5 cm) is immersed mixed liquor
In, after being stirred to react 5 h, sample is taken out, wash with distilled water, is placed in 60 DEG C of thermostatic drying chambers and dries.
(2), 2 mmol nitric hydrate nickel are dissolved in 30 ml methanol, gained sample in step (1) is immersed nickel nitrate
In solution, 20 min are stirred to react, sample is taken out, is cleaned respectively with distilled water and ethyl alcohol.
(3), it takes 6 mmol thioacetamides to be dissolved in 30 ml ethanol solutions, thioacetyl amine aqueous solution is placed in 50 ml hydro-thermals
In kettle, and sample obtained by step (2) is immersed in solution, 3 h are reacted at 120 DEG C, take out sample after reaction, respectively with steaming
Distilled water and ethyl alcohol are cleaned, and are placed in 70 DEG C of thermostatic drying chambers and are dried.
Embodiment 3
(1), carbon cloth is impregnated to 10 h in nitric acid, is cleaned with distilled water.By 0.5 mmol nitric hydrate cobalt and 5 mmol
2-methylimidazole be dissolved in 30 ml methanol respectively, after being stirred, by processed carbon cloth (2 cm*5 cm) immerse mix
In liquid, after being stirred to react 5 h, sample is taken out, wash with distilled water, is placed in 60 DEG C of thermostatic drying chambers and dries.
(2), 1 mmol nitric hydrate nickel is dissolved in 30 ml methanol, gained sample in step (1) is immersed nickel nitrate
In solution, 20 min are stirred to react, sample is taken out, is cleaned respectively with distilled water and ethyl alcohol.
(3), it takes 3 mmol thioacetamides to be dissolved in 30 ml ethanol solutions, thioacetyl amine aqueous solution is placed in 50 ml water
In hot kettle, and sample obtained by step (2) is immersed in solution, 3 h are reacted at 120 DEG C, take out sample after reaction, are used respectively
Distilled water and ethyl alcohol are cleaned, and are placed in 70 DEG C of thermostatic drying chambers and are dried.
Embodiment 4
(1), carbon cloth is impregnated to 10 h in nitric acid, is cleaned with distilled water.By 1 mmol nitric hydrate cobalt and 8 mmol
2-methylimidazole is dissolved in respectively in 30 ml n,N-Dimethylformamide, after being stirred, by processed carbon cloth (2 cm*5
Cm it) immerses in mixed liquor, after being stirred to react 5 h, sample is taken out, wash with distilled water, is placed in 60 DEG C of thermostatic drying chambers
Drying.
(2), 2 mmol nitric hydrate nickel are dissolved in 30 ml ethyl alcohol, gained sample in step (1) is immersed nickel nitrate
In solution, 20 min are stirred to react, sample is taken out, is cleaned respectively with distilled water and ethyl alcohol.
(3), it takes 6 mmol thioacetamides to be dissolved in 30 ml ethanol solutions, thioacetyl amine aqueous solution is placed in 50 ml water
In hot kettle, and sample obtained by step (2) is immersed in solution, 3 h are reacted at 120 DEG C, take out sample after reaction, are used respectively
Distilled water and ethyl alcohol are cleaned, and are placed in 70 DEG C of thermostatic drying chambers and are dried.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
The present invention will not be limited to the embodiments shown herein, and is to fit to special with principles disclosed herein and novelty
The consistent widest scope of point.
Claims (8)
1. hydrolyzing vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation method of regulation, it is characterised in that: specific step
Suddenly are as follows:
Step 1: the preparation of cobalt-based metal organic frame/carbon cloth composite material: preparing the reaction of cobalt-based metal-organic framework material
Carbon cloth is immersed in cobalt-based metal-organic framework material reaction solution and reacts 2-20h, after reaction taken out sample, then use by liquid
Distilled water and ethyl alcohol cleaning, it is dry, obtain cobalt-based metal organic frame/carbon cloth composite material；
Step 2: the preparation of porous nickel cobalt layered double hydroxide/carbon cloth composite material: the cobalt-based gold that step 1 is obtained
Belong to organic frame/carbon cloth composite material and immerse in nickel nitrate solution and react, be stirred to react 3-40min, after reaction with water and
Ethyl alcohol cleaning, obtains porous nickel cobalt layered double hydroxide/carbon cloth composite material；
Step 3: porous vulcanization nickel cobalt/carbon cloth composite material preparation: thioacetamide is as sulphur source, much with step 2 institute
Hole nickel cobalt layered double hydroxide/carbon cloth composite material is collectively disposed in reaction kettle and carries out hydro-thermal reaction, by sample after reaction
Product take out, and are washed and dried with distilled water and ethyl alcohol, obtain the porous vulcanization nickel cobalt/carbon cloth composite with hollow structure
Material.
2. vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation side of hydrolysis regulation according to claim 1
Method, it is characterised in that: in step 1, the carbon cloth is before immersing cobalt-based metal-organic framework material reaction solution also in nitric acid
9-24h is impregnated, is cleaned after immersion with distilled water.
3. vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation side of hydrolysis regulation according to claim 1
Method, it is characterised in that: in step 1, cobalt-based metal-organic framework material reaction solution includes the hydration nitre as metal ion center
The 2-methylimidazole of sour cobalt and the predecessor as organic ligand, nitric hydrate cobalt and 2-methylimidazole are also distinguished molten in a solvent
It solves and mixes.
4. vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation side of hydrolysis regulation according to claim 3
Method, it is characterised in that: the solvent of nitric hydrate cobalt and 2-methylimidazole is in water, methanol, ethyl alcohol and n,N-Dimethylformamide
One kind.
5. vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation side of hydrolysis regulation according to claim 3
Method, it is characterised in that: the molar ratio of nitric hydrate cobalt and 2-methylimidazole is 1:5-1:12.
6. vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation side of hydrolysis regulation according to claim 3
Method, it is characterised in that: the molar ratio of nitric hydrate nickel and nitric hydrate cobalt is 1:2-2:1.
7. vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation of hydrolysis regulation according to claim 1 or 6
Method, it is characterised in that: in step 2, the solvent of nickel nitrate solution is one of methanol and ethyl alcohol.
8. vulcanization nickel cobalt/carbon cloth porous super capacitance electrode material preparation side of hydrolysis regulation according to claim 1
Method, it is characterised in that: in step 3, thioacetamide and porous nickel cobalt layered double hydroxide/carbon cloth composite material
Reaction temperature is 90-200 DEG C, reaction time 1-10h, the total moles of thioacetamide and nitric hydrate cobalt and nitric hydrate nickel
Several ratios is 2:1-6:1.
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