CN113035589A - Zinc cobaltate nanosheet/carbon fiber cloth composite material and preparation method and application thereof - Google Patents
Zinc cobaltate nanosheet/carbon fiber cloth composite material and preparation method and application thereof Download PDFInfo
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- 239000004744 fabric Substances 0.000 title claims abstract description 210
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 202
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 202
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 239000011701 zinc Substances 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 70
- 239000002135 nanosheet Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000004070 electrodeposition Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 230000002457 bidirectional effect Effects 0.000 claims abstract description 17
- 238000005516 engineering process Methods 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000002848 electrochemical method Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 29
- 238000002791 soaking Methods 0.000 claims description 28
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002659 electrodeposit Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000000151 deposition Methods 0.000 description 14
- 230000008021 deposition Effects 0.000 description 14
- 238000010586 diagram Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000003814 drug Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 zinc cobalt hydrate hydroxide Chemical compound 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
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- 229940079593 drug Drugs 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005234 chemical deposition Methods 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
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
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- 238000011112 process operation Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
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- 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
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- 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
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- 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
- H01G11/40—Fibres
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Abstract
The invention discloses a zinc cobaltate nanosheet/carbon fiber cloth composite material and a preparation method and application thereof. The preparation method comprises the following steps: carrying out hydrophilization treatment on the surface of the carbon fiber cloth by adopting an electrochemical method to obtain hydrophilized carbon fiber cloth; the hydrophilized carbon fiber cloth is used as a counter electrode, and is matched with a working electrode, a reference electrode and a first electrolyte to form a first electrochemical system, and a bidirectional pulse electrodeposition technology is adopted, so that the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material is prepared; and carrying out high-temperature annealing treatment on the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material to obtain a zinc cobaltate nanosheet/carbon fiber cloth composite material. The electrochemical deposition system adopted by the invention is an organic system, and the prepared zinc cobaltate nanosheet/carbon fiber cloth composite material is more ultrathin compared with other methods and systems; meanwhile, the invention adopts the bidirectional pulse electrodeposition technology, and the deposited zinc cobaltate is more uniform.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a zinc cobaltate nanosheet/carbon fiber cloth composite material as well as a preparation method and application thereof.
Background
Energy plays an important role in the overall development of socioeconomic in China and is a basic condition for stable operation in various fields of modern society, but with the increase of energy demand, the ecological environment is continuously deteriorated due to the massive use of traditional fossil energy, and the research of new pollution-free materials and technologies is a necessary direction for the development of energy storage. The zinc cobaltate is used as a ternary transition metal oxide, has high environmental friendliness, higher theoretical capacity and low use cost, and has wide application in the fields of supercapacitors, catalysis and the like. The nanocrystallization of zinc cobaltate is a common method for exerting the advantages of materials thereof, such as nanospheres, nanocubes and the like, wherein the nanosheets have large specific surface areas and are more favorable for electron transfer and ion transmission.
At present, most of the existing zinc cobaltate nanosheets are prepared by a hydrothermal method, wherein a zinc source, a cobalt source and a ligand aqueous solution are placed in a high-temperature hydrothermal kettle to react for a long time to obtain a zinc cobalt salt or a zinc cobalt hydrated hydroxide, and then the zinc cobalt salt or the zinc cobalt hydrated hydroxide is calcined at a high temperature to obtain the zinc cobaltate. The electrochemical deposition method is that under the action of an electric field, zinc ions, cobalt ions and ligand ions migrate to the surface of a conductive matrix and nucleate and grow. However, the hydrothermal method requires high temperature and long time for growing the nanosheets, has high requirements on equipment, has more influencing factors of the preparation process, is unclear in growth mechanism, and has certain uncontrollable morphology and performance of zinc cobaltate products; the electrochemical deposition method selects a water solution system with better conductivity.
Disclosure of Invention
The invention mainly aims to provide a zinc cobaltate nanosheet/carbon fiber cloth composite material and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a zinc cobaltate nanosheet/carbon fiber cloth composite material, which comprises the following steps:
carrying out hydrophilization treatment on the surface of carbon fiber cloth (also called carbon cloth) by adopting an electrochemical method to obtain the hydrophilized carbon fiber cloth;
the hydrophilized carbon fiber cloth is used as a counter electrode, and is matched with a working electrode, a reference electrode and a first electrolyte to form a first electrochemical system, and a bidirectional pulse electrodeposition technology is adopted to electrodeposit zinc-cobalt hydrated hydroxide on the surface of the hydrophilized carbon fiber cloth, so that the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material is prepared, wherein the first electrolyte is a methanol salt solution;
and carrying out high-temperature annealing treatment on the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material to obtain a zinc cobaltate nanosheet/carbon fiber cloth composite material.
The embodiment of the invention also provides a zinc cobaltate nanosheet/carbon fiber cloth composite material prepared by the method, which comprises carbon fiber cloth and zinc cobaltate nanosheets loaded on the carbon fiber cloth, wherein the thickness of the zinc cobaltate nanosheets is 3-4 nm, and the loading amount is 0.5-2.0 mg/cm2。
The embodiment of the invention also provides application of the zinc cobaltate nanosheet/carbon fiber cloth composite material in the field of supercapacitors or catalysis.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with a plasma method, the electrochemical method is adopted for hydrophilic treatment of the carbon fiber cloth, the operation is simple and convenient, the device is simple to build, the operation is simple, the environment is protected, and the surface of the carbon fiber cloth has hydrophilicity;
(2) compared with the traditional hydrothermal method, the electrochemical deposition technology (bidirectional pulse electrodeposition technology) adopted by the invention has the advantages of simple and convenient operation, good controllability and repeatability, more uniform deposited zinc cobaltate and more possibility of realizing mass production;
(3) the electrochemical deposition system adopted by the invention is based on an organic solvent, the blank existing between the electrochemical deposition technology and the selection of the solvent system is filled, the surrounding effect of the solvent methanol molecules on the deposited ions avoids the disorder and disorder of deposition, the selected bidirectional pulse electrodeposition technology inhibits concentration polarization, and the clustering of the nano material in a large range can be avoided.
(4) According to the invention, the organic solvent is used for controlling ion deposition, the prepared zinc cobaltate nanosheet is thinner, and a technical possibility is provided for regulating and controlling the thickness of the nanosheet and improving the performance of the zinc cobaltate nanomaterial.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart illustrating the preparation of a zinc cobaltate/carbon fiber cloth composite material according to an exemplary embodiment of the present invention;
FIG. 2 is a schematic view of a hydrophilization apparatus for a carbon fiber cloth in example 1 of the present invention;
FIG. 3 is a schematic view of an electrodeposition apparatus in embodiment 1 of the present invention;
FIG. 4 is a schematic view of a high-temperature annealing apparatus in example 1 of the present invention;
5 a-5 b are graphs of the morphology of zinc cobaltate nanosheets in the zinc cobaltate nanosheet/carbon fiber cloth composite prepared in example 1 of the present invention;
FIGS. 6a to 6b are contact angle test charts of carbon fiber cloth before and after hydrophilization treatment in example 1 of the present invention;
fig. 7 a-7 b are performance graphs of zinc cobaltate nanosheet/carbon cloth composite prepared in example 1 of the present invention as a single electrode;
FIG. 8 is a graph showing the morphology of a hydrothermally grown zinc cobaltate nanosheet on a carbon fiber cloth in comparative example 1 of the present invention;
FIG. 9 is a graph showing the morphology of zinc cobaltate nanosheets grown on carbon fiber cloth when deionized water is used as an electrodeposition solution in comparative example 2 according to the present invention;
FIG. 10 is a graph showing the morphology of zinc cobaltate nanosheets grown on the carbon fiber cloth without hydrophilization treatment in comparative example 3 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made extensive studies and practices to provide a technical scheme of the present invention, which mainly uses carbon fiber cloth as a conductive substrate, hydrophilizes the carbon fiber cloth by using an electrochemical method, grows zinc-cobalt hydrated hydroxide in an organic system using methanol as a solvent by electrochemical deposition, and prepares an ultrathin zinc cobaltate nanosheet after high-temperature annealing treatment.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiment of the present invention provides a preparation method of a zinc cobaltate nanosheet/carbon fiber cloth composite material, which includes:
carrying out hydrophilization treatment on the surface of the carbon fiber cloth by adopting an electrochemical method to obtain hydrophilized carbon fiber cloth;
the hydrophilized carbon fiber cloth is used as a counter electrode, and is matched with a working electrode, a reference electrode and a first electrolyte to form a first electrochemical system, and a bidirectional pulse electrodeposition technology is adopted to electrodeposit zinc-cobalt hydrated hydroxide on the surface of the hydrophilized carbon fiber cloth, so that the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material is prepared, wherein the first electrolyte is a methanol salt solution;
and carrying out high-temperature annealing treatment on the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material to obtain a zinc cobaltate nanosheet/carbon fiber cloth composite material.
In some more specific embodiments, the preparation method comprises:
dissolving zinc salt, cobalt salt and organic amine in methanol to form the first electrolyte;
and taking the hydrophilized carbon fiber cloth as a counter electrode, matching the hydrophilized carbon fiber cloth with a working electrode, a reference electrode and the first electrolyte to form the first electrochemical system, and performing electrodeposition on the surface of the hydrophilized carbon fiber cloth to form zinc-cobalt hydrated hydroxide at the temperature of 60-70 ℃ by adopting a bidirectional pulse electrodeposition technology, wherein the bidirectional pulse electrodeposition technology adopts the following process conditions: the forward current density is 1.0-5.0 mA/cm2The negative current density is 0.1-0.5 mA/cm2The positive direction time is 1.0-5.0 s, the negative direction time is 0.1-0.5 s, and the electrodeposition time is 15-60 min.
Further, the zinc salt includes any one or a combination of two or more of zinc nitrate hexahydrate, zinc chloride, and zinc sulfate, and is not limited thereto.
Further, the cobalt salt includes any one or a combination of two or more of cobalt nitrate hexahydrate, cobalt chloride, and cobalt sulfate, and is not limited thereto.
Further, the organic amine includes any one or a combination of two or more of hexamethylenetetramine, ethylenediamine, and triethanolamine, and is not limited thereto.
Further, the concentration of the zinc salt in the first electrolyte is 0.01 mol/L-1.0 mol/L.
Further, the concentration of the cobalt salt in the first electrolyte is 0.02 mol/L-2.0 mol/L.
Further, the concentration of organic amine in the first electrolyte is 0.08-8.0 mol/L.
Further, the type of the carbon fiber cloth is W0S1009 of carbon technologies, ltd, and is not limited thereto.
Furthermore, the contact angle between the carbon fiber cloth and water before hydrophilic treatment is 100-150 degrees.
Furthermore, the surface of the hydrophilized carbon fiber cloth can be directly infiltrated with water.
Further, the working electrode includes a platinum electrode, and is not limited thereto.
Further, the reference electrode includes a saturated calomel electrode, and is not limited thereto.
Further, the preparation method further comprises the following steps: and after the electrodeposition is finished, cleaning and drying the obtained zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material.
Further, the cleaning process includes: and soaking the obtained carbon fiber cloth in water for 1-2 hours.
Furthermore, the drying treatment time is 6-12 h, and the temperature is 60-100 ℃.
In some more specific embodiments, the preparation method comprises:
and (3) placing the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material in a heating device, heating to 300-400 ℃ at the speed of 1-5 ℃/min in the air atmosphere, carrying out heat preservation treatment for 2-5 h, and naturally cooling to room temperature to obtain the zinc cobaltate nanosheet/carbon fiber cloth composite material.
In some more specific embodiments, the preparation method comprises:
the method comprises the following steps of taking carbon fiber cloth as a working electrode, forming a second electrochemical system with a platinum electrode as a counter electrode and a reference electrode and a second electrolyte, and performing hydrophilization treatment on the carbon fiber cloth by adopting cyclic voltammetry, wherein the cyclic voltammetry adopts the following process conditions: the voltage sweep rate of CV is 0.1-0.5V/s, the voltage interval is 1-2V, and the number of cycles is 20-100.
Further, the second electrolyte includes a sulfuric acid solution, and is not limited thereto.
Further, the concentration of the sulfuric acid solution is 0.5-5.0 mol/L.
Further, the preparation method further comprises the following steps: after the hydrophilization treatment is completed, the obtained hydrophilized carbon fiber cloth is washed and dried.
Further, the cleaning process includes: soaking the hydrophilized carbon fiber cloth in methanol
Furthermore, the soaking time is 1-2 h, and the soaking times are 2-3.
Furthermore, the drying treatment time is 6-12 h, and the temperature is 60-100 ℃.
In some more specific embodiments, the method for preparing the zinc cobaltate nanosheet/carbon fiber cloth composite material specifically comprises the following steps (a preparation flow chart of the zinc cobaltate/carbon fiber cloth composite material is shown in fig. 1):
(1) hydrophilization treatment of carbon fiber cloth (schematic diagram of hydrophilization apparatus of carbon fiber cloth is shown in fig. 2): preparation of 1mol/L H2SO4Putting carbon fiber cloth and a platinum sheet into a sulfuric acid solution together, taking the carbon fiber cloth as a working electrode, taking the platinum sheet as a counter electrode and a reference electrode, setting the CV voltage sweep speed to be 0.1V/s, circularly scanning for 20 circles within the interval range of 1-2V, taking out the carbon fiber cloth, soaking the carbon fiber cloth in deionized water for 1-2 hours, and drying the carbon fiber cloth in a 60 ℃ drying oven for later use;
(2) preparing electrolyte: weighing 1mmol of Zn (NO)3)2·6H2O, 2mmol of Co (NO)3)2·6H2Dissolving O and 8mmol of hexamethylenetetramine into 70mL of methanol, and mechanically stirring until the medicine is completely dissolved;
(3) preparation of zinc cobalt hydrate hydroxide/carbon fiber cloth composite material (schematic diagram of electrodeposition device is shown in fig. 3): and taking the dried carbon fiber cloth as a counter electrode, a platinum sheet as a working electrode, a saturated calomel electrode as a reference electrode, raising the temperature of the solution to 60-70 ℃, and performing electrochemical deposition by adopting bidirectional pulse current. The deposition parameters were: i forward direction is 3mA/cm2I minus direction is 0.3mA/cm2The positive direction of T is 1s, the negative direction of T is 0.1s, and the electrodeposition time is 15-60 min. And after the deposition is finished, taking out the carbon fiber cloth loaded with the zinc-cobalt hydrated hydroxide on the surface, soaking the carbon fiber cloth in a methanol solution for two hours, then repeatedly soaking the carbon fiber cloth in clean methanol for 2 hours, taking out the carbon fiber cloth, and drying the carbon fiber cloth in a 60 ℃ drying oven.
(4) Preparation of zinc cobaltate/carbon fiber cloth composite material (the schematic diagram of the high-temperature annealing device is shown in fig. 4): and (3) placing the dried zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material in a tubular furnace, heating the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material from room temperature to 350 ℃ in the air at the heating rate of 2 ℃/min, preserving the heat for 2 hours, and then naturally cooling the temperature to the room temperature to obtain the zinc cobaltate nanosheet/carbon fiber cloth composite material.
The embodiment of the invention also provides a zinc cobaltate nanosheet/carbon fiber cloth composite material prepared by the method, which comprises carbon fiber cloth and zinc cobaltate nanosheets loaded on the carbon fiber cloth, wherein the thickness of the zinc cobaltate nanosheets is 3-4 nm, and the loading amount is 0.5-2.0 mg/cm2。
In another aspect of the embodiment of the invention, the application of the zinc cobaltate nanosheet/carbon fiber cloth composite material in a supercapacitor is also provided.
The invention aims to control the quantity of ions transferred to the surface of a conductive substrate when zinc-cobalt hydrated hydroxide grows by using an organic solvent in electrochemical deposition, and prepare an ultrathin zinc cobaltate nanosheet simply, effectively and controllably by high-temperature calcination, and break the barrier of the current zinc cobaltate preparation electrochemical deposition and organic solvent system.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Hydrophilization treatment of carbon fiber cloth (schematic diagram of hydrophilization apparatus of carbon fiber cloth is shown in fig. 2): preparation of 1mol/L H2SO4Putting carbon fiber cloth and a platinum sheet into a sulfuric acid solution together, taking the carbon fiber cloth as a working electrode, taking the platinum sheet as a counter electrode and a reference electrode, setting the CV voltage sweep speed to be 0.1V/s, circularly scanning for 20 circles within the interval range of 1-2V, taking out the carbon fiber cloth, soaking the carbon fiber cloth in deionized water for 2 hours, and drying the carbon fiber cloth in a 60 ℃ drying oven for later use;
(2) electrolysisPreparing a liquid: weighing 1mmol of Zn (NO)3)2·6H2O, 2mmol of Co (NO)3)2·6H2Dissolving O and 8mmol of hexamethylenetetramine into 70mL of methanol, and mechanically stirring until the medicine is completely dissolved;
(3) preparation of zinc cobalt hydrate hydroxide/carbon fiber cloth composite material (schematic diagram of electrodeposition device is shown in fig. 3): taking the dried carbon fiber cloth as a counter electrode, a platinum sheet as a working electrode, a saturated calomel electrode as a reference electrode, raising the temperature of the solution to 65 ℃, and performing electrochemical deposition by adopting bidirectional pulse current. The deposition parameters were: i forward direction is 3mA/cm2I minus direction is 0.3mA/cm2The positive direction of T is 1s, the negative direction of T is 0.1s, and the electrodeposition time is 30 min. After deposition is finished, taking out the carbon fiber cloth loaded with the zinc-cobalt hydrated hydroxide on the surface, soaking the carbon fiber cloth in a methanol solution for two hours, then repeatedly soaking the carbon fiber cloth in clean methanol for 2 hours, taking out the carbon fiber cloth, and drying the carbon fiber cloth in a 60 ℃ drying oven;
(4) preparation of zinc cobaltate/carbon fiber cloth composite material (the schematic diagram of the high-temperature annealing device is shown in fig. 4): and (3) placing the dried zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material in a tubular furnace, heating the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material from room temperature to 350 ℃ in the air at the heating rate of 2 ℃/min, preserving the heat for 2 hours, and then naturally cooling the temperature to the room temperature to obtain the zinc cobaltate nanosheet/carbon fiber cloth composite material.
And (3) performance characterization:
5 a-5 b are graphs of the morphology of zinc cobaltate nanosheets in the zinc cobaltate nanosheet/carbon fiber cloth composite prepared in example 1 of the present invention; fig. 6a to 6b are contact angle test charts of the carbon fiber cloth before and after the hydrophilization treatment in example 1 of the present invention, the carbon fiber cloth before the hydrophilization treatment is in a hydrophobic state, the contact angle is 137.5 °, and water drops directly infiltrate the surface of the carbon fiber cloth after the hydrophilization treatment.
The zinc cobaltate nanosheet/carbon cloth composite material prepared in the embodiment 1 is used as a single electrode, and has good rate performance, as shown in fig. 7 a-7 b, the capacitance at 10A/g is 72% of the initial capacitance, and the capacity retention rate at 30A/g is still 44%. In an asymmetric supercapacitor device, after 10000 charge-discharge cycles, the capacity of the device is basically kept unchanged.
Example 2
(1) Hydrophilization treatment of carbon fiber cloth (schematic diagram of hydrophilization apparatus of carbon fiber cloth is shown in fig. 2): preparing 0.5mol/L H2SO4Putting carbon fiber cloth and a platinum sheet into a sulfuric acid solution together, taking the carbon fiber cloth as a working electrode, taking the platinum sheet as a counter electrode and a reference electrode, setting the CV voltage sweep speed to be 0.3V/s, circularly scanning for 50 circles within the interval range of 1-2V, taking out the carbon fiber cloth, soaking the carbon fiber cloth in deionized water for 1.5 hours, and drying the carbon fiber cloth in an oven at the temperature of 80 ℃ for later use;
(2) preparing electrolyte: weighing 1mmol of ZnSO42mmol of Co (NO)3)2·6H2Dissolving O and 8mmol triethanolamine in 70mL methanol, and mechanically stirring until the medicine is completely dissolved;
(3) preparation of zinc cobalt hydrate hydroxide/carbon fiber cloth composite material (schematic diagram of electrodeposition device is shown in fig. 3): taking the dried carbon fiber cloth as a counter electrode, a platinum sheet as a working electrode and a saturated calomel electrode as a reference electrode, raising the temperature of the solution to 70 ℃, and performing electrochemical deposition by adopting bidirectional pulse current. The deposition parameters were: i forward direction is 5.0mA/cm2I minus direction is 0.5mA/cm2The positive direction of T is 3.0s, the negative direction of T is 0.3s, and the electrodeposition time is 15 min. After deposition is finished, taking out the carbon fiber cloth loaded with the zinc-cobalt hydrated hydroxide on the surface, soaking the carbon fiber cloth in a methanol solution for 1.5h, then repeatedly soaking the carbon fiber cloth in clean methanol for 1.5h, taking out the carbon fiber cloth, and drying the carbon fiber cloth in an oven at 80 ℃;
(4) preparation of zinc cobaltate/carbon fiber cloth composite material (the schematic diagram of the high-temperature annealing device is shown in fig. 4): and (3) placing the dried zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material in a tubular furnace, heating the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material from room temperature to 400 ℃ in air at a heating rate of 5 ℃/min, preserving the heat for 3 hours, and naturally cooling the temperature to room temperature to obtain the zinc cobaltate loaded carbon cloth.
Example 3
(1) Hydrophilization treatment of carbon fiber cloth (schematic diagram of hydrophilization apparatus of carbon fiber cloth is shown in fig. 2): preparation of 1mol/L H2SO4Solution, putting carbon fiber cloth and platinum sheet into sulfuric acid solution together, and making carbon fiberThe method comprises the following steps of taking a piece of fiber cloth as a working electrode, taking a platinum sheet as a counter electrode and a reference electrode, setting the CV voltage sweep speed to be 0.5V/s, circularly scanning for 100 circles within the interval range of 1-2V, taking out the carbon fiber cloth, soaking the carbon fiber cloth in deionized water for 1 hour, and drying the carbon fiber cloth in a drying oven at 100 ℃ for later use;
(2) preparing electrolyte: weighing 1mmol of Zn (NO)3)2·6H2O, 2mmol of Co5O4Dissolving 8mmol of ethylenediamine into 70mL of methanol, and mechanically stirring until the medicine is completely dissolved;
(3) preparation of zinc cobalt hydrate hydroxide/carbon fiber cloth composite material (schematic diagram of electrodeposition device is shown in fig. 3): taking the dried carbon fiber cloth as a counter electrode, a platinum sheet as a working electrode and a saturated calomel electrode as a reference electrode, raising the temperature of the solution to 60 ℃, and performing electrochemical deposition by adopting bidirectional pulse current. The deposition parameters were: 1.0mA/cm in the I forward direction2I minus is 0.1mA/cm2The positive direction of T is 5.0s, the negative direction of T is 0.5s, and the electrodeposition time is 60 min. After deposition is finished, taking out the carbon fiber cloth loaded with the zinc-cobalt hydrated hydroxide on the surface, soaking the carbon fiber cloth in a methanol solution for 1h, then repeatedly soaking the carbon fiber cloth in clean methanol for 1h, taking out the carbon fiber cloth, and drying the carbon fiber cloth in a 100 ℃ oven;
(4) preparation of zinc cobaltate/carbon fiber cloth composite material (the schematic diagram of the high-temperature annealing device is shown in fig. 4): and (3) placing the dried zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material in a tubular furnace, heating the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material from room temperature to 300 ℃ in air at the heating rate of 1 ℃/min, preserving the heat for 5 hours, and naturally cooling the temperature to room temperature to obtain the zinc cobaltate loaded carbon cloth.
Comparative example 1
(1) Hydrophilization treatment of carbon fiber cloth: preparation of 1mol/L H2SO4Putting carbon fiber cloth and a platinum sheet into a sulfuric acid solution together, taking the carbon fiber cloth as a working electrode, taking the platinum sheet as a counter electrode and a reference electrode, setting the CV voltage sweep speed to be 0.1V/s, circularly scanning for 20 circles within the interval range of 1-2V, taking out the carbon fiber cloth, soaking the carbon fiber cloth in deionized water for 2 hours, and drying the carbon fiber cloth in a 60 ℃ drying oven for later use;
(2) preparing solvent heat precursor liquid: weighing 1mmol of Zn (NO)3)2·6H2O, 2mmol of Co (NO)3)2·6H2Dissolving O and 8mmol of hexamethylenetetramine into 70mL of methanol, and mechanically stirring until the medicine is completely dissolved;
(3) preparing a zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material: arranging the dried carbon fiber in a high-pressure hydrothermal kettle, reacting for 12h at 180 ℃, taking out the carbon fiber cloth with the zinc-cobalt hydrated hydroxide loaded on the surface, soaking in deionized water for 3h, repeatedly cleaning for 3 times, taking out, and drying in a 60 ℃ drying oven;
(4) preparing a zinc cobaltate/carbon fiber cloth composite material: and (3) placing the dried zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material in a tubular furnace, heating the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material from room temperature to 350 ℃ in the air at the heating rate of 2 ℃/min, preserving the heat for 2 hours, and naturally cooling the temperature to the room temperature to obtain the zinc cobaltate loaded carbon cloth.
Fig. 8 is a graph of zinc cobaltate nanosheets prepared in this comparative example under hydrothermal conditions, with low loading and very uneven nanosheet growth on the fibers.
Comparative example 2
(1) Hydrophilization treatment of carbon fiber cloth: preparation of 1mol/L H2SO4Putting carbon fiber cloth and a platinum sheet into a sulfuric acid solution together, taking the carbon fiber cloth as a working electrode, taking the platinum sheet as a counter electrode and a reference electrode, setting the CV voltage sweep speed to be 0.1V/s, circularly scanning for 20 circles within the interval range of 1-2V, taking out the carbon fiber cloth, soaking the carbon fiber cloth in deionized water for 2 hours, and drying the carbon fiber cloth in a 60 ℃ drying oven for later use;
(2) preparing solvent heat precursor liquid: weighing 1mmol of Zn (NO)3)2·6H2O, 2mmol of Co (NO)3)2·6H2Dissolving O and 8mmol of hexamethylenetetramine into 70mL of deionized water, and mechanically stirring until the medicines are completely dissolved;
(3) preparation of zinc cobalt hydrate hydroxide/carbon fiber cloth composite material (schematic diagram of electrodeposition device is shown in fig. 3): taking the dried carbon fiber cloth as a counter electrode, a platinum sheet as a working electrode, a saturated calomel electrode as a reference electrode, heating the solution to 65 ℃, and performing electricity by adopting bidirectional pulse currentAnd (4) chemical deposition. The deposition parameters were: i forward direction is 3mA/cm2I minus direction is 0.3mA/cm2The positive direction of T is 1s, the negative direction of T is 0.1s, and the electrodeposition time is 30 min. After deposition is finished, taking out the carbon fiber cloth loaded with the zinc-cobalt hydrated hydroxide on the surface, soaking the carbon fiber cloth in a methanol solution for 2 hours, then repeatedly soaking the carbon fiber cloth in clean methanol for 2 hours, taking out the carbon fiber cloth, and drying the carbon fiber cloth in a 60 ℃ drying oven;
(4) preparing a zinc cobaltate/carbon fiber cloth composite material: and (3) placing the dried zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material in a tubular furnace, heating the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material from room temperature to 350 ℃ in the air at the heating rate of 2 ℃/min, preserving the heat for 2 hours, and naturally cooling the temperature to the room temperature to obtain the zinc cobaltate loaded carbon cloth.
Fig. 9 shows zinc cobaltate nanosheets prepared in this comparative example in the presence of water as the electrolyte, the nanosheets having serious clusters.
Comparative example 3
(1) Treatment of carbon fiber cloth: soaking the carbon fiber cloth in deionized water for 2 hours, and drying in a 60 ℃ drying oven for later use;
(2) preparing solvent heat precursor liquid: weighing 1mmol of Zn (NO)3)2·6H2O, 2mmol of Co (NO)3)2·6H2Dissolving O and 8mmol of hexamethylenetetramine into 70mL of deionized water, and mechanically stirring until the medicines are completely dissolved;
(3) preparing a zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material: taking the dried carbon fiber cloth as a counter electrode, a platinum sheet as a working electrode, a saturated calomel electrode as a reference electrode, raising the temperature of the solution to 65 ℃, and performing electrochemical deposition by adopting bidirectional pulse current. The deposition parameters were: i forward direction is 3mA/cm2I minus direction is 0.3mA/cm2The positive direction of T is 1s, the negative direction of T is 0.1s, and the electrodeposition time is 30 min. After deposition is finished, taking out the carbon fiber cloth loaded with the zinc-cobalt hydrated hydroxide on the surface, soaking the carbon fiber cloth in a methanol solution for two hours, then repeatedly soaking the carbon fiber cloth in clean methanol for 2 hours, taking out the carbon fiber cloth, and drying the carbon fiber cloth in a 60 ℃ drying oven;
(4) preparation of zinc cobaltate/carbon fiber cloth composite material (the schematic diagram of the high-temperature annealing device is shown in fig. 4): and (3) placing the dried zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material in a tubular furnace, heating the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material from room temperature to 350 ℃ in the air at the heating rate of 2 ℃/min, preserving the heat for 2 hours, and naturally cooling the temperature to the room temperature to obtain the zinc cobaltate loaded carbon cloth.
FIG. 10 shows zinc cobaltate nanosheets prepared upon electrodeposition of a non-hydrophilized carbon cloth of this comparative example for 30min, with nucleation on the carbon fiber but the nanosheets being small at the same time.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A preparation method of a zinc cobaltate nanosheet/carbon fiber cloth composite material is characterized by comprising the following steps of:
carrying out hydrophilization treatment on the surface of the carbon fiber cloth by adopting an electrochemical method to obtain hydrophilized carbon fiber cloth;
the hydrophilized carbon fiber cloth is used as a counter electrode and matched with a working electrode, a reference electrode and a first electrolyte to form a first electrochemical system, and a bidirectional pulse electrodeposition technology is adopted to electrodeposit zinc-cobalt hydrated hydroxide on the surface of the hydrophilized carbon fiber cloth so as to prepare the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material, wherein the first electrolyte is a methanol salt solution;
and carrying out high-temperature annealing treatment on the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material to obtain a zinc cobaltate nanosheet/carbon fiber cloth composite material.
2. The production method according to claim 1, characterized by comprising:
dissolving zinc salt, cobalt salt and organic amine in methanol to form the first electrolyte;
and taking the hydrophilized carbon fiber cloth as a counter electrode, matching the hydrophilized carbon fiber cloth with a working electrode, a reference electrode and the first electrolyte to form the first electrochemical system, and performing electrodeposition on the surface of the hydrophilized carbon fiber cloth to form zinc-cobalt hydrated hydroxide at the temperature of 60-70 ℃ by adopting a bidirectional pulse electrodeposition technology, wherein the bidirectional pulse electrodeposition technology adoptsThe process conditions of (A) include: the forward current density is 1.0-5.0 mA/cm2The negative current density is 0.1-0.5 mA/cm2The positive direction time is 1.0-5.0 s, the negative direction time is 0.1-0.5 s, and the electrodeposition time is 15-60 min.
3. The method of claim 2, wherein: the zinc salt comprises any one or the combination of more than two of zinc nitrate hexahydrate, zinc chloride and zinc sulfate;
and/or the cobalt salt comprises any one or the combination of more than two of cobalt nitrate hexahydrate, cobalt chloride and cobalt sulfate;
and/or the organic amine comprises any one or the combination of more than two of hexamethylenetetramine, ethylenediamine and triethanolamine;
and/or the concentration of the zinc salt in the first electrolyte is 0.01-1.0 mol/L;
and/or the concentration of the cobalt salt in the first electrolyte is 0.02-2.0 mol/L;
and/or the concentration of organic amine in the first electrolyte is 0.08-8.0 mol/L.
4. The method of claim 2, wherein: the contact angle between the carbon fiber cloth and water before hydrophilic treatment is 100-150 degrees;
and/or the surface of the hydrophilized carbon fiber cloth can be directly infiltrated with water;
and/or, the working electrode comprises a platinum electrode;
and/or, the reference electrode comprises a saturated calomel electrode;
and/or, the preparation method further comprises the following steps: after the electrodeposition is finished, cleaning and drying the obtained zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material; preferably, the cleaning process includes: soaking the obtained zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material in water for 1-2 h; preferably, the drying treatment time is 6-12 h, and the temperature is 60-100 ℃.
5. The production method according to claim 1, characterized by comprising:
and (3) placing the zinc-cobalt hydrated hydroxide/carbon fiber cloth composite material in a heating device, heating to 300-400 ℃ at the speed of 1-5 ℃/min in the air atmosphere, and carrying out heat preservation treatment for 2-5 h to obtain the zinc cobaltate nanosheet/carbon fiber cloth composite material.
6. The production method according to claim 1, characterized by comprising:
the method comprises the following steps of taking carbon fiber cloth as a working electrode, forming a second electrochemical system with a platinum electrode as a counter electrode and a reference electrode and a second electrolyte, and performing hydrophilization treatment on the carbon fiber cloth by adopting cyclic voltammetry, wherein the cyclic voltammetry adopts the following process conditions: the voltage sweep rate of CV is 0.1-0.5V/s, the voltage interval is 1-2V, and the number of cycles is 20-100.
7. The method of claim 6, wherein: the second electrolyte comprises a sulfuric acid solution; preferably, the concentration of the sulfuric acid solution is 0.5-5.0 mol/L.
8. The method of claim 6, further comprising: after the hydrophilic treatment is finished, cleaning and drying the obtained hydrophilic carbon fiber cloth;
preferably, the cleaning process includes: soaking the hydrophilized carbon fiber cloth in methanol; preferably, the soaking time is 1-2 h, and the soaking times are 2-3; preferably, the drying treatment time is 6-12 h, and the temperature is 60-100 ℃.
9. The zinc cobaltate nanosheet/carbon fiber cloth composite material prepared by the method of any one of claims 1 to 8, which comprises carbon fiber cloth and zinc cobaltate nanosheets loaded on the carbon fiber cloth, wherein the thickness of the zinc cobaltate nanosheets is 3-4 nm, and the loading amount of the zinc cobaltate nanosheets is 0.5-2.0 mg/cm2。
10. Use of a zinc cobaltate nanosheet/carbon fiber cloth composite of claim 9 in a supercapacitor.
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| CN114284076A (en) * | 2021-12-31 | 2022-04-05 | 合肥工业大学 | Method for rapidly preparing high-activity carbon fiber supercapacitor electrode based on Joule heat at high temperature |
| CN116365055A (en) * | 2022-12-26 | 2023-06-30 | 起源智能科技(嘉兴)有限公司 | Neutral silver-zinc secondary battery based on electrochemical in-situ growth electrode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114284076A (en) * | 2021-12-31 | 2022-04-05 | 合肥工业大学 | Method for rapidly preparing high-activity carbon fiber supercapacitor electrode based on Joule heat at high temperature |
| CN114284076B (en) * | 2021-12-31 | 2023-12-01 | 合肥工业大学 | Method for rapidly preparing high-activity carbon fiber supercapacitor electrode at high temperature based on Joule heat |
| CN116365055A (en) * | 2022-12-26 | 2023-06-30 | 起源智能科技(嘉兴)有限公司 | Neutral silver-zinc secondary battery based on electrochemical in-situ growth electrode and preparation method thereof |
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