CN113593925B - Preparation method of copper sulfide/carbon composite material used as electrode material - Google Patents
Preparation method of copper sulfide/carbon composite material used as electrode material Download PDFInfo
- Publication number
- CN113593925B CN113593925B CN202110986811.3A CN202110986811A CN113593925B CN 113593925 B CN113593925 B CN 113593925B CN 202110986811 A CN202110986811 A CN 202110986811A CN 113593925 B CN113593925 B CN 113593925B
- Authority
- CN
- China
- Prior art keywords
- apf
- drying
- composite material
- solution
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 239000007772 electrode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 37
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229940018563 3-aminophenol Drugs 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 239000008098 formaldehyde solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229910021389 graphene Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000005580 one pot reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 4
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 4
- HRVYXNXPWHUJHF-UHFFFAOYSA-N 3-aminophenol;formaldehyde Chemical compound O=C.NC1=CC=CC(O)=C1 HRVYXNXPWHUJHF-UHFFFAOYSA-N 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- -1 transition metal chalcogenide Chemical class 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000081 effect on glucose Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
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
- H01G11/30—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
- H01G11/22—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
- H01G11/84—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
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for using as an electrodeA preparation method of copper sulfide/carbon composite material comprises the steps of (a) polymerizing m-aminophenol and formaldehyde, stirring, filtering, washing and drying to obtain APF; (b) Dispersing APF into aqueous solution containing copper ions, stirring, filtering, washing and drying to obtain APF/Cu 2+ A complex; (c) The APF/Cu obtained in the step (b) 2+ Roasting the compound in a tubular furnace to obtain a CuO/C compound; (d) And (C) dispersing the CuO/C composite obtained in the step (C) into a sulfur-containing solution, carrying out hydrothermal reaction in a reaction kettle, and then filtering, washing and drying to obtain the CuS/C composite material. The method has simple process and low cost, and the prepared composite material is nano-scale, has higher conductivity and can be used as an electrode material of a super capacitor or an electrode material of a lithium ion battery.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to a preparation method of a copper sulfide/carbon composite material used as an electrode material.
Background
The rapid consumption of fossil fuels and environmental crisis has created a great interest in developing clean and renewable energy storage devices. In the competition for energy in this development, supercapacitors, batteries and fuel cells are the most important competitors in recent times. The super capacitor mainly comprises a Faraday quasi-capacitance super capacitor double-point layer supercapacitors and hybrid supercapacitors. The double-electric-layer super capacitor realizes energy storage through reversible absorption and desorption of charges on the surface of the material, and the electrode material of the double-electric-layer super capacitor mainly comprises a carbon material with a high specific surface area, including activated carbon, graphene, carbon nanotubes, carbon fibers, carbon aerogel and the like.
Copper sulfide is a typical example of a transition metal chalcogenide, and has wide application in various fields such as electrochemical energy storage devices, super-ionic materials, photocatalysts, enzyme-free sensors and the like. Wherein, in the aspect of electrochemical performance, the theoretical capacity of copper sulfide (CuS) is up to 560mAhg -1 And has good conductivity.
At present, the research on the copper sulfide @ carbon compound mainly focuses on the aspects of lithium ion batteries, biological probes and photocatalysis. In the aspect of lithium ion batteries, due to the characteristics of high electronic conductivity, large specific surface area, strong toughness and the like of graphene, the cycle performance and the rate capability of the compounded copper sulfide/graphene electrode material are obviously enhanced. The Ren Yurong et al hydrothermal method prepares a CuS/RGO composite material with a double-layer sandwich structure, indicates that the graphene improves the conductivity and the electrode stability of the material, and the capacity is 710.7mAh g after 100 cycles at 0.2 DEG -1 The special structure of the material greatly reduces Li + Diffusion distance, and Li formed 2 S can be oxidized again. CuS/RGO is synthesized by Tao group one-pot method, the compound shows good lithium storage performance, and the excellent conductivity of RGO enables the material to have good electrochemical performance. As a photocatalyst, the introduction of graphene can improve the electron transfer rate, increase the specific surface area of the material and improve the light absorption rate, thereby improving the catalytic efficiency of the copper sulfide/graphene composite material. Shi Jingking et al prepared a CuS/rGO composite by a one-pot method with a specific surface area of 993.5m 2 g -1 The photocatalytic performance is remarkable. 5363 the copper sulfide modified carbon nanotube/paraffin/expanded graphite phase change energy storage composite material prepared by Xu Bin and the like has high thermal conductivity and light absorption, and is an excellent phase change energy storage composite material. The copper sulfide graphene nanocomposite prepared by the WangYongbin through a hydrothermal one-pot method is superior to copper sulfide in degrading methylene blue, and the catalytic activity is obviously improved.
And the sensitivity of the copper sulfide compounded with the graphene is obviously improved by using the copper sulfide as a probe, and the copper sulfide shows excellent stability. The CuS/RGO nano-composite is successfully prepared by Bai sting and Yang Yu Jun through a simple one-pot hydrothermal method and is used for detecting H 2 O 2 The sensitivity is greatly improved. Jiao Shoufeng synthesizes the reduced graphene nanocomposite modified by copper sulfide by a one-pot method, and the nanocomposite modified electrode is found to have a good electrocatalytic effect on glucose and is expected to be applied to enzyme-free sensing of glucose.
Disclosure of Invention
The invention aims to provide a preparation method of copper sulfide/carbon used as a composite electrode material, which has the advantages of simple process and low cost, and the prepared composite material is nano-scale, has higher conductivity and can be used as an electrode material of a super capacitor or an electrode material of a lithium ion battery.
The purpose of the invention is realized by the following technical scheme:
a preparation method of copper sulfide/carbon used as a composite electrode material comprises the following steps:
(a) Polymerizing M-aminophenol and formaldehyde, stirring, filtering, washing and drying to obtain M-aminophenol formaldehyde resin spheres (APF);
(b) Dispersing APF into aqueous solution containing copper ions, stirring, filtering, washing and drying to obtain APF/Cu 2+ A complex;
(c) The APF/Cu obtained in the step (b) 2+ Roasting the compound in a tubular furnace to obtain a CuO/C compound;
(d) And (C) dispersing the CuO/C composite obtained in the step (C) into a sulfur-containing solution, heating in a reaction kettle, and then filtering, washing and drying to obtain the CuS/C composite.
Preferably, in step (a), the preparation process of the spherical APF specifically comprises: adding m-aminophenol and formaldehyde into a mixed solution of ethanol, water and ammonia water in sequence, stirring for 10-18h, and then filtering, washing and drying to obtain spherical APF, wherein the formaldehyde is from a formaldehyde solution, the mass concentration of the formaldehyde in the formaldehyde solution is 35-40%, the ammonia water is from an ammonia water solution, the mass concentration of the ammonia water in the ammonia water solution is 25%, the addition ratio of the m-aminophenol to the formaldehyde solution to the ethanol to the water to the ammonia water solution is 0.6-0.8g, and the addition ratio of the m-aminophenol to the formaldehyde solution to the ethanol to the water to the ammonia water solution is 20-40mL.
Further preferably, the pH of the mixed solution of ethanol, water and ammonia water is 9-11, the addition ratio of the m-aminophenol, the formaldehyde solution, the ethanol, the water and the ammonia water solution is 0.71g, 1.034g, 9.6mL, 24mL, 1.956g, the stirring time is 24h, the drying temperature is 40 ℃, and the drying time is 12h.
Preferably, in the step (a), the stirring time is 10-18h, the drying temperature is 30-50 ℃, and the drying time is 10-14h. Further preferably, the stirring time is 12 hours, the drying temperature is 40 ℃, and the drying time is 12 hours, and the stirring is carried out in an oven.
Preferably, in step (b), the copper ions are selected from one or more of copper acetate or copper chloride. The molar concentration of the copper ions is 0.5-3mol/L, and the mass ratio of the APF to the copper ions is 1 (3.0-6.0).
Preferably, in the step (b), the second stirring time is 22-26h, the drying temperature is 40-120 ℃, and the drying time is 22-26h. Further preferably, the stirring time is 24 hours, the drying temperature is 50 ℃, and the drying time is 24 hours, and the stirring is carried out in an oven.
Preferably, in step (c), the roasting temperature is 600-800 ℃ and the roasting time is 2-4h.
Preferably, the calcination is carried out in step (c) by adopting temperature programming, wherein the temperature raising rate of the temperature programming is 1 ℃/min.
Preferably, in the step (d), the hydrothermal reaction temperature is 100-200 ℃, the hydrothermal time is 22-26h, the drying temperature is 40-120 ℃, and the drying time is 22-26h.
In the invention, m-aminophenol formaldehyde resin spheres are calcined in an inert gas atmosphere to serve as a carbon precursor, the high molecular resin spheres are calcined in a nitrogen atmosphere to become carbon, and a carbon sphere layer is formed, so that a spherical carbon/copper oxide composite material is obtained, wherein in the spherical composite material, the carbon is positioned at the inner layer, and the copper oxide is positioned at the outer layer. In the spherical composite, the metal oxide in the outer layer will cause the difference of ion diffusion speed and conductivity, and thus different electrochemical properties will be obtained. Metal sulfides have a higher specific capacitance than metal oxides. The invention obtains the CuS/C composite material with excellent electrochemical performance by a simple synthesis method.
Use of a copper sulphide/carbon composite material as a supercapacitor. The composite material contains both carbon and metal sulfide, so that the composite material has the conductivity of carbon and the high electrochemical performance of sulfide, such as the specific capacitance applicable to a super capacitor, and is an excellent electrode material. The carbon material with good conductivity and the metal sulfide are combined, and the formed metal sulfide and carbon composite material can be used as an electrode material and further applied to a super capacitor. In addition, composite materials with different morphologies may have different physical and chemical properties. Among them, the spherical composite material has a lower density, a higher specific surface area and a better electron-capturing ability.
The m-aminophenol formaldehyde resin spheres adopted by the invention contain amino with negative charges, and due to the bonding effect between the positive charges and the negative charges, metal ions with positive charges can be combined with the amino with negative charges and firmly adsorbed on the resin spheres, and the content of metal oxides can be quantitatively adjusted by controlling the number of the amino on the resin spheres, so that metal oxide sphere coating structures with different qualities and volumes can be prepared according to requirements.
The composite material prepared by the invention is nano-scale, has high conductivity, can be used in a super capacitor or a lithium ion battery, and has the advantages of simple process, convenient operation and wide raw material source.
Drawings
FIG. 1 is a scanning electron micrograph of the copper sulfide/carbon composite prepared in example 2.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A copper sulfide/carbon composite material used as an electrode material is prepared by the following steps:
(1) Preparing polymer spheres: adding 2.0 g of 25% ammonia water solution into 30-degree solution containing 24 g of deionized water and 10 ml of absolute ethyl alcohol, adding 0.71g of m-aminophenol, stirring to dissolve, then adding 1.0 g of 35% formaldehyde solution, continuing stirring for 24 hours, performing centrifugal separation to obtain a crude polymer ball (APF) product, and drying the crude polymer ball (APF) product in a 40-degree oven for 12 hours.
(2) Dispersing APF of macromolecule ball in (1) into 160 ml of 0.1-2mol/L cupric acetateIn solution. Stirred for 24 hours and then taken out. Placing the mixture into a 40-degree oven and standing for 24 hours. Obtaining APF/Cu 2+ And (c) a complex.
(3) Mixing APF/Cu 2+ And (3) programming the temperature of the composite to 600 ℃ under a nitrogen atmosphere, and keeping for 2 hours to obtain the CuO/C composite material.
Grinding the CuO/C composite material, and dispersing into 0.1-1mmol/L sodium sulfide nonahydrate solution. Taking out after hydrothermal for 24 hours at 100 ℃, centrifuging, washing and drying.
Example 2
A copper sulfide/carbon composite material used as a composite electrode material is prepared by adopting a preparation method comprising the following steps:
(1) Preparing polymer spheres: adding 2.0 g of 25% ammonia water solution into 30-degree solution containing 24 g of deionized water and 10 ml of absolute ethyl alcohol, adding 0.71g of m-aminophenol, stirring to dissolve, then adding 1.0 g of 35% formaldehyde solution, continuing stirring for 24 hours, performing centrifugal separation to obtain a crude polymer ball (APF) product, and drying the crude polymer ball (APF) product in a 40-degree oven for 12 hours.
(2) The macromolecular spheres APF in (1) are dispersed in 160 ml of 0.2mol/L copper chloride solution. Stirred for 24 hours and then taken out. Placing the mixture into a 40-degree oven and standing for 24 hours. Obtaining APF/Cu 2+ And (c) a complex.
(3) Mixing APF/Cu 2+ And (3) programming the temperature of the composite to 600 ℃ under a nitrogen atmosphere, and keeping for 2 hours to obtain the CuO/C composite material.
Grinding the CuO/C composite material, and dispersing into 0.1-1mmol/L sodium sulfide nonahydrate solution. Taking out after hydrothermal for 24 hours at 100 ℃, centrifuging, washing and drying.
The scanning electron micrograph of the composite material is shown in FIG. 1, and it can be seen that the size of the sample particles is about 500 nm.
Example 3
A copper sulfide/carbon composite material used as an electrode material is prepared by the following steps:
(1) Preparing polymer spheres: adding 2.0 g of 25% ammonia water solution into 30-degree solution containing 24 g of deionized water and 10 ml of absolute ethyl alcohol, adding 0.71g of m-aminophenol, stirring to dissolve, then adding 1.0 g of 35% formaldehyde solution, continuing stirring for 24 hours, performing centrifugal separation to obtain a crude polymer ball (APF) product, and drying the crude polymer ball (APF) product in a 40-degree oven for 12 hours.
(2) Dispersing the APF of the macromolecule ball in (1) into 160 ml of 0.1-2mol/L copper nitrate solution. Stirred for 24 hours and then taken out. Placing the mixture into a 40-degree oven and standing for 24 hours. Obtaining APF/Cu 2+ And (3) a compound.
(3) Mixing APF/Cu 2+ And (3) programming the temperature of the composite to 600 ℃ under a nitrogen atmosphere, and keeping for 2 hours to obtain the CuO/C composite material.
Grinding the CuO/C composite material, and dispersing into 0.1-1mmol/L sodium sulfide nonahydrate solution. Taking out the mixture after hydrothermal for 24 hours at 100 ℃, centrifuging, washing and drying.
Example 4
A copper sulfide/carbon composite material used as an electrode material is prepared by the following steps:
(1) Preparing polymer spheres: adding 2.0 g of 25% ammonia water solution into 30-degree solution containing 24 g of deionized water and 10 ml of absolute ethyl alcohol, adding 0.71g of m-aminophenol, stirring to dissolve, then adding 1.0 g of 35% formaldehyde solution, continuing stirring for 24 hours, performing centrifugal separation to obtain a crude polymer ball (APF) product, and drying the crude polymer ball (APF) product in a 40-degree oven for 12 hours.
(2) Dispersing APF of the macromolecule ball in (1) into 160 ml of 0.1-2mol/L copper sulfate solution. Stirred for 24 hours and then taken out. Placing the mixture into a 40-degree oven and standing for 24 hours. Obtaining APF/Cu 2+ And (c) a complex.
(3) APF/Cu 2+ And (3) programming the temperature of the composite to 600 ℃ under a nitrogen atmosphere, and keeping for 2 hours to obtain the CuO/C composite material.
Grinding the CuO/C composite material, and dispersing into 0.1-1mmol/L mixed solution of sodium sulfide nonahydrate and thiourea. Taking out the mixture after hydrothermal for 24 hours at 100 ℃, centrifuging, washing and drying.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A method for preparing a copper sulfide/carbon composite material used as an electrode material is characterized by comprising the following steps:
(a) Polymerizing m-aminophenol and formaldehyde, stirring, filtering, washing and drying to obtain APF;
(b) Dispersing APF into aqueous solution containing copper ions, stirring, filtering, washing and drying to obtain APF/Cu 2 + The compound is prepared from copper ions selected from copper acetate and/or copper chloride, the molar concentration of the copper ions is 0.5-3mol/L, and the mass ratio of APF to the copper ions is 1 (3.0-6.0);
(c) The APF/Cu obtained in the step (b) 2+ Roasting the compound in a tubular furnace to obtain a CuO/C compound;
(d) And (C) dispersing the CuO/C composite obtained in the step (C) into a sulfur-containing solution, carrying out hydrothermal reaction in a reaction kettle, and then filtering, washing and drying to obtain the CuS/C composite material.
2. The method for preparing the copper sulfide/carbon composite material used as the electrode material according to claim 1, wherein in the step (a), the APF is prepared by a specific process comprising: adding m-aminophenol and formaldehyde into a mixed solution of ethanol, water and ammonia water in sequence, stirring, and filtering, washing and drying in sequence to obtain the spherical APF.
3. The method for preparing a copper sulfide/carbon composite material for an electrode material according to claim 2, wherein the addition ratio of m-aminophenol, the formaldehyde solution, the ethanol, the water and the aqueous ammonia solution is 0.6 to 0.8g:0.2-2g:5-15mL:20-40mL:1.0-3.0g, the mass concentration of formaldehyde in the formaldehyde solution is 35-40%, and the mass concentration of ammonia water in the ammonia water solution is 25%.
4. The method of claim 1, wherein in the step (b), the stirring time is 22-26h, the drying temperature is 40-120 ℃, and the drying time is 22-26h.
5. The method of claim 1, wherein the stirring time is 24 hours, the drying temperature is 50 ℃, and the drying time is 24 hours in the step (b).
6. The method of claim 1, wherein the firing temperature is 600-800 ℃ and the firing time is 2-4h in the step (c).
7. The method of claim 1, wherein in the step (d), the sulfur-containing solution is one or both of sodium sulfide and thiourea, and the concentration is 0.1 to 1 mmol/L.
8. The method for preparing a copper sulfide/carbon composite material for an electrode material according to claim 1, wherein the hydrothermal reaction temperature in step (d) is 100-200 ℃ and the hydrothermal time is 22-26h.
9. The method of claim 1, wherein the drying temperature is 40-120 ℃ and the drying time is 22-26h in step (d).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110986811.3A CN113593925B (en) | 2021-08-26 | 2021-08-26 | Preparation method of copper sulfide/carbon composite material used as electrode material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110986811.3A CN113593925B (en) | 2021-08-26 | 2021-08-26 | Preparation method of copper sulfide/carbon composite material used as electrode material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113593925A CN113593925A (en) | 2021-11-02 |
CN113593925B true CN113593925B (en) | 2022-11-15 |
Family
ID=78239461
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110986811.3A Active CN113593925B (en) | 2021-08-26 | 2021-08-26 | Preparation method of copper sulfide/carbon composite material used as electrode material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113593925B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115770622A (en) * | 2022-11-30 | 2023-03-10 | 四川蓉仕环保科技有限公司 | CuS @ MIL-88A (Fe) composite material, preparation and application thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108745283A (en) * | 2018-06-04 | 2018-11-06 | 王子韩 | A kind of preparation method of carbon complex |
CN109659145A (en) * | 2018-12-17 | 2019-04-19 | 上海应用技术大学 | A method of preparing porous spherical manganese oxide/carbon complex |
CN110534354B (en) * | 2019-08-12 | 2021-10-12 | 江苏大学 | Preparation method and application of composite film electrode with carbon nano tubes inserted in CuS nano particles |
CN110713203B (en) * | 2019-11-20 | 2022-07-08 | 南京信息工程大学 | CuS/carbon black composite photothermal conversion material and preparation method thereof |
CN110993367B (en) * | 2019-12-18 | 2022-05-27 | 上海应用技术大学 | Spherical carbon @ manganese oxide @ carbon @ iron oxide composite material and preparation and application thereof |
-
2021
- 2021-08-26 CN CN202110986811.3A patent/CN113593925B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN113593925A (en) | 2021-11-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Kumar | NiCo 2 O 4 nano-/microstructures as high-performance biosensors: a review | |
CN108231426B (en) | Molybdenum disulfide/porous carbon nanosphere composite material and preparation method thereof | |
CN108927185B (en) | Oxygen reduction catalyst of heteroatom-doped carbon nanotube-loaded iron phosphide nanoparticles and preparation method thereof | |
CN109908938A (en) | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT | |
CN110467182A (en) | A kind of multi-stage porous carbon sill and its preparation method and application based on reaction template | |
CN107658474A (en) | A kind of nitrogen sulphur codope porous carbon microsphere and preparation method, purposes and oxygen reduction electrode | |
CN107649160A (en) | A kind of graphene-supported magnesium-yttrium-transition metal single dispersing catalyst atom and its preparation method and application | |
Atchudan et al. | One-pot synthesis of Fe3O4@ graphite sheets as electrocatalyst for water electrolysis | |
CN109243862B (en) | Dual-modified carbon hollow sphere compound and preparation method and application thereof | |
CN109546162A (en) | A kind of recyclable preparation method of microporous iron-nitrogen-doped carbon catalyst material | |
CN106876682A (en) | A kind of manganese oxide with loose structure/nickel micron ball and its preparation and application | |
CN110721713A (en) | Mo2C catalytic material and preparation method and application thereof | |
CN112044429B (en) | Carbon-doped tungsten oxide hollow microsphere rich in oxygen vacancy as well as preparation and application thereof | |
CN113593925B (en) | Preparation method of copper sulfide/carbon composite material used as electrode material | |
Medany et al. | Nickel–cobalt oxides decorated Chitosan electrocatalyst for ethylene glycol oxidation | |
CN114284515B (en) | Ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Preparation method and application of composite material | |
CN110690425B (en) | Boron-doped reduced carbon nanotube-loaded ferric oxide composite material and preparation method thereof | |
Lin et al. | Hydrothermal synthesis of nano-sized MnO2 supported on attapulgite electrode materials for supercapacitors | |
Hua et al. | Green synthesis and electrochemical properties of A3 (PO4) 2 (A= Mn, Zn, and Co) hydrates for supercapacitors with long-term cycling stability | |
CN107958792B (en) | A kind of carbon@CoO composite material of core-shell structure and its preparation method and application | |
CN113638007A (en) | Hydrogen electrolysis catalyst and preparation method thereof | |
CN111193039B (en) | Method for preparing oxygen reduction catalyst from biomass and product | |
CN113594476B (en) | Carbon nitride modified methanol electrocatalyst and preparation method and application thereof | |
CN114843118A (en) | Electrode composite material GO-C @ M (OH) with hierarchical pores 2 And preparation method and application thereof | |
CN110255631B (en) | Preparation method of rice husk-based porous metal oxide |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |