CN110797207B - Preparation method and application of silkworm cocoon derived carbon/graphene/copper sulfide composite material - Google Patents
Preparation method and application of silkworm cocoon derived carbon/graphene/copper sulfide composite material Download PDFInfo
- Publication number
- CN110797207B CN110797207B CN201911070729.5A CN201911070729A CN110797207B CN 110797207 B CN110797207 B CN 110797207B CN 201911070729 A CN201911070729 A CN 201911070729A CN 110797207 B CN110797207 B CN 110797207B
- Authority
- CN
- China
- Prior art keywords
- graphene
- silkworm cocoon
- derived carbon
- silkworm
- composite material
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 104
- 241000255789 Bombyx mori Species 0.000 title claims abstract description 95
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 238000004729 solvothermal method Methods 0.000 claims abstract description 11
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 7
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000835 electrochemical detection Methods 0.000 description 5
- -1 graphene compound Chemical class 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- 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
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method and application of a silkworm cocoon derived carbon/graphene/copper sulfide composite material. The preparation method comprises the following steps: 1) pretreating the silkworm cocoons by using water and isopropanol; 2) loading graphene oxide on the pretreated silkworm cocoons; 3) calcining and carbonizing the silkworm cocoon loaded with the graphene oxide under the protection of inert gas; 4) adding the calcined silkworm cocoon derived carbon/graphene oxide compound into a glycol solution containing copper nitrate and a sulfur-containing compound, and preparing the silkworm cocoon derived carbon/graphene/copper sulfide composite material by utilizing solvothermal reaction. According to the invention, the silkworm cocoon derived carbon with the three-dimensional porous structure is used for effectively loading graphene and copper sulfide, so that the aggregation of the graphene and the copper sulfide is weakened, the obtained composite material can be cut into any shape and can be directly used as an electrode material of a super capacitor, the capacitance performance is good, the preparation process is simple, and the large-scale production is easy.
Description
Technical Field
The invention belongs to the field of new materials and functional materials, and particularly relates to a preparation method and application of a silkworm cocoon derived carbon/graphene/copper sulfide composite material.
Background
Graphite and diamond are well known to be the most common elemental carbon materials. The fullerene and the carbon nano tube discovered in the later period of the last century expand families of carbon materials, and the graphene discovered in the last century enriches people's understanding of the diversity of carbon elements. The graphene is single-layer graphite, is one of the thinnest materials at present, is easy to obtain raw materials, and has excellent electrical property and heat conduction property, large specific surface area and high mechanical strength. These unique microscopic nanostructures and properties make graphene useful as photovoltaic materials and energy storage materials, among others.
The super capacitor is an energy storage device with power density and energy density between those of a traditional capacitor and a battery, has the advantages of high energy density and power density, long cycle life, rapid charge and discharge and the like, and is a novel energy storage device developed in recent years. Due to the excellent performance of graphene, graphene is an ideal electrode material of a supercapacitor, and the graphene and other materials are compounded to prepare the electrode material of the supercapacitor, so that more and more attention is paid to the preparation of the electrode material of the supercapacitor. However, the graphene surface has no hydrophilic functional group, so that the graphene has poor dispersibility in water, is easy to aggregate and is not beneficial to preparing a composite material. Therefore, it is very critical to develop a novel binary or ternary composite material containing graphene to realize uniform distribution of graphene and other components in the composite material, and to directly use the graphene and other components as an electrode material of a supercapacitor.
Disclosure of Invention
The invention aims to provide a preparation method and application of a silkworm cocoon derived carbon/graphene/copper sulfide composite material. According to the invention, the silkworm cocoon derived carbon with the three-dimensional porous structure is used for effectively loading graphene and copper sulfide, and the aggregation of the graphene and the copper sulfide is weakened, so that the obtained composite material can be cut into any shape and can be directly used as an electrode material of a super capacitor, the capacitance performance is good, the preparation process is simple, and the large-scale production is easy.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of a silkworm cocoon derived carbon/graphene/copper sulfide composite material, which comprises the following steps:
1) sequentially soaking the silkworm cocoons in water and isopropanol to carry out cleaning pretreatment;
2) soaking the pretreated silkworm cocoons in a graphene oxide aqueous solution, and loading graphene oxide on the silkworm cocoons;
3) calcining and carbonizing the silkworm cocoon loaded with the graphene oxide under inert gas;
4) and adding the calcined silkworm cocoon derived carbon/graphene oxide compound into a glycol solution containing copper nitrate and a sulfur-containing compound, and carrying out solvothermal reaction to obtain the silkworm cocoon derived carbon/graphene/copper sulfide composite material.
According to the scheme, in the step 2), the silkworm cocoon accounts for 50-100 parts, the graphene oxide accounts for 1-4 parts, and the water accounts for 400-1000 parts.
According to the scheme, the inert gas in the step 3) is nitrogen or argon
According to the scheme, the sulfur-containing compound in the step 4) is thiourea or thioacetamide.
According to the scheme, in the step 4), the calcined silkworm cocoon derived carbon/graphene oxide compound is 2-5 parts by weight, copper nitrate is 0.5-1 part by weight, a sulfur-containing compound is 0.5-1 part by weight, and ethylene glycol is 50-100 parts by weight.
According to the scheme, the soaking time in water and isopropanol in the step 1) is 1-3h, and the soaking temperature is 20-30 ℃.
According to the scheme, the soaking time in the step 2) is 1-3 h.
According to the scheme, the calcination temperature in the step 3) is 600-800 ℃, and the calcination time is 1-3 h.
According to the scheme, the solvothermal reaction temperature in the step 4) is 140-.
The application of the silkworm cocoon derived carbon/graphene/copper sulfide composite material prepared by the method in the super capacitor is characterized in that the composite material is directly used as a super capacitor electrode material, and no binder or conductive agent is required to be added additionally.
Compared with the prior art, the invention has the following outstanding effects:
1. the silkworm cocoon derived carbon/graphene/copper sulfide composite material keeps the self-supporting performance of the silkworm cocoon, can be cut into any shape, does not need to be added with other binders and conductive agents, can be directly used as an electrode material of a super capacitor, and has good capacitance performance.
2. In the silkworm cocoon derived carbon/graphene/copper sulfide composite material, graphene and copper sulfide are uniformly distributed on silkworm cocoon derived carbon, the graphene increases the conductive capacity of the silkworm cocoon derived carbon, the three-dimensional structure of the silkworm cocoon derived carbon is favorable for the transmission of electrolyte, the double-layer capacitance of the silkworm cocoon derived carbon and the graphene is combined with the pseudo-capacitance of the copper sulfide, and the capacitance performance of the composite material is improved.
3. In the preparation process, the silkworm cocoons with the three-dimensional porous structures can effectively adsorb the hydrophilic graphene oxide in the graphene oxide aqueous solution, and the graphene oxide is promoted to be uniformly distributed on the silkworm cocoons; in the hydrothermal reaction process, the graphene oxide is reduced into graphene, and simultaneously copper sulfide is generated and uniformly distributed on the silkworm cocoon derived carbon loaded with the graphene, so that the aggregation of the graphene and the copper sulfide is reduced.
4. In the process of solvothermal reaction, graphene and copper sulfide can be generated simultaneously, so that the step of independently reducing graphene is reduced, and the preparation process is simplified.
5. The preparation process has simple operation steps, does not need complex equipment, has cheap and easily obtained raw materials and is beneficial to popularization.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.
Example 1:
the preparation method of the silkworm cocoon derived carbon/graphene/copper sulfide composite material comprises the following specific steps:
1) sequentially and respectively soaking the silkworm cocoons in water and isopropanol for 1h at the soaking temperature of 20 ℃ for cleaning pretreatment;
2) soaking the pretreated silkworm cocoons in a graphene oxide aqueous solution for 1h, and loading graphene oxide on the silkworm cocoons, wherein the silkworm cocoons are 50 parts, the graphene oxide is 1 part, and the water is 900 parts;
3) calcining the silkworm cocoon loaded with the graphene oxide at 600 ℃ for 1h in an argon atmosphere;
4) adding the calcined silkworm cocoon derived carbon/graphene oxide compound into an ethylene glycol solution containing copper nitrate and thiourea, and carrying out solvothermal reaction to obtain a silkworm cocoon derived carbon/graphene/copper sulfide composite material, wherein the calcined silkworm cocoon derived carbon/graphene compound comprises 2 parts, 0.5 part of copper nitrate, 0.5 part of a sulfur-containing compound and 60 parts of ethylene glycol; the reaction temperature is 140 ℃ and the reaction time is 7 h.
The electrochemical detection is carried out on the prepared silkworm cocoon derived carbon/graphene/copper sulfide composite material, and the capacity retention rate is 92.3% after the silkworm cocoon derived carbon/graphene/copper sulfide composite material is circularly charged and discharged for 1000 times at the current density of 1A/g.
Example 2:
the preparation method of the silkworm cocoon derived carbon/graphene/copper sulfide composite material comprises the following specific steps:
1) sequentially and respectively soaking the silkworm cocoons in water and isopropanol for 2h at the soaking temperature of 30 ℃ for cleaning pretreatment;
2) soaking the pretreated silkworm cocoons in a graphene oxide aqueous solution for 2 hours, and loading graphene oxide on the silkworm cocoons, wherein the silkworm cocoons are 60 parts, the graphene oxide is 2 parts, and the water is 800 parts;
3) calcining the silkworm cocoon loaded with the graphene oxide at 700 ℃ for 3h in an argon atmosphere;
4) adding the calcined silkworm cocoon derived carbon/graphene oxide compound into an ethylene glycol solution containing copper nitrate and thioacetamide, and performing solvothermal reaction to obtain a silkworm cocoon derived carbon/graphene/copper sulfide composite material, wherein the calcined silkworm cocoon derived carbon/graphene compound comprises 5 parts of copper nitrate, 1 part of a sulfur-containing compound and 100 parts of ethylene glycol; the reaction temperature is 160 ℃, and the reaction time is 10 h.
Electrochemical detection is carried out on the prepared silkworm cocoon derived carbon/graphene/copper sulfide composite material, and the capacitance retention rate is 93.1% after 1000 times of charge and discharge in a 1A/g current density cycle.
Example 3:
the preparation method of the silkworm cocoon derived carbon/graphene/copper sulfide composite material comprises the following specific steps:
1) sequentially and respectively soaking the silkworm cocoons in water and isopropanol for 3h at the soaking temperature of 25 ℃ for cleaning pretreatment;
2) soaking the pretreated silkworm cocoons in a graphene oxide aqueous solution for 2 hours, and loading graphene oxide on the silkworm cocoons, wherein the silkworm cocoons are 100 parts, the graphene oxide is 4 parts, and the water is 1000 parts;
3) calcining the silkworm cocoon loaded with the graphene oxide at 800 ℃ for 1h in a nitrogen atmosphere;
4) adding the calcined silkworm cocoon derived carbon/graphene oxide compound into an ethylene glycol solution containing copper nitrate and thiourea, and carrying out solvothermal reaction to obtain a silkworm cocoon derived carbon/graphene/copper sulfide composite material, wherein the calcined silkworm cocoon derived carbon/graphene compound accounts for 3 parts, the copper nitrate accounts for 0.6 part, the sulfur-containing compound accounts for 0.6 part, and the ethylene glycol accounts for 70 parts; the reaction temperature is 150 ℃, and the reaction time is 15 h.
The electrochemical detection is carried out on the prepared silkworm cocoon derived carbon/graphene/copper sulfide composite material, and the capacity retention rate is 92.6% after the silkworm cocoon derived carbon/graphene/copper sulfide composite material is circularly charged and discharged for 1000 times at the current density of 1A/g.
Example 4:
the preparation method of the silkworm cocoon derived carbon/graphene/copper sulfide composite material comprises the following specific steps:
1) sequentially and respectively soaking the silkworm cocoons in water and isopropanol for 1.5h at the soaking temperature of 30 ℃ for cleaning pretreatment;
2) soaking the pretreated silkworm cocoons in a graphene oxide aqueous solution for 1h, and loading graphene oxide on the silkworm cocoons, wherein the silkworm cocoons are 80 parts, the graphene oxide is 3 parts, and the water is 500 parts;
3) calcining the silkworm cocoon loaded with the graphene oxide at 700 ℃ for 2h in an argon atmosphere;
4) adding the calcined silkworm cocoon derived carbon/graphene oxide compound into an ethylene glycol solution containing copper nitrate and thioacetamide, and performing solvothermal reaction to obtain a silkworm cocoon derived carbon/graphene/copper sulfide composite material, wherein the calcined silkworm cocoon derived carbon/graphene compound comprises 4 parts, 0.8 part of copper nitrate, 0.8 part of a sulfur-containing compound and 90 parts of ethylene glycol; the reaction temperature is 140 ℃ and the reaction time is 12 h.
The electrochemical detection is carried out on the prepared silkworm cocoon derived carbon/graphene/copper sulfide composite material, and the capacity retention rate is 92.7% after the silkworm cocoon derived carbon/graphene/copper sulfide composite material is circularly charged and discharged for 1000 times at the current density of 1A/g.
Example 5:
the preparation method of the silkworm cocoon derived carbon/graphene/copper sulfide composite material comprises the following specific steps:
1) sequentially and respectively soaking the silkworm cocoons in water and isopropanol for 2h at the soaking temperature of 20 ℃, and performing cleaning pretreatment;
2) soaking the pretreated silkworm cocoons in a graphene oxide aqueous solution for 3 hours, and loading graphene oxide on the silkworm cocoons, wherein the silkworm cocoons are 100 parts, the graphene oxide is 3 parts, and the water is 1000 parts;
3) calcining the silkworm cocoon loaded with the graphene oxide at 800 ℃ for 1h in an argon atmosphere;
4) adding the calcined silkworm cocoon derived carbon/graphene oxide compound into an ethylene glycol solution containing copper nitrate and thiourea, and carrying out solvothermal reaction to obtain a silkworm cocoon derived carbon/graphene/copper sulfide composite material, wherein the calcined silkworm cocoon derived carbon/graphene compound accounts for 3 parts, the copper nitrate accounts for 0.7 part, the sulfur-containing compound accounts for 0.7 part, and the ethylene glycol accounts for 70 parts; the reaction temperature is 150 ℃, and the reaction time is 8 h.
Electrochemical detection is carried out on the prepared silkworm cocoon derived carbon/graphene/copper sulfide composite material, and the capacitance retention rate is 93.2% after 1000 times of charge and discharge cycles at the current density of 1A/g.
The invention can be realized by all the listed raw materials, and the invention can be realized by the upper and lower limit values and interval values of all the raw materials; the examples are not to be construed as limiting the scope of the invention. The upper and lower limit values and interval values of the process parameters can realize the invention, and the embodiments are not listed.
Claims (8)
1. A preparation method of a silkworm cocoon derived carbon/graphene/copper sulfide composite material is characterized by comprising the following steps:
1) sequentially soaking the silkworm cocoons in water and isopropanol to carry out cleaning pretreatment;
2) soaking the pretreated silkworm cocoons in a graphene oxide aqueous solution for 1-3h, and loading graphene oxide on the silkworm cocoons;
3) calcining and carbonizing the silkworm cocoon loaded with the graphene oxide under inert gas, wherein the calcining temperature is 600-800 ℃, and the calcining time is 1-3 h;
4) and adding the calcined silkworm cocoon derived carbon/graphene oxide compound into a glycol solution containing copper nitrate and a sulfur-containing compound, and carrying out solvothermal reaction to obtain the silkworm cocoon derived carbon/graphene/copper sulfide composite material.
2. The preparation method according to claim 1, wherein the silkworm cocoon in step 2) is 50-100 parts, the graphene oxide is 1-4 parts, and the water is 400-1000 parts.
3. The method according to claim 1, wherein the inert gas in step 3) is nitrogen or argon.
4. The method according to claim 1, wherein the sulfur-containing compound in step 4) is thiourea or thioacetamide.
5. The preparation method of claim 1, wherein in the step 4), the calcined silkworm cocoon-derived carbon/graphene oxide composite comprises 2-5 parts by weight of copper nitrate, 0.5-1 part by weight of a sulfur-containing compound and 50-100 parts by weight of ethylene glycol.
6. The preparation method according to claim 1, wherein the soaking time in water and isopropanol in the step 1) is 1-3h, and the soaking temperature is 20-30 ℃.
7. The method as claimed in claim 1, wherein the solvothermal reaction temperature in step 4) is 140 ℃ and the reaction time is 6-16 h.
8. Use of a silkworm cocoon-derived carbon/graphene/copper sulfide composite material prepared by the method according to any one of claims 1 to 7 in a supercapacitor, wherein the composite material is directly used as a supercapacitor electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911070729.5A CN110797207B (en) | 2019-11-05 | 2019-11-05 | Preparation method and application of silkworm cocoon derived carbon/graphene/copper sulfide composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911070729.5A CN110797207B (en) | 2019-11-05 | 2019-11-05 | Preparation method and application of silkworm cocoon derived carbon/graphene/copper sulfide composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110797207A CN110797207A (en) | 2020-02-14 |
| CN110797207B true CN110797207B (en) | 2022-03-15 |
Family
ID=69442813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911070729.5A Active CN110797207B (en) | 2019-11-05 | 2019-11-05 | Preparation method and application of silkworm cocoon derived carbon/graphene/copper sulfide composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110797207B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101427731B1 (en) * | 2013-06-04 | 2014-09-22 | 인하대학교 산학협력단 | Manufacturing method of carbon aerogels |
| CN108538630B (en) * | 2017-10-08 | 2020-01-07 | 北京化工大学 | Preparation method of biomass charcoal/graphene flexible composite membrane |
| CN108597906B (en) * | 2018-06-13 | 2020-02-14 | 常熟理工学院 | Preparation method of fiber/graphene/copper sulfide flexible electrode material |
| CN108760851B (en) * | 2018-07-30 | 2020-08-04 | 江南大学 | Application of CuS/GO/MWCNTs composite nanoparticle modified electrode in electrochemical detection of hydrogen peroxide |
-
2019
- 2019-11-05 CN CN201911070729.5A patent/CN110797207B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110797207A (en) | 2020-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yuan et al. | Si-based materials derived from biomass: synthesis and applications in electrochemical energy storage | |
| CN106935855B (en) | A kind of porous carbon nanotubular materials and its preparation method and application | |
| CN105789575B (en) | silicon dioxide-carbon composite negative electrode material, modified silicon dioxide-carbon composite negative electrode material, and preparation methods and applications thereof | |
| CN108987729B (en) | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery | |
| CN108899530B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN105514434A (en) | Preparation method of whisker-shaped carbon nano tube film | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN102324501A (en) | Silicon-based cathode composite material for lithium ion battery and preparation method thereof | |
| CN101355150B (en) | Method for preparing graphitic carbon nanometer tube combination electrode material for lithium ion battery | |
| CN112086642B (en) | Graphitized carbon-coated high-specific-surface-area porous carbon sphere and preparation method and application thereof | |
| CN110611092A (en) | Preparation method of nano silicon dioxide/porous carbon lithium ion battery cathode material | |
| CN112736235A (en) | Biomass/carbon nanotube induced Fe3O4Nano composite material and application thereof as negative electrode material of lithium ion battery | |
| CN109301246B (en) | Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode | |
| CN111974430A (en) | Preparation method of monoatomic copper catalyst and application of monoatomic copper catalyst in positive electrode of lithium-sulfur battery | |
| Li et al. | Preparation of biochar from different biomasses and their application in the Li-S battery | |
| CN110808177B (en) | Preparation method and application of silkworm cocoon derived carbon/carbon nanotube/copper sulfide composite material | |
| Yu et al. | Advancements and Prospects of Graphite Anode for Potassium‐Ion Batteries | |
| CN102887504A (en) | Method for preparing carbon material for lithium ion battery cathode | |
| CN110790253B (en) | Preparation method and application of silkworm cocoon derived carbon/MXene/manganese dioxide composite material | |
| CN112331845A (en) | Preparation method of cobaltosic oxide nanowire array negative electrode material | |
| CN111653774A (en) | Method for preparing biomass carbon lithium ion battery cathode material | |
| CN110797207B (en) | Preparation method and application of silkworm cocoon derived carbon/graphene/copper sulfide composite material | |
| CN108155022B (en) | Preparation method of lithium ion capacitor using microcrystalline graphite material | |
| CN116724411A (en) | Method for preparing hard carbon anode material by using fiber biomass, product and application thereof | |
| CN110642239B (en) | Preparation method and application of eggshell membrane derived carbon/graphene/copper sulfide composite material |
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 |