CN115028158A - Preparation method of kapok-based conductive carbon tube - Google Patents
Preparation method of kapok-based conductive carbon tube Download PDFInfo
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- CN115028158A CN115028158A CN202210729362.9A CN202210729362A CN115028158A CN 115028158 A CN115028158 A CN 115028158A CN 202210729362 A CN202210729362 A CN 202210729362A CN 115028158 A CN115028158 A CN 115028158A
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- kapok
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- based conductive
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- 244000146553 Ceiba pentandra Species 0.000 title claims abstract description 145
- 235000003301 Ceiba pentandra Nutrition 0.000 title claims abstract description 145
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 91
- 239000011347 resin Substances 0.000 claims abstract description 91
- 239000002131 composite material Substances 0.000 claims abstract description 65
- 241000332382 Ceiba Species 0.000 claims abstract description 57
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000005011 phenolic resin Substances 0.000 claims description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 13
- 229920001568 phenolic resin Polymers 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000003763 carbonization Methods 0.000 description 23
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- 241000405414 Rehmannia Species 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention provides a preparation method of a ceiba-based conductive carbon tube, which comprises the following steps: (1) preparing a resin solution; (2) drying the kapok in vacuum; (3) soaking the dried ceiba in a resin solution to obtain a composite ceiba; taking out the composite kapok, drying and curing, and then cooling to room temperature to obtain cured composite kapok; (4) placing the cured composite kapok in an inert atmosphere, carbonizing at a constant temperature for a period of time, and cooling to room temperature to obtain composite kapok carbon; (5) and (3) crushing and crushing the composite ceiba carbon to obtain the ceiba-based conductive carbon tube. The method can prepare the kapok-based conductive carbon tube with higher yield, and the conductivity of the kapok-based conductive carbon tube is obviously improved.
Description
Technical Field
The invention relates to the technical field of conductive carbon materials, in particular to a preparation method of a ceiba-based conductive carbon tube.
Background
Ion batteries are increasingly used in large-scale energy storage systems, and due to scarcity of lithium and other rare metal elements and potential safety hazards of lithium ion batteries, people are looking for organic materials as active substances in batteries to replace active substances such as original rare inorganic mineral resources.
The biomass is the most abundant substance in the carbon storage amount in nature, and has the advantages of wide source, low price, environmental friendliness and the like. The biomass resource is used as a precursor to prepare the activated carbon, on one hand, the preparation process of the biomass material is simpler, and the influence on the environment is smaller; on the other hand, the use of abundant biomass materials can reduce costs. Kapok fiber is a plant fiber with a natural tubular structure extracted from seed pods of kapok trees, and has the advantages of being rich in content, renewable and the like.
The molecular structure of the organic material is composed of elements such as carbon, hydrogen, oxygen, nitrogen and the like, and the organic material has unlimited resources in nature. Once prepared into prepared rhizome of rehmannia for the field of energy storage, the prepared rhizome of rehmannia has wide prospect.
The active carbon prepared by taking the kapok fiber as the precursor has a hollow tubular structure and can be used as a carrier of an organic active substance to prepare an electrode of an energy storage device. However, kapok carbon and organic active materials are poor conductors of electrons, so that electrodes prepared by using the kapok carbon and the organic active materials in the prior art often have the problem of low conductivity, and the rate performance of the battery is poor.
Disclosure of Invention
The invention aims to provide a preparation method of a ceiba-based conductive carbon tube, which improves the conductivity of the ceiba-based conductive carbon tube obtained by the preparation method, thereby improving the rate capability of a battery.
Another object of the present invention is to provide a ceiba-based conductive carbon tube prepared using the above preparation method.
In order to solve the technical problems, the invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of a kapok-based conductive carbon tube, which comprises the following steps:
(1) dissolving resin in a solvent to form a solution, and uniformly stirring; wherein the mass fraction of the resin in the solution is 1-50 wt%; the solvent comprises one or more of water, ethanol, acetone, formaldehyde and tetrahydrofuran;
(2) drying the kapok in vacuum;
(3) placing the dried ceiba in a vacuum container, dropwise adding a resin solution, and soaking the dried ceiba in the resin solution to obtain a composite ceiba; taking out the composite kapok, placing the composite kapok in an environment with the temperature of 100-200 ℃ for drying and curing for 5-20 hours, and then cooling to obtain cured composite kapok;
(4) placing the cured composite kapok in an inert atmosphere, heating at the speed of 1-10 ℃/min, carbonizing at the constant temperature of 800-1600 ℃ for 1-10 h, and cooling to obtain composite kapok carbon;
(5) and (3) crushing and crushing the composite ceiba carbon to obtain the ceiba-based conductive carbon tube.
The kapok is used as a carrier of resin, and the conductivity of the prepared kapok-based conductive carbon tube is improved by the preparation method.
Preferably, the mass fraction of the resin in the solution is 1 wt% to 20 wt%.
More preferably, the mass fraction of the resin in the solution is 2 wt% to 12 wt%.
Preferably, the composite kapok is taken out and placed in an environment with the temperature of 110-180 ℃ for drying and curing, and the drying and curing lasts for 5-15 hours.
Preferably, the composite kapok is taken out and placed in an environment with the temperature of 120-160 ℃ for drying and curing for 5-12 hours.
Preferably, the cured composite kapok is placed in an inert atmosphere, the temperature is increased at the speed of 2-8 ℃/min, and the carbonization is carried out at the constant temperature of 1000-1500 ℃ for 1-8 h.
Preferably, the cured composite kapok is placed in an inert atmosphere, the temperature is increased at the speed of 2-5 ℃/min, and the carbonization is carried out at the constant temperature of 1100-1400 ℃ for 2-6 h.
Preferably, the resin comprises thermosetting phenolic resin, so that the conductivity of the prepared kapok-based conductive carbon tube is higher.
More preferably, the thermosetting phenolic resin has a free phenol content of 5 wt% to 10 wt%.
Preferably, the solid content of the resin is 85 wt% -95 wt%, the viscosity is 500-3000 mPas at 25 ℃, and the water content is 1 wt% -5 wt%.
The method for testing the solid content of the resin comprises the following steps: weighing the resin to obtain an original mass, drying and curing the resin, putting the cured resin into a solid content detector, heating to remove water, free phenol and other volatile substances in the resin, weighing the remaining resin to obtain a cured mass, wherein the ratio of the cured mass to the original mass is the solid content of the resin.
The free phenol test method of the resin comprises the following steps: the free phenol content of the resin can be measured by adopting a gas chromatograph.
The method for testing the viscosity of the resin comprises the following steps: and (3) putting the viscometer into resin at the temperature of 25 ℃, and reading to obtain the viscosity of the resin.
The water content of the resin refers to the water content of the resin when the resin does not participate in the preparation of the kapok-based conductive carbon tube, and the testing method comprises the following steps: and testing by adopting a Karl Fischer method, and putting a certain amount of resin into a Karl Fischer reagent to obtain the water content of the resin.
More preferably, the viscosity of the resin is 2000 to 3000mPas at 25 ℃.
Preferably, the resin has a residual carbon content of 35 wt% to 55 wt%.
Wherein the residual carbon amount is the property of the resin, and the test method of the residual carbon amount is as follows: and respectively weighing the resin before and after carbonization, wherein the ratio of the mass of the resin after carbonization to the mass of the resin before carbonization is the residual carbon amount.
The resin with the parameters can be used for preparing the wood cotton-based conductive carbon tube with higher conductivity. Because the resin with the carbon residue is selected, the conductivity of the kapok-based conductive carbon tube is ensured, and the yield of the carbonized product can be improved.
Preferably, in the step (2), the air pressure of the vacuum drying treatment is-0.10 to-0.01 MPa, the temperature of the vacuum drying treatment is 10 to 200 ℃, and the time duration of the vacuum drying treatment is 1 to 24 hours.
Further preferably, the temperature of the vacuum drying treatment is 50-150 ℃, and the duration of the vacuum drying treatment is 5-22 h.
Further preferably, the temperature of the vacuum drying treatment is 50-120 ℃, and the time duration of the vacuum drying treatment is 6-20 hours.
Preferably, in the step (3), the pressure in the vacuum vessel is from-0.10 to-0.02 MPa.
Further preferably, in the step (3), the pressure in the vacuum vessel is in the range of-0.10 to-0.08 MPa.
Preferably, in the step (3), the mass ratio of the dried kapok to the resin solution is 1:10 to 100.
Further preferably, in the step (3), the mass ratio of the dried kapok to the resin solution is 1:20 to 60.
More preferably, in the step (3), the mass ratio of the dried kapok to the resin solution is 1: 20-45.
Preferably, in the step (3), the dried kapok is soaked in the resin solution for 1-36 hours.
Further preferably, in the step (3), the dried ceiba is soaked in the resin solution for 5-30 h.
Still further preferably, in the step (3), the dried ceiba is soaked in the resin solution for 10 to 15 hours.
Preferably, in the step (4), the inert gas in the inert atmosphere comprises one or a combination of nitrogen and argon.
The second aspect of the invention provides a kapok-based conductive carbon tube prepared by the preparation method of the kapok-based conductive carbon tube, wherein the conductivity of the kapok-based conductive carbon tube is 60-150 s/cm, and the specific surface area of the kapok-based conductive carbon tube is 1-500 m 2 The pipe diameter is 10-15 mu m.
Preferably, the kapok-based conductive carbon tube has the conductivity of 120-150 s/cm and the specific surface area of 1-10 m 2 /g。
Compared with the prior art, the invention has the following advantages:
the invention takes the ceiba as the carrier of the resin, and can prepare the ceiba-based conductive carbon tube with high conductivity and high yield by adopting the preparation method, the process is relatively simple, the environment is friendly, and the energy consumption is lower, so the preparation cost is lower, and the preparation method is suitable for large-scale industrial production.
Drawings
The beneficial effects of the invention described above can be embodied by the following figures:
FIG. 1 is a microscopic structure view of a composite kapok carbon prepared in example 1 of the present invention;
fig. 2 is a microscopic structure view of kawo carbon prepared in comparative example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
The natural tubular structure of the kapok fiber provides a large number of positions for storing adsorbates, and the kapok-based conductive carbon tube prepared by using the kapok as a resin carrier can be used as a raw material for preparing an electrode of an energy storage device. Because of the hollow tubular structure of the kapok fiber, the kapok is soaked in the resin, the material utilization rate of the kapok can be improved, and the defect of poor conductivity after the kapok with low density is singly carbonized is overcome.
On one hand, the ceiba-based conductive carbon tube prepared by the invention improves the preparation yield of the ceiba-based conductive carbon tube because the ceiba is used as the carrier of the resin to prepare the ceiba-based conductive carbon tube; on the other hand, because the resin has certain solid content, viscosity, carbon residue, free phenol and water content, the kapok-based conductive carbon tube prepared by the method provided by the invention has a unique physical structure, the utilization rate of active substances can be improved, the conductivity of the kapok-based conductive carbon tube can be further improved, and further the inside of an electrode prepared by taking the kapok-based conductive carbon tube as a raw material can be always in an electrolyte-rich state, and the movement distance of ions in the electrolyte is reduced, so that a battery with the electrode can have better rate multiplying performance.
Therefore, the kapok-based conductive carbon tube provided by the invention is used as a raw material for preparing an electrode, and a battery prepared by using the kapok-based conductive carbon tube has better rate capability.
The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples. The conditions of practice not stated in the examples are conventional in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other. In the examples of the present invention, the raw materials used are all commercially available.
Example 1:
(1) 10 grams of thermosetting phenolic resin was dissolved in 200ml of deionized water. Wherein the thermosetting phenolic resin has a solid content of 91 wt%, a viscosity of 2000mpas at 25 ℃, a residual carbon content of 45 wt%, a free phenol content of 6 wt% and a water content of 3 wt%.
(2) Drying kapok in vacuum at 110 deg.C for 12 hr in a first container with pressure of-0.08 MPa.
(3) Weighing 5g of dried ceiba, placing the ceiba in a closed second container, vacuumizing to-0.1 MPa, slowly dripping a resin solution, soaking the dried ceiba in the resin solution for 10 hours, and taking out to obtain the composite ceiba. And (3) drying and curing the composite kapok in an oven at 160 ℃ for 12 hours, and cooling to room temperature to obtain the cured composite kapok.
(4) And (3) placing the cured composite kapok in a high-temperature carbonization furnace, introducing nitrogen into the high-temperature carbonization furnace at the flow rate of 80ml/min, heating to 1300 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen atmosphere, keeping for 2 hours, and then continuously cooling to room temperature under the protection of nitrogen atmosphere to obtain a black carbon-like substance, namely the composite kapok carbon. Wherein, the yield of the composite kapok carbon is 30.66 percent.
(5) And (3) crushing the composite kapok carbon, and selecting the particle size to obtain the kapok-based conductive carbon tube. Wherein the specific surface area of the kapok-based conductive carbon tube is 15m 2 And the pipe diameter of the kapok-based conductive carbon pipe is 13 mu m, and the conductivity of the kapok-based conductive carbon pipe is 126 s/cm.
Example 2:
(1) 20 grams of thermosetting phenolic resin was dissolved in 200ml of acetone. Wherein the thermosetting phenolic resin has a solid content of 87 wt%, a viscosity of 2000mpas at 25 ℃, a residual carbon content of 50 wt%, a free phenol content of 8 wt% and a water content of 5 wt%.
(2) Drying kapok in vacuum at 120 deg.C for 10 hr in a first container with pressure of-0.08 MPa.
(3) Weighing 10 g of dried ceiba, placing the ceiba in a closed second container, vacuumizing to-0.1 MPa, slowly dripping a resin solution, soaking the dried ceiba in the resin solution for 10 hours, and taking out the ceiba to obtain the composite ceiba. And (3) drying and curing the composite kapok in an oven at 160 ℃ for 6 hours, and cooling to room temperature to obtain the cured composite kapok.
(4) And (3) placing the cured composite kapok in a high-temperature carbonization furnace, introducing nitrogen into the high-temperature carbonization furnace at the flow rate of 50ml/min, heating to 1400 ℃ at the heating rate of 2 ℃/min under the protection of nitrogen atmosphere, keeping for 2 hours, and then continuously cooling to room temperature under the protection of nitrogen atmosphere to obtain a black carbon-like substance, namely the composite kapok carbon. Wherein, the yield of the composite kapok carbon is 34.52 percent.
(5) Pulverizing the composite kapok carbonAnd then selecting the particle size to obtain the kapok-based conductive carbon tube. Wherein the specific surface area of the kapok-based conductive carbon tube is 10m 2 And g, the pipe diameter of the kapok-based conductive carbon pipe is 12 mu m, and the conductivity of the kapok-based conductive carbon pipe is 145 s/cm.
Example 3:
(1) 8 grams of thermosetting phenolic resin was dissolved in 200ml of ethanol. Wherein the thermosetting phenolic resin has a solid content of 91 wt%, a viscosity of 2000mpas at 25 ℃, a residual carbon content of 45 wt%, a free phenol content of 6 wt% and a water content of 3 wt%.
(2) Drying kapok in vacuum at 50 deg.C for 20 hr in a first container with pressure of-0.08 MPa.
(3) Weighing 5g of dried ceiba, placing the ceiba in a closed second container, vacuumizing to-0.1 MPa, slowly dripping a resin solution, soaking the dried ceiba in the resin solution for 30 hours, and taking out to obtain the composite ceiba. And (3) drying and curing the composite kapok in an oven at 160 ℃ for 12 hours, and cooling to room temperature to obtain the cured composite kapok.
(4) And (3) placing the cured composite kapok in a high-temperature carbonization furnace, introducing nitrogen into the high-temperature carbonization furnace at the flow rate of 80ml/min, heating to 1100 ℃ at the heating rate of 3 ℃/min under the protection of nitrogen atmosphere, keeping for 4 hours, and then continuously cooling to room temperature under the protection of nitrogen atmosphere to obtain a black carbon-like substance, namely the composite kapok carbon. Wherein, the yield of the composite kapok carbon is 35.66%.
(5) And (3) crushing the composite kapok carbon, and selecting the particle size to obtain the kapok-based conductive carbon tube. Wherein the specific surface area of the kapok-based conductive carbon tube is 315m 2 And g, the pipe diameter of the kapok-based conductive carbon pipe is 14 mu m, and the conductivity of the kapok-based conductive carbon pipe is 75 s/cm.
As can be seen from example 3, the soaking time of kapok in the resin solution in example 3 is significantly longer than that in examples 1 and 2, and the partial crosslinking reaction of the resin occurs due to the long soaking time of kapok in the resin solution, so that the ratio of the mass of the resin to the mass of kapok in the composite kapok obtained in example 3 is greater than that in examples 1 and 2, and the conductivity of the kapok-based conductive carbon tube prepared in example 3 is significantly lower than that of the kapok-based conductive carbon tube prepared in examples 1 and 2.
Example 4:
(1) 5 grams of thermosetting phenolic resin was dissolved in 200ml of deionized water. Wherein the thermosetting phenolic resin has a solid content of 91 wt%, a viscosity of 2000mpas at 25 ℃, a residual carbon content of 45 wt%, a free phenol content of 6 wt% and a water content of 3 wt%.
(2) Drying kapok in vacuum at 110 deg.C for 12 hr in a first container with pressure of-0.08 MPa.
(3) Weighing 5g of dried ceiba, placing the ceiba in a closed second container, vacuumizing to-0.1 MPa, slowly dripping a resin solution, soaking the dried ceiba in the resin solution for 10 hours, and taking out to obtain the composite ceiba. And (3) drying and curing the composite kapok in a drying oven at 150 ℃ for 5 hours, and cooling to room temperature to obtain the cured composite kapok.
(4) And (3) placing the cured composite kapok in a high-temperature carbonization furnace, introducing nitrogen into the high-temperature carbonization furnace at the flow rate of 50ml/min, heating to 1100 ℃ at the heating rate of 2 ℃/min under the protection of nitrogen atmosphere, keeping for 6 hours, and then continuously cooling to room temperature under the protection of nitrogen atmosphere to obtain a black carbon-like substance, namely the composite kapok carbon. Wherein, the yield of the composite kapok carbon is 31.46 percent.
(5) Crushing the composite ceiba carbon, selecting the particle size to obtain ceiba-based conductive carbon tube with specific surface area of 12m 2 G, pipe diameter of 13 μm. Wherein, the conductivity of the kapok-based conductive carbon tube is 109 s/cm.
It can be seen from comparison of example 3 and example 4 that the concentrations of the thermosetting phenol resin solutions are equivalent, but the soaking time of the kapok in the resin solution in example 3 is significantly longer than that in example 4, resulting in higher resin quality in the composite kapok prepared in example 3 compared to comparative example 4. Therefore, the conductivity of the kapok-based conductive carbon tube prepared in example 3 was lower than that of example 4. However, the conductivity of the kapok-based conductive carbon tube in example 3 is still significantly improved compared to the kapok carbon and resin bulk carbonization, which is detailed in the following comparative examples.
Moreover, comparing example 4 with example 1 and example 2, it can be seen that the concentration of the resin solution in example 4 is significantly lower than that in example 1 and example 2, and in all of examples 1, example 2 and example 4, the kapok is soaked in the resin solution for 10 hours when the composite kapok is prepared. Therefore, the mass of the resin in the composite kapok obtained in example 4 was low compared to comparative examples 1 and 2. Therefore, the kapok-based conductive carbon tube prepared in example 4 has lower conductivity than those of examples 1 and 2.
In conclusion, the mass ratio of the resin to the kapok in the composite kapok is influenced by the concentration of the resin solution for soaking the kapok and the soaking time of the kapok in the resin. In the composite kapok, the mass of the resin is too large or too small relative to the mass of the kapok, which can cause the conductivity of the finally prepared kapok-based conductive carbon tube to be reduced.
Example 5:
the preparation of the cathode of the organic aqueous battery adopts a cage electrode, organic azines are taken as active substances of the electrode, and the kapok-based conductive carbon tube is taken as a carrier and a conductive agent of the active substances in the example 1.
Specifically, phenazine and a ceiba-based conductive carbon tube are uniformly mixed according to the mass ratio of 10:3 to serve as a negative electrode material, wherein the tap density of the negative electrode material is 0.45g/cm 3 And the theoretical specific capacity is 210 mAh/g.
And (3) placing the uniformly mixed negative electrode material into a cage made of foamed nickel with the pore diameter of 110PPI to prepare an electrode, wherein the depth of the lower groove cage box is 2mm, the thickness of the foamed nickel at the bottom of the cage and the cover plate is 0.8mm, and the compression ratio of the rolling thickness is 1.5.
Soaking the electrode in polytetrafluoroethylene emulsion with solid content of 10 wt% for 0.5 min; and then, drying the electrode in an oven at the temperature of 90 ℃ for 20 min.
The electrode prepared by the method is used as a negative electrode, the sintered nickel oxide is used as a positive electrode, and the 6M KOH solution is used as an electrolyte, so that the organic water-based battery is prepared. Through actual tests, the utilization rate of the phenazine in the negative electrode of the organic water system battery reaches 86%, and the capacity retention rate of the organic water system battery after 5000 times of 1C charging and discharging is 85%.
In comparative examples 1 to 4, the factors affecting the kapok-based carbon conductive tube mainly include:
1. the mass ratio of the kapok to the resin in the composite kapok; the mass fraction of the resin in the composite kapok is influenced by the properties of the solid content, free phenol, water content and the like of the resin, and the mass fraction of the resin in the composite kapok is also influenced by the concentration of a resin solution and the soaking time of the kapok in the resin solution;
2. the temperature of carbonization; wherein, the higher the carbonization temperature, the higher the conductivity of the kapok-based conductive carbon tube is.
In addition, under the synergistic effect of other comprehensive factors such as the drying temperature of the kapok, the drying time of the kapok, the feeding mass ratio of the kapok to the resin solution, the residual carbon content of the resin, the carbonization temperature rise rate, the carbonization time and the like, the conductivity of the kapok-based conductive carbon tube is further improved.
Comparative example 1:
(1) 10 grams of kapok was weighed into a high temperature carbonization furnace.
(2) Introducing nitrogen at the flow rate of 50ml/min, heating to 1300 ℃ at the heating rate of 2 ℃/min under the protection of nitrogen atmosphere, keeping for 2 hours, and then continuously cooling to room temperature under the protection of nitrogen atmosphere to obtain black carbon-like substances, namely the ceiba carbon. Wherein, the yield of the ceiba carbon is 21.37%, and the conductivity is 1.75 s/cm.
Comparative example 2:
(1) 10 g of thermosetting phenolic resin is put into an oven for curing, cured for 6 hours at 160 ℃, taken out and put into a high-temperature carbonization furnace.
(2) Introducing nitrogen at the flow rate of 50ml/min, heating to 1300 ℃ at the temperature rise rate of 2 ℃/min under the protection of nitrogen atmosphere, keeping for 2 hours, and then continuously cooling to room temperature under the protection of nitrogen atmosphere to obtain black carbon-like substances, wherein the conductivity of the black carbon-like substances is 25.62 s/cm.
Comparing the respective comparative examples and examples, it can be seen that the conductivity of the kawo-based conductive carbon tube prepared by the method is much higher than that of kawo-or resin carbonized alone due to the synergistic effect of kawo-e-and-kawo-kah-k-a-k-a-k-a-.
In addition, as shown in fig. 1 and 2, since kapok is used as a support for a resin, the structure of the composite kapok carbon prepared in example 1 (fig. 1) is significantly more complete than that of the kapok carbon prepared in comparative example 1 (fig. 2), and the yield of the composite kapok carbon prepared in each example is also significantly higher than that of the kapok carbon prepared in comparative example 1. Under the synergistic effect of comprehensive factors such as the drying temperature of the ceiba, the drying time of the ceiba, the feeding mass ratio of the ceiba and the resin solution, the soaking time of the ceiba in the resin solution, the carbonization temperature, the carbonization heating rate, the carbonization time, the property of the resin and the like, the yield of the composite ceiba carbon is further improved.
The present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of a kapok-based conductive carbon tube is characterized by comprising the following steps of:
(1) dissolving resin in a solvent to form a solution, and uniformly stirring; wherein the mass fraction of the resin in the solution is 1-50 wt%; the solvent comprises one or more of water, ethanol, acetone, formaldehyde and tetrahydrofuran;
(2) drying the kapok in vacuum;
(3) placing the dried ceiba in a vacuum container, dropwise adding a resin solution, and soaking the dried ceiba in the resin solution to obtain a composite ceiba; taking out the composite kapok, placing the composite kapok in an environment with the temperature of 100-200 ℃ for drying and curing for 5-20 hours, and then cooling to obtain cured composite kapok;
(4) placing the cured composite kapok in an inert atmosphere, heating at the speed of 1-10 ℃/min, carbonizing at the constant temperature of 800-1600 ℃ for 1-10 h, and cooling to obtain composite kapok carbon;
(5) and (3) crushing and crushing the composite ceiba carbon to obtain the ceiba-based conductive carbon tube.
2. The method of claim 1, wherein the resin comprises a thermosetting phenolic resin.
3. The method for preparing a kapok-based conductive carbon tube according to claim 2, wherein the thermosetting phenolic resin has a free phenol content of 5 to 10 wt%.
4. The method of claim 1, wherein the resin has a solid content of 85 wt% to 95 wt%, a viscosity of 500 to 3000mpas at 25 ℃, and a water content of 1 wt% to 5 wt%.
5. The method for preparing a kapok-based conductive carbon tube according to claim 1, wherein the resin has a carbon residue of 35 to 55 wt%.
6. The method for preparing kapok-based carbon conductive tubes according to claim 1, wherein in the step (2), the air pressure of the vacuum drying treatment is-0.10 to-0.01 MPa, the temperature of the vacuum drying treatment is 10 to 200 ℃, and the time duration of the vacuum drying treatment is 1 to 24 hours.
7. The method for producing a ceiba-based conductive carbon tube according to claim 1, wherein, in the step (3), the pressure of the gas in the vacuum vessel is-0.10 to-0.02 MPa.
8. The method for preparing the kapok-based conductive carbon tube according to claim 1, wherein in the step (3), the mass ratio of the dried kapok to the resin solution is 1: 10-100; and/or the dried ceiba is soaked in the resin solution for 1-36 hours.
9. The method for preparing a kapok-based conductive carbon tube according to claim 1, wherein in the step (4), the inert gas in the inert atmosphere comprises one or a combination of nitrogen and argon.
10. A kapok-based conductive carbon tube, characterized in that it is prepared by the preparation method according to any one of claims 1 to 9, having a conductivity of 60 to 150s/cm and a specific surface area of 1 to 500m 2 The pipe diameter is 10-15 mu m.
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| US5776385A (en) * | 1994-04-15 | 1998-07-07 | Corning Incorporated | Method of making activated carbon composites from supported crosslinkable resins |
| JP2006188366A (en) * | 2004-12-08 | 2006-07-20 | Lignyte Co Ltd | Composite carbonized material, its manufacturing method, composite activated carbon, conductive resin composition, electrode for secondary battery and polarizable electrode for electric double layer capacitor |
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| US5776385A (en) * | 1994-04-15 | 1998-07-07 | Corning Incorporated | Method of making activated carbon composites from supported crosslinkable resins |
| JP2006188366A (en) * | 2004-12-08 | 2006-07-20 | Lignyte Co Ltd | Composite carbonized material, its manufacturing method, composite activated carbon, conductive resin composition, electrode for secondary battery and polarizable electrode for electric double layer capacitor |
| CN107973286A (en) * | 2017-11-20 | 2018-05-01 | 福州大学 | A kind of preparation method and application of baobab scytoblastema multiporous biological matter Carbon Materials |
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