CN112713006A - Activated carbon-NiCo of tobacco rod2S4Composite electrode material and preparation method thereof - Google Patents
Activated carbon-NiCo of tobacco rod2S4Composite electrode material and preparation method thereof Download PDFInfo
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- 241000208125 Nicotiana Species 0.000 title claims abstract description 163
- 235000002637 Nicotiana tabacum Nutrition 0.000 title claims abstract description 163
- 239000007772 electrode material Substances 0.000 title claims abstract description 81
- 229910003266 NiCo Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000010902 straw Substances 0.000 claims abstract description 36
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 17
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 17
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000000197 pyrolysis Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Power Engineering (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of electrode material preparation, and particularly discloses tobacco rod activated carbon-NiCo2S4A composite electrode material and a preparation method thereof. The method comprises the following steps: firstly, preparing a tobacco stem-based active carbon electrode material by adopting tobacco straws; then adding the tobacco stem-based active carbon electrode material into the mixture containing Co (NO)3)2·6H2O、Ni(NO3)2·6H2Uniformly stirring in an aqueous solution of O, hexamethylenetetramine and urea, reacting for 18-30 h at 160-200 ℃, and separating solids to obtain grayish blue powder; finally, adding the grayish blue powder into Na2Reacting in the S solution for 12-48 h at 100-300 ℃ to obtain the tobacco rod activated carbon-NiCo2S4A composite electrode material. By the method of the inventionThe active carbon-NiCo of the tobacco rod prepared by the method2S4The composite electrode material has excellent specific capacitance value and specific capacitance retention rate.
Description
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to activated carbon-NiCo of a tobacco rod2S4A composite electrode material and a preparation method thereof.
Background
The tobacco stems are tobacco stems, and a large amount of tobacco stems are generated after tobacco leaves are picked every year; for tobacco straw, incineration and disposal are mainly adopted at present. However, the burning and discarding of the tobacco straw can cause certain pollution to the atmosphere and the environment; therefore, it is necessary to develop a method for recycling tobacco straw.
In order to reduce the pollution to the environment, improve the utilization rate of tobacco straws and improve the economic value of tobacco planting, the preparation of the tobacco rod activated carbon electrode material by taking the tobacco straws as a raw material is one of the utilization modes of the tobacco straws. The tobacco stem activated carbon electrode material can be used as an electrode material for preparing a super capacitor, but the specific capacitance value of the pure tobacco stem activated carbon material is low, and the specific capacitance value of the activated carbon material must be increased.
Disclosure of Invention
In order to overcome the technical problem that the specific capacitance value of a pure tobacco rod activated carbon material is low, the invention provides a tobacco rod activated carbon-NiCo2S4A preparation method of the composite electrode material; the tobacco rod active carbon-NiCo prepared by the method2S4The composite electrode material has a high specific capacitance value.
The technical problem to be solved by the invention is realized by the following technical scheme:
activated carbon-NiCo of tobacco rod2S4A method of making a composite electrode material, comprising the steps of:
(1) taking tobacco straws, crushing the tobacco straws to obtain tobacco straw powder, and then drying the tobacco straw powder;
(2) carrying out pyrolysis treatment on the dried tobacco stalk powder to obtain a tobacco stalk carbon powder precursor;
(3) mixing the tobacco stem carbon powder precursor with KOH, adding water for further grinding and kneading, and drying to obtain a tobacco stem carbon powder/KOH mixture;
(4) then carrying out heat treatment on the tobacco stem carbon powder/KOH mixture to obtain a tobacco stem-based active carbon electrode material;
(5) adding the tobacco stem-based active carbon electrode material prepared in the step (4) into the mixture containing Co (NO)3)2·6H2O、Ni(NO3)2·6H2Uniformly stirring in an aqueous solution of O, hexamethylenetetramine and urea, reacting for 18-30 h at 160-200 ℃, and separating solids to obtain grayish blue powder;
(6) putting the grayish blue powder prepared in the step (5) into Na2Reacting in the S solution for 12-48 h at 100-300 ℃ to obtain the tobacco rod activated carbon-NiCo2S4A composite electrode material.
The carbon source used in the invention is a smoke rod activated carbon material, has a porous structure, and increases the specific surface area and reduces the transmission path of ions and electrons under the condition of not changing the nature of the oxidation-reduction reaction during the charge and discharge of the NiCo compound, thereby reducing the impedance and realizing the improvement of the performance; and the tobacco stem raw material has low cost and rich sources, and realizes resource recycling.
Further, the tobacco stem is carbonized and activated to prepare the tobacco stem-based active carbon electrode material, the tobacco stem-based active carbon electrode material is used as a substrate, and NiCo grows on the surface of the tobacco stem-based active carbon electrode material by a hydrothermal method2S4The prepared composite material has active carbon base to raise the conductivity of the material and make NiCo2S4The oxidation-reduction reaction can be carried out more fully and more quickly, and the specific capacitance value is effectively improved, so that the pseudocapacitance effect is better exerted.
Furthermore, the invention successfully grows NiCo in the substrate of the electrode material of the base activated carbon by the secondary hydrothermal method of the step (5) and the step (6)2S4Effectively reduces the interface resistance between the two substances and greatly improves the NiCo2S4The conductivity of (a); has the advantages of low reaction temperature, simple method and the like, and has wide industrial application prospect.
Preferably, the heat treatment conditions in step (2) are: under the atmosphere of nitrogen at the temperature of 3-6 DEG Cmin-1The temperature is increased to 500-600 ℃ and kept for 1-3 h.
The heat treatment conditions in the step (4) are as follows: under the atmosphere of nitrogen at 3-6 ℃ per minute-1The temperature is increased to 800-900 ℃ and kept for 1-3 h.
Preferably, the weight ratio of the tobacco stalk carbon powder precursor to KOH in the step (3) is 1: 3-8.
Most preferably, the weight ratio of the tobacco stalk carbon powder precursor to KOH in the step (3) is 1: 5.
Preferably, in step (5), the tobacco rod-based activated carbon electrode material is mixed with Co (NO)3)2·6H2O、Ni(NO3)2·6H2The weight ratio of the O, the hexamethylenetetramine and the urea is 1: 2.5-3.5: 1-2: 3-5.
Further preferably, the tobacco rod-based activated carbon electrode material is mixed with Co (NO)3)2·6H2O、Ni(NO3)2·6H2The weight ratio of the O, the hexamethylenetetramine and the urea is 1: 2.8-3.1: 1.3-1.5: 1.1-1.2: 3.5-4.5.
Most preferably, the tobacco rod-based activated carbon electrode material is mixed with Co (NO)3)2·6H2O、Ni(NO3)2·6H2The weight ratio of the O to the hexamethylenetetramine to the urea is 1:2.91:1.45:1.12: 4.
Preferably, Co (NO) in the aqueous solution of step (5)3)2·6H2O、Ni(NO3)2·6H2The ratio of the total weight of the O, the hexamethylenetetramine and the urea to the amount of water is 15-25 g: 1L.
Most preferably, Co (NO) is present in the aqueous solution of step (5)3)2·6H2O、Ni(NO3)2·6H2The ratio of the total weight of the O, the hexamethylenetetramine and the urea to the amount of water is 18-20 g: 1L.
Preferably, the reaction in the step (5) is carried out for 20-25 h at 170-190 ℃.
Most preferably, step (5) is reacted at 180 ℃ for 24 h.
Preferably, in step (6), Na2The concentration of the S solution is 0.08-0.15M.
Most preferably, Na in step (6)2The concentration of the S solution was 0.1M.
Preferably, in step (6), the grayish blue powder is mixed with Na2The dosage ratio of the S solution is 1g: 400-800 mL.
Most preferably, grayish blue powder is mixed with Na2The dosage ratio of the S solution is 1g:500 mL.
Preferably, in the step (6), the reaction is carried out for 4-16 h at 140-160 ℃; then reacting for 4-16 h at 170-190 ℃; finally, reacting for 4-16 h at 240-260 ℃.
On the basis of the above, the inventors further found out that the results are surprising through a great deal of experimental study; reacting for 4-16 h at 140-160 ℃; then reacting for 4-16 h at 170-190 ℃; finally reacting for 4-16 h at 240-260 ℃; the reaction mode can lead Ni to be generated in the hydrothermal vulcanization process2+、Co2+And S2-Have different diffusion rates; the non-uniform diffusion velocity enables the preparation of the prepared tobacco rod activated carbon-NiCo2S4The composite electrode material has a plurality of defect structures inside, reaction sites are increased, the specific surface area is further improved, and the specific capacitance value and the specific capacitance retention rate can be further greatly improved.
Most preferably, in step (6), the reaction is carried out for 10h at 150 ℃; then reacting for 10 hours at 180 ℃; finally, the reaction is carried out for 4h at 250 ℃.
The invention also provides the tobacco rod active carbon-NiCo prepared by the preparation method2S4A composite electrode material.
Has the advantages that: the invention provides a brand new tobacco rod active carbon-NiCo2S4Preparation method of composite electrode material, and tobacco rod active carbon-NiCo prepared by method2S4Compared with a pure tobacco stem activated carbon material, the composite electrode material has higher specific capacitance, and further better plays a pseudocapacitance effect. In addition, the raw material of the tobacco straw is low in cost and rich in source, and the resource recycling is realized; the method has the advantages of low reaction temperature, simple method and wide industrial application prospect.
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
EXAMPLE 1 tobacco rod activated carbon-NiCo2S4Preparation of composite electrode material
(1) Taking tobacco straws, crushing the tobacco straws into 200 meshes to obtain tobacco straw powder, and then putting the tobacco straw powder into an oven to be dried for 24 hours at the temperature of 70 ℃;
(2) putting the dried tobacco stalk powder into a tube furnace under the atmosphere of nitrogen (the flow rate is 3 mL/min)-1) At 5 ℃ in min-1The temperature is increased to 550 ℃ and kept for 2 hours for pyrolysis treatment; cooling to room temperature along with the furnace after heat treatment, and taking out to obtain a tobacco stem carbon powder precursor;
(3) mixing the tobacco stalk carbon powder precursor with KOH, adding water for further grinding and kneading, then putting the mixture into a vacuum drying oven for drying at 70 ℃ for 12 hours, and drying to obtain a tobacco stalk carbon powder/KOH mixture; wherein the weight ratio of the tobacco stalk carbon powder precursor to KOH is 1: 5; the ratio of the added weight of the water to the total weight of the tobacco stalk carbon powder precursor and the KOH is 1: 1;
(4) then putting the tobacco stalk carbon powder/KOH mixture into a tube furnace under the atmosphere of nitrogen (the flow rate is 3mL & min)-1) At 5 ℃ in min-1The temperature is increased to 850 ℃ and kept for 2h, and then pyrolysis treatment is carried out; cooling to room temperature, taking out, and fully washing the obtained sample by using 1M hydrochloric acid solution; obtaining the tobacco stem-based activated carbon electrode material;
(5) taking 100mg of the tobacco stem-based active carbon electrode material prepared in the drying step (4), adding 50mL of the active carbon electrode material containing 0.291g of Co (NO)3)2·6H2O、0.145g Ni(NO3)2·6H2Stirring the mixture for 2 hours in an aqueous solution of O, 0.112g of hexamethylenetetramine and 0.4g of urea to fully mix the mixture evenly, pouring the mixture into a hydrothermal reaction kettle, reacting for 24 hours at 180 ℃, and carrying out suction filtration on the reacted solution to obtain grayish blue powder;
(6) putting 100mg of the grayish blue powder prepared in the step (5) into a hydrothermal reaction kettle, and then adding 50mL of Na with the concentration of 0.1M2The S solution reacts for 24 hours at 180 ℃, is washed by deionized water and dried after being filtered to obtain dark blue black powder, namely the tobacco rod activated carbon-NiCo2S4A composite electrode material.
EXAMPLE 2 tobacco rod activated carbon-NiCo2S4Preparation of composite electrode material
(1) Taking tobacco straws, crushing the tobacco straws into 200 meshes to obtain tobacco straw powder, and then putting the tobacco straw powder into an oven to be dried for 24 hours at the temperature of 70 ℃;
(2) putting the dried tobacco stalk powder into a tube furnace under the atmosphere of nitrogen (the flow rate is 3 mL/min)-1) At 3 ℃ min-1The temperature is increased to 500 ℃ and is preserved for 3 hours for pyrolysis treatment; cooling to room temperature along with the furnace after heat treatment, and taking out to obtain a tobacco stem carbon powder precursor;
(3) mixing the tobacco stalk carbon powder precursor with KOH, adding water for further grinding and kneading, then putting the mixture into a vacuum drying oven for drying at 70 ℃ for 12 hours, and drying to obtain a tobacco stalk carbon powder/KOH mixture; wherein the weight ratio of the tobacco stalk carbon powder precursor to KOH is 1: 3; the ratio of the added weight of the water to the total weight of the tobacco stalk carbon powder precursor and the KOH is 1: 1;
(4) then putting the tobacco stalk carbon powder/KOH mixture into a tube furnace under the atmosphere of nitrogen (the flow rate is 3mL & min)-1) At 3 ℃ min-1The temperature is increased to 800 ℃ and kept for 2h for pyrolysis treatment; cooling to room temperature, taking out, and fully washing the obtained sample by using 1M hydrochloric acid solution; obtaining the tobacco stem-based activated carbon electrode material;
(5) taking 100mg of the tobacco stem-based active carbon electrode material prepared in the drying step (4), adding 50mL of the active carbon electrode material containing 0.291g of Co (NO)3)2·6H2O、0.145g Ni(NO3)2·6H2Stirring the mixture for 2 hours in an aqueous solution of O, 0.112g of hexamethylenetetramine and 0.4g of urea to fully mix the mixture evenly, pouring the mixture into a hydrothermal reaction kettle, reacting for 25 hours at 170 ℃, and carrying out suction filtration on the reacted solution to obtain grayish blue powder;
(6) putting 100mg of the grayish blue powder prepared in the step (5) into a hydrothermal reaction kettle, and then adding 40mL of Na with the concentration of 0.12M2S solutionReacting at 170 ℃ for 30h, filtering, washing with deionized water, and drying to obtain dark blue black powder, namely the active carbon-NiCo of the tobacco rod2S4A composite electrode material.
EXAMPLE 3 tobacco rod activated carbon-NiCo2S4Preparation of composite electrode material
(1) Taking tobacco straws, crushing the tobacco straws into 200 meshes to obtain tobacco straw powder, and then putting the tobacco straw powder into an oven to be dried for 24 hours at the temperature of 70 ℃;
(2) putting the dried tobacco stalk powder into a tube furnace under the atmosphere of nitrogen (the flow rate is 3 mL/min)-1) At 6 ℃ min-1The temperature is increased to 600 ℃ and is kept for 1.5h for pyrolysis treatment; cooling to room temperature along with the furnace after heat treatment, and taking out to obtain a tobacco stem carbon powder precursor;
(3) mixing the tobacco stalk carbon powder precursor with KOH, adding water for further grinding and kneading, then putting the mixture into a vacuum drying oven for drying at 70 ℃ for 12 hours, and drying to obtain a tobacco stalk carbon powder/KOH mixture; wherein the weight ratio of the tobacco stalk carbon powder precursor to KOH is 1: 8; the ratio of the added weight of the water to the total weight of the tobacco stalk carbon powder precursor and the KOH is 1: 1;
(4) then putting the tobacco stalk carbon powder/KOH mixture into a tube furnace under the atmosphere of nitrogen (the flow rate is 3mL & min)-1) At 6 ℃ min-1The temperature is increased to 900 ℃ and is kept for 1.5h for pyrolysis treatment; cooling to room temperature, taking out, and fully washing the obtained sample by using 1M hydrochloric acid solution; obtaining the tobacco stem-based activated carbon electrode material;
(5) taking 100mg of the tobacco stem-based active carbon electrode material prepared in the drying step (4), adding 50mL of the active carbon electrode material containing 0.291g of Co (NO)3)2·6H2O、0.145g Ni(NO3)2·6H2Stirring the mixture for 2 hours in an aqueous solution of O, 0.112g of hexamethylenetetramine and 0.4g of urea to fully mix the mixture evenly, pouring the mixture into a hydrothermal reaction kettle, reacting for 20 hours at 190 ℃, and carrying out suction filtration on the reacted solution to obtain grayish blue powder;
(6) putting 100mg of the grayish blue powder prepared in the step (5) into a hydrothermal reaction kettle, and then adding 60mL of Na with the concentration of 0.08M2The solution of S is added into the solution of S,reacting for 20h at 190 ℃, filtering, washing with deionized water, and drying to obtain dark blue black powder, namely the active carbon-NiCo of the tobacco rod2S4A composite electrode material.
EXAMPLE 4 tobacco rod activated carbon-NiCo2S4Preparation of composite electrode material
(1) Taking tobacco straws, crushing the tobacco straws into 200 meshes to obtain tobacco straw powder, and then putting the tobacco straw powder into an oven to be dried for 24 hours at the temperature of 70 ℃;
(2) putting the dried tobacco stalk powder into a tube furnace under the atmosphere of nitrogen (the flow rate is 3 mL/min)-1) At 5 ℃ in min-1The temperature is increased to 550 ℃ and kept for 2 hours for pyrolysis treatment; cooling to room temperature along with the furnace after heat treatment, and taking out to obtain a tobacco stem carbon powder precursor;
(3) mixing the tobacco stalk carbon powder precursor with KOH, adding water for further grinding and kneading, then putting the mixture into a vacuum drying oven for drying at 70 ℃ for 12 hours, and drying to obtain a tobacco stalk carbon powder/KOH mixture; wherein the weight ratio of the tobacco stalk carbon powder precursor to KOH is 1: 5; the ratio of the added weight of the water to the total weight of the tobacco stalk carbon powder precursor and the KOH is 1: 1;
(4) then putting the tobacco stalk carbon powder/KOH mixture into a tube furnace under the atmosphere of nitrogen (the flow rate is 3mL & min)-1) At 5 ℃ in min-1The temperature is increased to 850 ℃ and kept for 2h, and then pyrolysis treatment is carried out; cooling to room temperature, taking out, and fully washing the obtained sample by using 1M hydrochloric acid solution; obtaining the tobacco stem-based activated carbon electrode material;
(5) taking 100mg of the tobacco stem-based active carbon electrode material prepared in the drying step (4), adding 50mL of the active carbon electrode material containing 0.291g of Co (NO)3)2·6H2O、0.145g Ni(NO3)2·6H2Stirring the mixture for 2 hours in an aqueous solution of O, 0.112g of hexamethylenetetramine and 0.4g of urea to fully mix the mixture evenly, pouring the mixture into a hydrothermal reaction kettle, reacting for 24 hours at 180 ℃, and carrying out suction filtration on the reacted solution to obtain grayish blue powder;
(6) putting 100mg of the grayish blue powder prepared in the step (5) into a hydrothermal reaction kettle, and then adding 50mL of Na with the concentration of 0.1M2S solution, first of allReacting for 10 hours at 150 ℃; then reacting for 10 hours at 180 ℃; finally reacting for 4 hours at 250 ℃; washing with deionized water after suction filtration, and drying to obtain dark blue black powder, namely the active carbon-NiCo of the tobacco rod2S4A composite electrode material.
Comparative example 1 preparation of tobacco-stalk-based activated carbon electrode Material
(1) Taking tobacco straws, crushing the tobacco straws into 200 meshes to obtain tobacco straw powder, and then putting the tobacco straw powder into an oven to be dried for 24 hours at the temperature of 70 ℃;
(2) putting the dried tobacco stalk powder into a tube furnace under the atmosphere of nitrogen (the flow rate is 3 mL/min)-1) At 5 ℃ in min-1The temperature is increased to 550 ℃ and kept for 2 hours for pyrolysis treatment; cooling to room temperature along with the furnace after heat treatment, and taking out to obtain a tobacco stem carbon powder precursor;
(3) mixing the tobacco stalk carbon powder precursor with KOH, adding water for further grinding and kneading, then putting the mixture into a vacuum drying oven for drying at 70 ℃ for 12 hours, and drying to obtain a tobacco stalk carbon powder/KOH mixture; wherein the weight ratio of the tobacco stalk carbon powder precursor to KOH is 1: 5; the ratio of the added weight of the water to the total weight of the tobacco stalk carbon powder precursor and the KOH is 1: 1;
(4) then putting the tobacco stalk carbon powder/KOH mixture into a tube furnace under the atmosphere of nitrogen (the flow rate is 3mL & min)-1) At 5 ℃ in min-1The temperature is increased to 850 ℃ and kept for 2h, and then pyrolysis treatment is carried out; cooling to room temperature, taking out, and fully washing the obtained sample by using 1M hydrochloric acid solution; and obtaining the tobacco stem-based activated carbon electrode material.
The tobacco stem activated carbon-NiCo prepared in the examples 1 to 42S4The composite electrode material and the tobacco stem-based active carbon electrode material prepared in the proportion 1 are respectively and uniformly mixed with the binder according to the weight ratio of 9:1 to prepare slurry, then the slurry is respectively coated on aluminum foil, and the aluminum foil is dried and pressed into a sheet-shaped electrode. The three-electrode system is adopted to test the concentration of the carbon dioxide in the solution of 1 A.g-1Specific capacitance value at current density of (1) and (1) g-1Specific capacity retention after 1000 cycles at current density of (a); the test results are shown in Table 1.
TABLE 1 specific capacitance value and specific capacitance retention ratio test results
| Specific capacitance value | Specific capacity retention ratio | |
| EXAMPLE 1 tobacco rod activated carbon-NiCo2S4Composite electrode material | 867.7F·g-1 | 62.6％ |
| EXAMPLE 2 tobacco rod activated carbon-NiCo2S4Composite electrode material | 814.1F·g-1 | 60.9％ |
| EXAMPLE 3 tobacco rod activated carbon-NiCo2S4Composite electrode material | 833.5F·g-1 | 63.1％ |
| EXAMPLE 4 tobacco rod activated carbon-NiCo2S4Composite electrode material | 1315.9F·g-1 | 88.2％ |
| Comparative example 1 tobacco rod-based activated carbon electrode Material | 261.3F·g-1 | 54.1％ |
As can be seen from Table 1, in the embodiments 1 to 3 of the present invention, NiCo is grown on the surface of the electrode material by a hydrothermal method by using a tobacco rod-based activated carbon electrode material as a substrate2S4The prepared active carbon-NiCo of the tobacco rod2S4Compared with the tobacco stem-based activated carbon electrode material, the specific capacitance of the composite electrode material is greatly improved; meanwhile, the specific capacitance retention rate is improved to a certain extent; however, the improvement of the specific capacitance retention ratio is not so large, and is only 60% of the head, and still needs to be further improved.
In addition, the activated carbon NiCo rods prepared from example 4 and example 12S4Compared with the composite electrode material, the specific capacitance value is improved to 1315.9F g-1Meanwhile, the capacitance retention rate is also improved to 88.2%; it can be seen that the activated carbon NiCo rods prepared under the conditions of example 4 were made of2S4The specific capacitance value and the capacitance retention rate of the composite electrode material are further remarkably improved; this shows that in the method of the invention, the step (6) is firstly reacted for 4-16 h at 140-160 ℃; then reacting for 4-16 h at 170-190 ℃; finally reacting for 4-16 h at 240-260 ℃; the specific capacitance value and the specific capacitance retention rate can be further greatly improved.
Claims (10)
1. Activated carbon-NiCo of tobacco rod2S4The preparation method of the composite electrode material is characterized by comprising the following steps:
(1) taking tobacco straws, crushing the tobacco straws to obtain tobacco straw powder, and then drying the tobacco straw powder;
(2) carrying out pyrolysis treatment on the dried tobacco stalk powder to obtain a tobacco stalk carbon powder precursor;
(3) mixing the tobacco stem carbon powder precursor with KOH, adding water for further grinding and kneading, and drying to obtain a tobacco stem carbon powder/KOH mixture;
(4) then carrying out heat treatment on the tobacco stem carbon powder/KOH mixture to obtain a tobacco stem-based active carbon electrode material;
(5) taking the product prepared in the step (4)Adding tobacco stem base active carbon electrode material into Co (NO) -containing3)2·6H2O、Ni(NO3)2·6H2Uniformly stirring in an aqueous solution of O, hexamethylenetetramine and urea, reacting for 18-30 h at 160-200 ℃, and separating solids to obtain grayish blue powder;
(6) putting the grayish blue powder prepared in the step (5) into Na2Reacting in the S solution for 12-48 h at 100-300 ℃ to obtain the tobacco rod activated carbon-NiCo2S4A composite electrode material.
2. The tobacco rod activated carbon-NiCo of claim 12S4The preparation method of the composite electrode material is characterized in that,
the heat treatment conditions in the step (2) are as follows: under the atmosphere of nitrogen at 3-6 ℃ per minute-1The temperature is increased to 500-600 ℃ and is kept for 1-3 h;
the heat treatment conditions in the step (4) are as follows: under the atmosphere of nitrogen at 3-6 ℃ per minute-1The temperature is increased to 800-900 ℃ and kept for 1-3 h.
3. The tobacco rod activated carbon-NiCo of claim 12S4The preparation method of the composite electrode material is characterized in that,
the weight ratio of the tobacco stalk carbon powder precursor to KOH in the step (3) is 1: 3-8;
most preferably, the weight ratio of the tobacco stalk carbon powder precursor to KOH in the step (3) is 1: 5.
4. The tobacco rod activated carbon-NiCo of claim 12S4The preparation method of the composite electrode material is characterized in that in the step (5),
tobacco stem based active carbon electrode material and Co (NO)3)2·6H2O、Ni(NO3)2·6H2The weight ratio of the O, the hexamethylenetetramine and the urea is 1: 2.5-3.5: 1-2: 3-5;
further preferably, the tobacco rod-based activated carbon electrode material is mixed with Co (NO)3)2·6H2O、Ni(NO3)2·6H2The weight ratio of the O, the hexamethylenetetramine and the urea is 1: 2.8-3.1: 1.3-1.5: 1.1-1.2: 3.5-4.5;
most preferably, the tobacco rod-based activated carbon electrode material is mixed with Co (NO)3)2·6H2O、Ni(NO3)2·6H2The weight ratio of the O to the hexamethylenetetramine to the urea is 1:2.91:1.45:1.12: 4.
5. The tobacco rod activated carbon-NiCo of claim 12S4The preparation method of the composite electrode material is characterized in that,
co (NO) in the aqueous solution of the step (5)3)2·6H2O、Ni(NO3)2·6H2The ratio of the total weight of the O, the hexamethylenetetramine and the urea to the amount of water is 15-25 g: 1L;
most preferably, Co (NO) is present in the aqueous solution of step (5)3)2·6H2O、Ni(NO3)2·6H2The ratio of the total weight of the O, the hexamethylenetetramine and the urea to the amount of water is 18-20 g: 1L.
6. The tobacco rod activated carbon-NiCo of claim 12S4The preparation method of the composite electrode material is characterized in that the step (5) is carried out for 20-25 h at the temperature of 170-190 ℃;
most preferably, step (5) is reacted at 180 ℃ for 24 h.
7. The tobacco rod activated carbon-NiCo of claim 12S4The preparation method of the composite electrode material is characterized in that in the step (6),
Na2the concentration of the S solution is 0.08-0.15M;
most preferably, Na in step (6)2The concentration of the S solution was 0.1M.
8. The tobacco rod activated carbon-NiCo of claim 12S4A method for preparing a composite electrode material,it is characterized in that in the step (6),
grayish blue powder and Na2The dosage ratio of the S solution is 1g: 400-800 mL;
most preferably, grayish blue powder is mixed with Na2The dosage ratio of the S solution is 1g:500 mL.
9. The tobacco rod activated carbon-NiCo of claim 12S4The preparation method of the composite electrode material is characterized in that in the step (6), the reaction is carried out for 4-16 h at the temperature of 140-160 ℃; then reacting for 4-16 h at 170-190 ℃; finally reacting for 4-16 h at 240-260 ℃;
most preferably, in step (6), the reaction is carried out for 10h at 150 ℃; then reacting for 10 hours at 180 ℃; finally, the reaction is carried out for 4h at 250 ℃.
10. The activated carbon-NiCo rod prepared by the preparation method of any one of claims 1 to 92S4A composite electrode material.
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