CN113078000A - Preparation method of flexible electrode material of high-load lignin carbon spheres - Google Patents
Preparation method of flexible electrode material of high-load lignin carbon spheres Download PDFInfo
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- CN113078000A CN113078000A CN202110356603.5A CN202110356603A CN113078000A CN 113078000 A CN113078000 A CN 113078000A CN 202110356603 A CN202110356603 A CN 202110356603A CN 113078000 A CN113078000 A CN 113078000A
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- 229920005610 lignin Polymers 0.000 title claims abstract description 93
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 83
- 239000007772 electrode material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 45
- 229920002678 cellulose Polymers 0.000 claims abstract description 33
- 239000001913 cellulose Substances 0.000 claims abstract description 33
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000005457 ice water Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000011068 loading method Methods 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 241000143432 Daldinia concentrica Species 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000758 substrate Substances 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
- H01G11/84—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of a high-load lignin carbon sphere flexible electrode material, which comprises the steps of adding monomers of lignin carbon spheres and a conductive polymer into a sulfosalicylic acid solution, ultrasonically mixing and dispersing, then placing in an ice water bath, dropwise adding an ammonium persulfate oxidant to initiate polymerization, then filtering and washing a product obtained by polymerization to obtain lignin carbon spheres coated by the conductive polymer, preparing the lignin carbon spheres coated by the conductive polymer into a dispersion solution, blending and stirring the dispersion solution, microfibrillated cellulose and distilled water, and performing suction filtration and drying after stirring to obtain a flexible electrode material finished product. The invention can solve the problems of poor dispersion and easy agglomeration of the lignin carbon spheres, improves the problem of low loading capacity of the lignin carbon spheres in the flexible electrode material, and has the advantages of simple process and easily obtained raw materials.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a preparation method of a flexible electrode material of a high-load lignin carbon sphere.
Background
Energy and environmental problems are challenges that have existed in the past decades and for a long period of time in the future, how to efficiently and environmentally store energy is an important problem facing human beings at present, and the use of renewable biomass resources in the development of novel energy storage devices can be an effective way to solve energy and environmental problems.
The cellulose is a renewable resource with the largest global reserve, the microfibrillated cellulose is taken from natural cellulose, is a nano-grade cellulose material, has the diameter of nano grade and the length of micron grade, has low price, wide sources and reproducibility, has a unique structure, is easy to functionally modify, is a good nano material, and meets the requirement of sustainable energy storage when being applied to the development of electrode materials of super capacitors.
The lignin is a renewable resource with the global reserve second to cellulose, the lignin carbon spheres are carbon materials obtained by direct pyrolysis of the lignin, the shapes of the lignin carbon spheres are spherical or hemispherical, a large number of pores exist on the surfaces, the surfaces are rough, the lignin carbon spheres have a fluctuating structure, and the lignin carbon spheres have the advantages of low price, easiness in obtaining, environmental friendliness and the like. The lignin carbon spheres with high porosity have the characteristics of high chemical and thermal stability in chemical properties; the conductive material has the characteristics of small density, large specific surface area and the like in physical properties and structures, has excellent conductive performance, and is an electrode material which is widely researched at present. Electric double layer capacitors made from lignin carbon sphere materials generally have high power density, excellent cycle stability, long cycle life characteristics, and excellent electrical conductivity. Moreover, the structural units of the guaiacyl and syringyl lignin contain a large number of methyl aryl ether bonds, the polyphenol hydroxyl lignin prepared by demethylation reaction has excellent electrochemical characteristics, and the interconversion characteristic of the phenol quinone enables the lignin to be an electrode material of a pseudo capacitor with excellent performance. Based on the advantages of the above resource reserves and chemical properties of lignin, researchers have developed a series of biomass-based supercapacitor electrode materials with good electrochemical properties and performance stability. Currently, lignin-based supercapacitors have become a key research direction in the field of developing biomass-based supercapacitors.
Therefore, the preparation of the flexible supercapacitor electrode material by compounding the microfibrillated cellulose and the lignin carbon spheres is a promising research direction. However, the specific surface area of the lignin carbon spheres is large, strong interaction exists among the carbon spheres, the lignin carbon spheres are easy to agglomerate, so that the lignin carbon spheres are difficult to disperse in water, and the agglomeration phenomenon becomes more serious when the dispersion concentration is high, so that the lignin carbon spheres can only be compounded with microfibrillated cellulose to prepare the flexible electrode material at low concentration, and thus the loading capacity of the lignin carbon spheres in the lignin carbon sphere/microfibrillated cellulose flexible supercapacitor electrode material is low, so that the energy storage performance is low, and the wide application of the lignin carbon spheres in flexible electronic equipment is limited.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible electrode material of a high-load lignin carbon sphere. The invention can solve the problems of poor dispersion and easy agglomeration of the lignin carbon spheres, improves the problem of low loading capacity of the lignin carbon spheres in the flexible electrode material, and has the advantages of simple process and easily obtained raw materials.
The technical scheme of the invention is as follows: a preparation method of a high-load lignin carbon ball flexible electrode material comprises the steps of adding monomers of lignin carbon balls and conductive polymers into a sulfosalicylic acid solution, carrying out ultrasonic mixing and dispersion, then placing the mixture into an ice water bath, dropwise adding an ammonium persulfate oxidant to initiate polymerization, then filtering and washing a product obtained by polymerization to obtain lignin carbon balls coated by the conductive polymers, preparing the lignin carbon balls coated by the conductive polymers into a dispersion liquid, blending and stirring the dispersion liquid, microfibrillated cellulose and distilled water, and carrying out suction filtration and drying after stirring to obtain a flexible electrode material finished product.
According to the preparation method of the high-load lignin carbon sphere flexible electrode material, the preparation process of the conductive polymer coated lignin carbon sphere is as follows: uniformly dispersing 1-15 parts of lignin carbon spheres in 100-200 parts of 0.4M sulfosalicylic acid aqueous solution, adding 0.1-1.5 parts of conductive polymer monomer into a container under the condition of magnetic stirring, mixing and dispersing for 20-40min under the ultrasonic condition, then placing the container into an ice water bath, dropwise adding 30-80 parts of 0.1M ammonium persulfate solution into the container to initiate polymerization, stirring for 50-70min, and then filtering and fully washing a product obtained by polymerization to be neutral to obtain the lignin carbon spheres coated by the conductive polymer.
The preparation method of the high-load lignin carbon sphere flexible electrode material comprises the steps of uniformly dispersing 2 parts of lignin carbon spheres in 150 parts of 0.4M sulfosalicylic acid aqueous solution in a container, adding 0.5 part of conductive polymer monomer into the container under the condition of magnetic stirring, placing the container under the ultrasonic condition for mixing and dispersing for 30min, placing the container in an ice water bath, dropwise adding 50 parts of 0.1M ammonium persulfate solution into the container to initiate polymerization, stirring for 60min, filtering a product obtained by polymerization, and fully washing to be neutral to obtain the lignin carbon spheres coated by the conductive polymer.
The preparation method of the flexible electrode material with the high-load lignin carbon spheres comprises the following steps: and (2) putting 1-15 parts of microfibrillated cellulose with the mass concentration of 0.5-2% into a container, adding 3-10 parts of dispersion liquid, adding 10-30 parts of distilled water, stirring for 20-40min, fully mixing, performing suction filtration, and drying at 50-70 ℃ for 5-7h to obtain a finished product of the flexible electrode material.
The preparation method of the flexible electrode material with the high-load lignin carbon spheres comprises the steps of putting 10 parts of microfibrillated cellulose with the mass concentration of 1% into a container, adding 5 parts of dispersion liquid, adding 20 parts of distilled water, stirring for 30min to fully mix the materials, performing suction filtration, and drying at 60 ℃ for 6h to obtain a finished product of the flexible electrode material.
Compared with the prior art, the method has the advantages that the conductive polymer is used for coating the lignin carbon spheres, so that the surface energy of the lignin carbon spheres can be reduced, and the dispersion performance of the lignin carbon spheres is improved, so that a high-concentration lignin carbon sphere dispersion liquid is obtained, and then the dispersion liquid of the conductive polymer coated lignin carbon spheres is mixed with microfibrillated cellulose, so that the composition with the microfibrillated cellulose at a higher concentration is facilitated, the loading capacity of the lignin carbon spheres in the flexible electrode material is improved, and the high-loading lignin carbon sphere microfibrillated cellulose supercapacitor flexible electrode material can be prepared. The conductive polymer is used as a pseudo-capacitor material with a conjugated structure, and can store charges on the surface of an electrode material and in a bulk phase through reversible redox reaction, so that higher energy density is obtained. Therefore, in the flexible electrode material prepared by the invention, on one hand, the coating of the conductive polymer can provide more conductive paths for the electrode material, so that the conductivity of the flexible electrode material is improved, and on the other hand, the conductive polymer has the pseudocapacitance energy storage characteristic, so that the conductive polymer can form an energy storage synergistic effect with lignin carbon spheres, and the energy density and the capacitance performance of the flexible electrode material are improved.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1: a preparation method of a flexible electrode material of a high-load lignin carbon sphere comprises the following steps:
(1) in a 250mL beaker, 3g of lignin carbon spheres were uniformly dispersed in 180mL of 0.4M sulfosalicylic acid aqueous solution, then 0.8mL of conductive polymer monomer was added to the beaker under magnetic stirring, and mixed and dispersed for 25min under ultrasonic conditions. And then placing the beaker in an ice-water bath, dropwise adding 40mL of 0.1M ammonium persulfate solution into the beaker under the condition of continuous stirring, stirring for 55min, filtering and fully washing a product obtained by polymerization to be neutral to obtain the conductive polymer coated lignin carbon spheres, and preparing the conductive polymer coated lignin carbon spheres into a dispersion liquid for later use.
(2) Preparing a flexible electrode material: and (3) putting 8mL of 0.9% microfibrillated cellulose into a beaker, transferring 10mL of dispersion into the beaker by using a liquid transfer gun, adding 15mL of distilled water, stirring for 25min by using a magnetic stirrer, fully mixing, finally carrying out suction filtration, and drying for 5h at 65 ℃ to obtain a finished product of the flexible electrode material.
The microfibrillated cellulose is a cheap and abundant degradable nano-scale cellulose functional material, is a highly swollen colloidal cellulose with the diameter of 1-100 nm and the length of less than 20 microns, is nontoxic and harmless to the environment and is easy to recycle. In this example, a mechanical microfibrillated cellulose (hereinafter the same) prepared by a laboratory method using an enzyme pretreatment was used. The microfibrillated cellulose has abundant hydroxyl on the surface, can be mixed with other functional materials to prepare a composite membrane material, endows other materials with excellent mechanical strength and flexibility, and is an excellent framework material and a substrate material. In this example, the lignin carbon spheres used were alkali lignin carbon spheres prepared by spray drying and carbonization of alkali lignin as a raw material in a laboratory (the same applies below). The conductive polymer electrode material mainly includes polyaniline, polypyrrole, poly (3,4 ethylenedioxythiophene), and the like, and in this embodiment, polyaniline (the same applies below) is used.
Example 2: a preparation method of a flexible electrode material of a high-load lignin carbon sphere comprises the following steps:
(1) in a 250mL beaker, 5g of lignin carbon spheres were uniformly dispersed in 140mL of 0.4M sulfosalicylic acid aqueous solution, then under magnetic stirring, 1mL of conductive polymer monomer was added to the beaker, and mixed and dispersed for 35min under ultrasonic conditions. And then placing the beaker in an ice-water bath, dropwise adding 60mL of 0.1M ammonium persulfate solution into the beaker under the condition of continuous stirring, stirring for 65min, filtering and fully washing a product obtained by polymerization to be neutral to obtain the conductive polymer coated lignin carbon spheres, and preparing the conductive polymer coated lignin carbon spheres into a dispersion liquid for later use.
(2) Preparing a flexible electrode material: taking 12mL of 0.5% microfibrillated cellulose, placing the microfibrillated cellulose into a beaker, transferring 8mL of dispersion into the beaker by using a liquid transfer gun, adding 25mL of distilled water, stirring for 35min by using a magnetic stirrer, fully mixing, finally carrying out suction filtration, and drying for 7h at 55 ℃ to obtain a finished product of the flexible electrode material.
Example 3: a preparation method of a flexible electrode material of a high-load lignin carbon sphere comprises the following steps:
(1) in a 250mL beaker, 2g of lignin carbon spheres were uniformly dispersed in 150mL of 0.4M sulfosalicylic acid aqueous solution, then 0.5mL of conductive polymer monomer was added to the beaker under magnetic stirring, and mixed and dispersed for 30min under ultrasonic conditions. And then placing the beaker in an ice-water bath, dropwise adding 50mL of 0.1M ammonium persulfate solution into the beaker under the condition of continuous stirring, stirring for 60min, filtering and fully washing a product obtained by polymerization to be neutral to obtain the conductive polymer coated lignin carbon spheres, and preparing the conductive polymer coated lignin carbon spheres into a dispersion liquid for later use.
(2) Preparing a flexible electrode material: taking 10mL of 1% microfibrillated cellulose, placing the microfibrillated cellulose into a beaker, using a liquid transfer gun to transfer 5mL of dispersion liquid, adding 20mL of distilled water into the beaker, stirring the mixture for 30min by using a magnetic stirrer, fully mixing the dispersion liquid and the distilled water, finally performing suction filtration, and drying the mixture for 7h at the temperature of 60 ℃ to obtain a finished product of the flexible electrode material.
Example 4: in this example, a controlled variable method was used to compare the flexible electrode material prepared according to the present invention with the electrode material prepared by removing the conductive polymer in the present invention, wherein the component ratios and performance parameters of the flexible electrode material prepared according to the steps of the present invention are shown in table 1.
| Sample (I) | Lignin carbon sphere | Distilled water | Concentration of | Conductive polymers | Microfibrillated cellulose | Electrical conductivity of | Specific capacitance |
| g | mL | g/mL | g | g | S/m | F/g | |
| 1 | 0.01 | 10 | 0.001 | 0.02 | 0.1 | 1.20 | 4.52 |
| 2 | 0.02 | 10 | 0.005 | 0.04 | 0.1 | 19.24 | 15.46 |
| 3 | 0.05 | 10 | 0.01 | 0.10 | 0.1 | 192.55 | 69.21 |
| 4 | 0.10 | 10 | 0.02 | 0.20 | 0.1 | 475.23 | 145.58 |
| 5 | 0.15 | 10 | 0.05 | 0.30 | 0.1 | 758.65 | 252.59 |
TABLE 1
The composition ratios and performance parameters of the electrode materials obtained after removing the conductive polymer are shown in table 2.
| Sample (I) | Lignin carbon sphere | Distilled water | Concentration of | Microfibrillated cellulose | Electrical conductivity of | Specific capacitance |
| g | mL | g/mL | g | S/m | F/g | |
| 1 | 0.01 | 10 | 0.001 | 0.1 | 0.11 | 0.81 |
| 2 | 0.02 | 10 | 0.005 | 0.1 | 9.72 | 2.21 |
| 3 | 0.05 | 10 | 0.01 | 0.1 | 59.83 | 10.52 |
| 4 | 0.10 | 10 | 0.02 | 0.1 | 144.23 | 20.55 |
| 5 | 0.15 | 10 | 0.05 | 0.1 | 245.22 | 50.42 |
TABLE 2
As can be seen from the comparison between tables 1 and 2, the flexible electrode formed by adding the conductive polymer in table 1 has great improvement in both the conductivity and the specific heat capacity. According to the invention, the surface energy of the lignin carbon spheres is reduced and the dispersion performance of the lignin carbon spheres is improved by coating the lignin carbon spheres with the conductive polymer, so that a high-concentration lignin carbon sphere dispersion liquid is obtained, and then the dispersion liquid of the lignin carbon spheres coated with the conductive polymer is blended with the microfibrillated cellulose, so that the lignin carbon sphere dispersion liquid is combined with the microfibrillated cellulose at a higher concentration, the loading capacity of the lignin carbon spheres in the flexible electrode material is improved, and the high-loading lignin carbon sphere/microfibrillated cellulose supercapacitor flexible electrode material can be prepared. The conductive polymer is used as a pseudo-capacitor material with a conjugated structure, and can store charges on the surface of an electrode material and in a bulk phase through reversible redox reaction, so that higher energy density is obtained. Therefore, in the flexible electrode material prepared by the invention, on one hand, the coating of the conductive polymer can provide more conductive paths for the electrode material, so that the conductivity of the flexible electrode material is improved, and on the other hand, the conductive polymer has the pseudocapacitance energy storage characteristic, so that the conductive polymer can form an energy storage synergistic effect with lignin carbon spheres, and the energy density and the capacitance performance of the flexible electrode material are improved.
Claims (5)
1. A preparation method of a flexible electrode material of a high-load lignin carbon sphere is characterized by comprising the following steps: adding monomers of lignin carbon spheres and a conductive polymer into a sulfosalicylic acid solution, ultrasonically mixing and dispersing, then placing in an ice water bath, dropwise adding an ammonium persulfate oxidant to initiate polymerization, then filtering and washing a product obtained by polymerization to obtain lignin carbon spheres coated by the conductive polymer, then preparing the lignin carbon spheres coated by the conductive polymer into a dispersion liquid, blending and stirring the dispersion liquid, microfibrillated cellulose and distilled water, and performing suction filtration and drying after stirring to obtain a finished product of the flexible electrode material.
2. The method for preparing the flexible electrode material with high-load lignin carbon spheres according to claim 1, wherein the method comprises the following steps: the preparation process of the conductive polymer coated lignin carbon spheres is as follows: uniformly dispersing 1-15 parts of lignin carbon spheres in 100-200 parts of 0.4M sulfosalicylic acid aqueous solution, adding 0.1-1.5 parts of conductive polymer monomer into a container under the condition of magnetic stirring, mixing and dispersing for 20-40min under the ultrasonic condition, then placing the container into an ice water bath, dropwise adding 30-80 parts of 0.1M ammonium persulfate solution into the container to initiate polymerization, stirring for 50-70min, and then filtering and fully washing a product obtained by polymerization to be neutral to obtain the lignin carbon spheres coated by the conductive polymer.
3. The method for preparing the flexible electrode material of the high-load lignin carbon sphere according to claim 2, wherein the method comprises the following steps: in a container, uniformly dispersing 2 parts of lignin carbon spheres in 150 parts of 0.4M sulfosalicylic acid aqueous solution, then adding 0.5 part of conductive polymer monomer into the container under the condition of magnetic stirring, placing the container under the ultrasonic condition for mixing and dispersing for 30min, then placing the container in an ice water bath, dropwise adding 50 parts of 0.1M ammonium persulfate solution into the container to initiate polymerization, stirring for 60min, and then filtering and fully washing a product obtained by polymerization to be neutral to obtain the lignin carbon spheres coated by the conductive polymer.
4. The method for preparing the flexible electrode material with high-load lignin carbon spheres according to claim 1, wherein the method comprises the following steps: the preparation process of the flexible electrode material is as follows: and (2) putting 1-15 parts of microfibrillated cellulose with the mass concentration of 0.5-2% into a container, adding 3-10 parts of dispersion liquid, adding 10-30 parts of distilled water, stirring for 20-40min, fully mixing, performing suction filtration, and drying at 50-70 ℃ for 5-7h to obtain a finished product of the flexible electrode material.
5. The method for preparing the flexible electrode material with high-load lignin carbon spheres according to claim 4, wherein the method comprises the following steps: and (2) taking 10 parts of microfibrillated cellulose with the mass concentration of 1% in a container, adding 5 parts of dispersion liquid, adding 20 parts of distilled water, stirring for 30min to fully mix, and finally performing suction filtration and drying at 60 ℃ for 6h to obtain a finished product of the flexible electrode material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113981568A (en) * | 2021-10-25 | 2022-01-28 | 大连工业大学 | Biomass-based flexible flame-retardant carbon nanofiber and preparation method and application thereof |
| CN115287941A (en) * | 2022-08-10 | 2022-11-04 | 浙江科技学院 | Preparation method of three-dimensional conductive carbon fiber paper |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20120171561A1 (en) * | 2009-09-18 | 2012-07-05 | Nec Corporation | Polymer radical material-activated carbon-conductive material composite, method for producing conductive material composite, and electricity storage device |
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| US20120171561A1 (en) * | 2009-09-18 | 2012-07-05 | Nec Corporation | Polymer radical material-activated carbon-conductive material composite, method for producing conductive material composite, and electricity storage device |
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| CN107640757A (en) * | 2017-09-07 | 2018-01-30 | 中南大学 | A kind of preparation method of compound carbosphere and compound carbosphere and its lithium-ion capacitor being prepared |
| CN107722932A (en) * | 2017-10-24 | 2018-02-23 | 浙江理工大学 | A kind of carbon/polyaniline inhales the preparation method of ripple microballoon |
| CN110808175A (en) * | 2019-10-12 | 2020-02-18 | 湖南大学 | Electroactive biomass/polypyrrole hydrogel and preparation method and application thereof |
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| CN113981568A (en) * | 2021-10-25 | 2022-01-28 | 大连工业大学 | Biomass-based flexible flame-retardant carbon nanofiber and preparation method and application thereof |
| CN113981568B (en) * | 2021-10-25 | 2023-10-27 | 大连工业大学 | Biomass-based flexible flame-retardant carbon nanofiber as well as preparation method and application thereof |
| CN115287941A (en) * | 2022-08-10 | 2022-11-04 | 浙江科技学院 | Preparation method of three-dimensional conductive carbon fiber paper |
| CN115287941B (en) * | 2022-08-10 | 2023-10-20 | 浙江科技学院 | Preparation method of three-dimensional conductive carbon fiber paper |
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