WO2023159969A1 - 一种手风琴状木质素立方体碳材料及其制备与在超级电容器中的应用 - Google Patents

一种手风琴状木质素立方体碳材料及其制备与在超级电容器中的应用 Download PDF

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WO2023159969A1
WO2023159969A1 PCT/CN2022/124434 CN2022124434W WO2023159969A1 WO 2023159969 A1 WO2023159969 A1 WO 2023159969A1 CN 2022124434 W CN2022124434 W CN 2022124434W WO 2023159969 A1 WO2023159969 A1 WO 2023159969A1
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lignin
carbon material
oxalate
accordion
solution
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French (fr)
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邱学青
杨东杰
符方宝
易聪华
张文礼
楼宏铭
黄锦浩
庞煜霞
刘伟峰
秦延林
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华南理工大学
广东工业大学
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • 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
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the technical field of biomass carbon materials, and in particular relates to an accordion-shaped lignin cubic carbon material and its preparation and application in supercapacitors.
  • supercapacitors As a new type of energy storage device, supercapacitors have the advantages of high power density, fast charging and discharging, long cycle life, and wide application temperature, and are widely used in the fields of power grid frequency modulation and backup power supply. Electrode materials are the key factors affecting the performance of supercapacitors. Carbon materials have the advantages of wide sources, adjustable pore structure, and good electrical conductivity. They are currently widely used electrode materials. Activated carbon has high specific surface area, low cost, and stable chemical properties, but its mass specific capacitance is low due to its disordered structure; the theoretical specific capacity of graphene is 550F/g, but its carbon nanosheets are easy to accumulate, resulting in low utilization of effective specific surface area.
  • Lignin is the second largest plant resource, accounting for about 30% of the dry weight of the plant. Its structural unit is phenylpropane, which contains a large number of benzene ring structures and oxygen-containing functional groups. The carbon content is as high as 60%, and it is an ideal carbon material precursor. body. It can be converted into functional carbon materials by pyrolysis, which has become a research hotspot in recent years as an energy storage electrode material.
  • the microstructural properties of lignin-based carbon materials are key factors affecting the performance of supercapacitors.
  • the ordered hierarchical porous structure can improve the effective surface utilization of carbon materials, thereby enhancing the capacitive performance.
  • Two-dimensional carbon nanosheets have open active sites and good structural continuity, which can accelerate ion transport and electron transport. Therefore, 2D carbon nanosheets have received extensive attention.
  • Chinese patent application CN109485029A discloses a preparation of porous carbon nanosheets using lignin and its application in supercapacitors.
  • the method uses water-soluble sulfonated lignin as carbon precursor and dispersant, and weakly corrosive oxalate as activation agent, the two were dissolved in water solvent, and then dropwise added ethanol for multiple hydrophobic self-assembly to prepare lignin/oxalate composites, and then carbonized lignin porous carbon nanosheets, the carbon nanosheets specific surface area reached 1069m 2 /g, and the specific capacitance at 1A/g current density is 320F/g.
  • the process uses at least 6 self-assembly processes, and the operation process is cumbersome and difficult.
  • Fu et al. (Chemical Engineering Journal 392 (2020) 12372) used sodium lignosulfonate as a carbon source, and zinc oxalate generated from zinc nitrate and sodium oxalate as a template and an activator.
  • Sodium oxalate was added to form a suspension, and then ethanol was gradually added dropwise for hydrophobic self-assembly to prepare a lignin/zinc oxalate composite, and then carbonized to prepare a lignin quasi-nanosheet carbon material with two-dimensional interconnection.
  • Synthetic zinc oxalate as a template has a more orderly sheet structure than the lignin carbon prepared directly by zinc oxalate, but the stacking of nanosheets is serious, resulting in thick lignin carbon sheets, which reduces the effective utilization of the specific surface area of the material .
  • Liu et al. (RSC Adv., 2017, 7, 48537) prepared lignin carbon nanosheets by direct carbonization using alkali lignin as a raw material and ice crystals formed by freeze casting in liquid nitrogen as a template.
  • the carbon nanosheets prepared by the method have a specific capacitance of 281F/g at a current density of 0.5A/g.
  • the overall structure of the two-dimensional carbon nanosheets obtained by the above preparation method is disordered, the specific surface area is high, and there are problems such as unsupported sheets, poor structural stability and low effective utilization of the specific surface area, resulting in a low area specific capacity. Therefore, in order to improve the structural stability of carbon nanosheets, researchers have prepared carbon materials with a three-dimensional structure composed of nanosheets. Zhang Binpeng (B.
  • Zhang et al./Carbon 162(2020) 256-266) combined enzymatic lignin with two-dimensional sheet-like nano-MgO to obtain flower-like lignin/Mg(OH) through a volatilization-induced self-assembly process 2 composite, and then the composite was carbonized and the template was removed to obtain a lignin-based flower-like carbon material with a diameter of 5 ⁇ m.
  • the material has a stable flower-like structure, which enhances the photocatalytic performance of zinc oxide compared with two-dimensional carbon nanosheets, but the specific surface area is only 827m 2 /g, and the overall structure of the flower-like carbon is larger, so it is active as an electrode material. Insufficient sites are not suitable as electrode materials.
  • flower-like carbon materials have better structural stability and exhibit good rate performance.
  • the dense inner core of the flower-like structure reduces the specific surface area of carbon nanosheets, resulting in a reduction in the active sites of electrolyte ions, especially at low current densities with low mass specific capacitance.
  • the three-dimensional cubic carbon material has a stable framework structure and sufficient space to load active materials inside, which has significant advantages as an energy storage electrode material.
  • carbon materials derived from metal-organic framework materials such as ZIF-8, ZIF-67
  • ZIF-8, ZIF-67 metal-organic framework materials
  • the lignin carbon materials prepared by the current existing technologies or processes have problems such as poor structural stability and low effective utilization of surface area, resulting in low specific capacitance and poor rate performance.
  • the following key problems need to be solved: First, the interaction force between the activator or templating agent used in the existing preparation technology and lignin is weak, and the two cannot be effectively compounded to construct macroscopically ordered precursors, resulting in the overall structure of lignin carbon materials Disorder, which significantly reduces the mass specific capacity and rate performance; second, the activator or templating agent used does not have a good confinement effect on the lignin carbon skeleton, resulting in poor structural stability and serious accumulation of lignin carbon nanosheets, which significantly reduces The effective specific surface area is reduced, resulting in a lower areal specific capacity.
  • the primary purpose of the present invention is to provide a method for preparing an accordion-shaped lignin cubic carbon material.
  • the method of the invention is to prepare the accordion-shaped lignin cubic carbon material by adopting the evaporation assembly carbonization method. Firstly, the industrial lignin is dissolved in alkali, and then the lignin is purified under weak acid to enhance its solubility in the alcohol-water mixed solvent, and the hydrogen bond between the purified lignin and the block copolymer is further utilized in the alcohol-water mixed solvent Form lignin/block copolymer mixed micelles, then add soluble zinc salt and oxalate in sequence, use solvent evaporation to induce co-deposition of mixed micelles and zinc oxalate under neutral conditions, and control the evaporation rate to make lignin/block copolymer Block copolymer mixed micelles were deposited between the zinc oxalate layers to construct a structured cubic lignin/block copolymer/zinc oxalate composite. Subsequent carbonization yielded accordion-shaped lignin cubic carbon materials with ordered structure
  • Another object of the present invention is to provide a kind of accordion-shaped lignin cubic carbon material prepared by the above method, which has abundant ion migration space, and has interconnected support nano-sheets inside, which solves the problem of easy accumulation of carbon nano-sheets Problems, improve the effective surface utilization, thereby significantly improving the quality and area specific capacitance and rate performance of supercapacitors.
  • the specific surface area of the accordion-shaped lignin cubic carbon material is not less than 1000m 2 /g, the size is not more than 2 ⁇ m, and the sheet thickness is less than 20nm.
  • Another object of the present invention is to provide the application of the above-mentioned accordion-shaped lignin cubic carbon material in supercapacitors.
  • a preparation method of an accordion-shaped lignin cubic carbon material comprising the following steps:
  • the ratio of purified lignin, block copolymer, soluble zinc salt, soluble oxalate and ethanol-water mixed solvent in step (2) is 100g: 5-50g: 20-100g: 20-100g: 2000- 5000mL.
  • the ratio of purified lignin, block copolymer, soluble zinc salt, soluble oxalate and ethanol-water mixed solvent in step (2) is 100g: 20-30g: 50-80g: 50-80g: 2000 ⁇ 3000mL.
  • the industrial lignin in step (1) is selected from wood pulp alkali lignin, bamboo pulp alkali lignin, wheat straw pulp alkali lignin, bagasse pulp alkali lignin, wood pulp black liquor lignin, bamboo pulp black liquor lignin At least one of lignin, wheat straw pulp black liquor lignin and bagasse pulp black liquor lignin.
  • the alkali solution with a pH of 12 or higher in step (1) is at least one of ammonia water, sodium hydroxide solution and potassium hydroxide solution.
  • the mass concentration of the industrial lignin in step (1) in the alkaline solution is 10-30%; more preferably 10-20%.
  • the pH of the solution adjusted by adding acid in step (1) is 5-7, and the pH is preferably 6.
  • the acid is at least one of 0.5-1.5 mol/L hydrochloric acid, sulfuric acid and phosphoric acid.
  • the block copolymer described in step (2) is polyethylene glycol-b-poly N-isopropylacrylamide-b-polyglycolide, star polylactic acid-polyethylene glycol, polyethylene glycol At least one of alcohol monomethyl ether-polystyrene-polyglycolide, polyethylene glycol-aliphatic polyester-polyamino acid and polylactic acid-biotin dextran amine-DTMPDOL, more preferably polyethylene glycol Alcohol-b-poly-N-isopropylacrylamide-b-polyglycolide.
  • the volume ratio of ethanol to water in the ethanol-water mixed solvent in step (2) is 1-4:1, more preferably 2-3:1.
  • the dropping rate of the soluble zinc salt solution and the oxalate solution in step (2) is 10-50mL/min;
  • the soluble zinc salt is at least one of zinc nitrate, zinc chloride, zinc acetate and zinc citrate.
  • the soluble oxalate is at least one of sodium oxalate, potassium oxalate and ammonium oxalate.
  • the mass concentrations of both the soluble zinc salt solution and the oxalate solution in step (2) are 2-10%, more preferably 2-6%.
  • vacuum rotary evaporation is used for the evaporation in step (2), and the vacuum degree is 0.02-0.08 MPa, more preferably 0.04-0.06 MPa.
  • the carbonization in step (3) refers to carbonization at 600-900° C. for 1-3 hours.
  • the carbonization in step (3) is carried out under an inert gas or nitrogen atmosphere.
  • the washing in step (3) refers to washing the carbonized product in 0.1-1.5 mol/L acid solution for 1-3 hours, and then washing with water.
  • the 0.1-1.5 mol/L acid solution is at least one of hydrochloric acid, sulfuric acid and nitric acid.
  • the drying in step (3) is at least one of freeze drying, blast drying, vacuum drying and infrared drying, more preferably freeze drying.
  • the drying temperature in step (3) is 50-100° C., and the time is 2-8 hours; more preferably, the drying temperature is 60-80° C., and the time is 4-6 hours.
  • the alkali-soluble acid precipitation method is used to separate and purify lignin, and at the same time, the ethanol/water mixed system in step (2) needs to meet the requirement of good solubility of lignin, so the pH of the acid solution is adjusted to 5-7.
  • the solubility of lignin in the ethanol/water system is too large, and in the process of evaporating the solvent in step (2), it is difficult for the lignin/block copolymer mixed micelles to co-deposit with zinc oxalate, and the mixed glue Agglomeration between bundles is easy to occur, and the limited growth effect of zinc oxalate on lignin cannot be exerted; if the pH>7, the solubility of lignin in the ethanol/water system is too small, and the lignin/embedding formed in the ethanol/water system The number of segment copolymer mixed micelles is small, which cannot be effectively deposited on the surface and interlayer of zinc oxalate, and the zinc oxalate sheets are prone to agglomeration, which is not conducive to the formation of a stable lignin/block copolymer/zinc oxalate composite .
  • step (2) Add a certain amount of lignin and block copolymer purified in step (1) into the ethanol-water mixing system, stir for 2-4 hours and let it stand for 3-6 hours, then slowly add soluble zinc salt and oxalate in sequence The solution is then evaporated at a certain evaporation rate at 70-90°C for 4-8 hours, then filtered and dried to obtain a lignin/block copolymer/zinc oxalate composite;
  • This step is to form uniformly dispersed lignin/block copolymer mixed micelles, which are then deposited on the surface and interlayer of zinc oxalate, and form a structurally stable lignin/block with the help of the confinement effect of zinc oxalate on lignin
  • the copolymer/zinc oxalate composite is conducive to the formation of a continuous and stable cubic carbon material in the subsequent carbonization process.
  • This step must control the rate of addition of soluble zinc salt and oxalate. If the rate of addition is too slow, a large amount of lignin/block copolymer mixed micelles will deposit multilayer micellar balls on the surface of zinc oxalate, zinc oxalate sheet layer A stable interconnected structure cannot be formed between them, and the confinement effect of zinc oxalate cannot be exerted; if the dropping rate is too fast, a large amount of zinc oxalate will be generated in a short period of time and then agglomerated, and the accumulation between the sheets is serious, which is not conducive to the subsequent carbonization process.
  • the template zinc oxalate in the system is generated by the reaction of two soluble salts.
  • Zinc oxalate cannot be used directly. If zinc oxalate is used directly, the lignin/block copolymer mixed micelles cannot be effectively deposited between the zinc oxalate sheets. At the same time, The severe agglomeration of zinc oxalate, likewise, is not conducive to the subsequent carbonization process.
  • step (3) carbonize the lignin/block copolymer/zinc oxalate composite in step (2), wash, centrifuge, and dry to obtain an accordion-shaped lignin cubic carbon material.
  • the carbonization atmosphere in this step is nitrogen, argon or other inert gases.
  • the carbonization temperature is required to be in the range of 600-900°C, and the time is 1-3 hours. If the temperature is too low and the time is too short, it will lead to incomplete carbonization; if the temperature is too high and the time is too long, it will not only increase the production cost, but also The structure of the cubic carbon material is unstable.
  • the present invention has the following advantages and beneficial effects:
  • the accordion-shaped lignin cubic carbon material prepared by the present invention has an orderly interconnected sheet structure and excellent structural stability, which can not only increase the diffusion rate of electrolyte ions, but also improve the effective use of the specific surface area of the carbon material Rate.
  • As a supercapacitor electrode material it has excellent mass and area specific capacitance and rate performance.
  • Fig. 1 is a scanning electron micrograph of the accordion-shaped lignin cubic carbon material prepared in Example 1 of the present invention.
  • Fig. 2 is a transmission electron microscope image (1 ⁇ 2 micron) of the accordion-shaped lignin cubic carbon material prepared in Example 1 of the present invention.
  • Fig. 3 is a nitrogen adsorption-desorption curve and a pore size distribution diagram of the accordion-shaped lignin cubic carbon material prepared in Example 1 of the present invention.
  • Fig. 4 is a cyclic voltammetry curve of the accordion-shaped lignin cubic carbon material prepared in Example 1 of the present invention.
  • Fig. 5 is a constant DC charge and discharge curve of the accordion-shaped lignin cubic carbon material prepared in Example 1 of the present invention.
  • Polystyrene-polyglycolide, polylactic acid-biotin dextran amine-DTMPDOL were purchased from Sigma Aldrich.
  • the mixed solution was rotary evaporated at 80°C and a vacuum of 0.05MPa for 4h, left to stand and filtered to obtain a precipitate, and the precipitate was dried in an infrared oven at 60°C for 5h to obtain lignin/polyethylene glycol Alcohol-b-poly-N-isopropylacrylamide-b-polyglycolide/zinc oxalate complex.
  • the mixed solution was rotary evaporated at 70°C and a vacuum of 0.06MPa for 6h, left to stand and filtered to obtain a precipitate, and the precipitate was dried in an infrared oven at 70°C for 6h to obtain lignin/star polymer Lactic acid-polyethylene glycol/zinc oxalate complex.
  • the mixed solution was rotary evaporated at 75°C and a vacuum of 0.05MPa for 4h, left to stand and filtered to obtain a precipitate, and the precipitate was dried in a blast oven at 80°C for 4h to obtain lignin/polyethylene Glycol monomethyl ether-polystyrene-polyglycolide/zinc oxalate complex.
  • the mixed solution was rotary evaporated at 70°C and a vacuum of 0.04MPa for 6h, left to stand and filtered to obtain a precipitate, and the precipitate was dried in a blast oven at 80°C for 6h to obtain lignin/polylactic acid -Biotin-dextran amine-DTMPDOL/zinc oxalate complex.
  • Example 1 The accordion-shaped lignin cubic carbon material prepared in Example 1 was applied to supercapacitor electrode materials and subjected to material characterization and electrochemical tests. The results are shown in Table 1 and Figures 1-5.
  • the microscopic morphology and structure of the samples were characterized by scanning electron microscopy (SEM, Hitachi S-550) and high-resolution field emission transmission electron microscopy (HRTEM, JEOL JEM-2100F, 200kV).
  • SEM scanning electron microscopy
  • HRTEM high-resolution field emission transmission electron microscopy
  • the specific surface area and pore structure of the samples were tested using a fully automatic specific surface and porosity analyzer (Micromeritics ASAP 2020instrument).
  • Electrochemical tests were performed on an electrochemical workstation (CHI660E, Shanghai Chenhua), and all tests used a three-electrode system.
  • the preparation process of the working electrode is as follows: disperse the prepared lignin cubic carbon material, acetylene black and polytetrafluoroethylene emulsion (solid content 60wt%) in absolute ethanol with a mass ratio of 8:1:1, fully grind, and wait for ethanol After it is completely volatilized, it is coated on a nickel foam of 1 cm ⁇ 1 cm, and the working electrode is obtained after pressing into a tablet.
  • the counter electrode was a platinum sheet electrode, and the reference electrode was a saturated calomel electrode.
  • the cyclic voltammetry test was completed at a voltage window of -1-0V at a scanning speed of 5-200mv/s.
  • the constant DC charge and discharge curve test is completed at a voltage window of -1 to 0V and a current density of 0.5 to 20.0A/g.
  • Table 1 is a comparison of the electrochemical properties of the accordion-shaped lignin cubic carbon materials prepared in the above examples and the samples prepared in the following comparative examples.
  • the preparation technology of comparative example sample is as follows:
  • Comparative example 2 water-soluble sulfonated lignin
  • Comparative example 3 (directly adopt zinc oxalate)
  • the mixed solution was rotary evaporated at 70°C and a vacuum of 0.04MPa for 4 hours, left to stand and filtered to obtain a precipitate, and the precipitate was dried in a blast oven at 80°C for 4 hours to obtain lignin/zinc oxalate Complex.
  • the mixed solution was rotary evaporated at 70°C and a vacuum of 0.04MPa for 4h, left to stand and filtered to obtain a precipitate, and the precipitate was dried in a blast oven at 80°C for 4h to obtain lignin/polyoxygen Propylene polyoxyethylene copolymer F127/zinc oxalate complex.
  • Comparative example 6 purification of industrial wood pulp alkali lignin with pH ⁇ 5
  • Comparative example 7 purification of industrial wood pulp alkali lignin with pH>7
  • the mass and area specific capacitance of the accordion-shaped lignin cubic carbon material prepared in Example 1 at a current density of 0.5A/g are 358F/g and 34.1 ⁇ F/cm 2 , respectively.
  • the current density is 20A/g
  • the mass and area specific capacitance of the material are 255F/g and 24.3 ⁇ F/cm 2 , respectively, and the specific capacitance retention rate, that is, the rate performance is as high as 71.2%.
  • the mass specific capacitance of all samples in the examples is higher than 330F/g, the area specific capacitance is higher than 34.1 ⁇ F/cm 2 , and the rate performance is higher than 71.2%, which is much higher than that of the samples in the comparative example, which is mainly due to the following two points: (1) The orderly interconnected sheet structure of lignin cubic carbon materials accelerates the ion transport rate and improves the effective utilization of the specific surface area of the material; (2) The confinement effect of zinc oxalate on lignin strengthens the cubic carbon materials structural stability. The synergistic effect of the two makes the lignin cubic carbon material have both high quality and area specific capacitance and rate performance. Therefore, the accordion-shaped lignin cubic carbon material prepared by the present invention exhibits very excellent electrochemical properties in terms of specific capacitance and rate performance.
  • the unsulfonated lignin in the sample of Comparative Example 1 has low solubility in aqueous solution, and cannot form sufficient binary mixed micelles with the block copolymer and deposit on the surface and interlayer of zinc oxalate, Zinc oxalate self-agglomeration is serious, and disordered precipitates are obtained after hydrophobic self-assembly.
  • the carbonized product presents a two-dimensional sheet structure, the macroscopic structure is disordered, and the sheet is thicker, and the accordion-shaped cubic structure, quality and area
  • the specific capacitances are 288F/g and 23.0 ⁇ F/cm 2 respectively, and the rate capability is only 52.0%.
  • the water-soluble sulfonated lignin has a low solubility in the ethanol/water system, and the zinc oxalate sheet cannot be effectively dispersed by the binary mixed micelles and then piles up disorderly and randomly.
  • the prepared carbon material The sheets are disordered, and the interconnections cannot be effectively supported between the sheets.
  • the mass and area specific capacitances are 276F/g and 21.6 ⁇ F/cm 2 , and the rate performance is only 50.7%.
  • the final prepared lignin The plain carbon material is in a large block shape, and the mass and area specific capacitance of the material in Comparative Example 6 are only 140F/g and 14.8 ⁇ F/cm 2 ; the mass and area specific capacitance of the material in Comparative Example 7 are only 138F/g and 14.5 ⁇ F /cm 2 .
  • the solubility of lignin in the ethanol/water system is too large, and in the process of evaporating the solvent in step (2), it is difficult for the lignin/block copolymer mixed micelles to co-deposit with zinc oxalate, and the mixed glue Agglomeration between bundles is easy to occur, and the limited growth effect of zinc oxalate on lignin cannot be exerted; if the pH>7, the solubility of lignin in the ethanol/water system is too small, and the lignin/embedding formed in the ethanol/water system The number of segment copolymer mixed micelles is small, which cannot be effectively deposited on the surface and interlayer of zinc oxalate, and the zinc oxalate sheets are prone to agglomeration, which is not conducive to the formation of a stable lignin/block copolymer/zinc oxalate composite .
  • Fig. 1 is a scanning electron micrograph of the accordion-shaped lignin cubic carbon material prepared in Example 1 of the present invention. It can be seen from the figure that the as-prepared lignin cubic carbon material has a typical accordion-shaped cubic structure, and the sheets are interconnected in an orderly manner with good structural stability.
  • Fig. 2 is a transmission electron microscope image of the accordion-shaped lignin cubic carbon material prepared in Example 1 of the present invention. It can be seen from the figure that the sheets of the lignin cubic carbon material are interconnected in an orderly manner, and there is a rich pore structure between the sheets, which greatly improves the effective utilization of the specific surface area of the carbon cubic material.
  • Fig. 3 is a nitrogen adsorption-desorption curve and a pore size distribution diagram of the accordion-shaped lignin cubic carbon material prepared in Example 1 of the present invention. It can be seen from the figure that the adsorption-desorption curve of the lignin cubic carbon material belongs to type IV, and has a hysteresis loop of type H3. In the region of low relative pressure, the amount of nitrogen adsorption increased rapidly, indicating a microporous structure, while hysteresis loops appeared in the region of high relative pressure, indicating a mesoporous structure.
  • the total BET specific surface area of the lignin porous carbon nanosheets is 1050m 2 /g, of which the micropore specific surface area is 647m 2 /g, the mesopore specific surface area is 403m 2 /g, and the total pore volume is 0.918cm 3 /g. Its pore size distribution is very wide, and the reasonable pore structure and rich pore size distribution are conducive to the improvement of electrochemical performance.
  • Fig. 4 is a cyclic voltammetry curve of the accordion-shaped lignin cubic carbon material prepared in Example 1 of the present invention. It can be seen from the figure that the curves of the material at different scan rates are all quasi-rectangular, which indicates that the material has an ideal electric double layer capacitance. Excellent performance.
  • Fig. 5 is a constant DC charge and discharge curve of the accordion-shaped lignin cubic carbon material prepared in Example 1 of the present invention. It can be seen from the figure that the curve shapes of the prepared lignin cubic carbon materials at different current densities are similar to isosceles triangles, which indicates that the carbon materials have typical electric double layer capacitance characteristics.

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Abstract

一种手风琴状木质素立方体碳材料、制备方法以及其在超级电容器中的应用。首先将工业木质素碱溶并在弱酸下提纯，然后在醇水混合溶剂中与嵌段共聚物形成胶束，再依次加入可溶性锌盐和草酸盐，在中性条件下采用溶剂蒸发诱导使混合胶束和草酸锌共沉积，同时控制蒸发速率使木质素/嵌段共聚物混合胶束在草酸锌层间沉积，构建结构有序的立方体状木质素/嵌段共聚物/草酸锌复合物，最后碳化得到手风琴状木质素立方体碳材料。该材料具有丰富的离子迁移空间，内部具有互连的支撑纳米片层，解决了碳纳米片易堆积的问题，提高了有效表面利用率，从而显著提升了超级电容器的质量和面积比电容以及倍率性能。

Description

一种手风琴状木质素立方体碳材料及其制备与在超级电容器中的应用 技术领域
本发明属于生物质碳材料技术领域，具体涉及一种手风琴状木质素立方体碳材料及其制备与在超级电容器中的应用。
背景技术
超级电容器作为新一类储能器件，具有高功率密度、快速充放电、循环寿命长、适用温度宽等优点，在电网调频和备用电源等领域得到广泛应用。电极材料是影响超级电容器性能的关键因素，碳材料具有来源广泛、孔道结构可调控、导电性能良好等优点，是目前应用广泛的电极材料。活性炭比表面积高、成本低、化学性质稳定，但由于结构无序使得其质量比电容较低；石墨烯理论比容量为550F/g，但其碳纳米片易堆积，导致有效比表面积利用低，显著降低了面积比容量，且石墨烯的成本高，不利于实现工业化应用。因此，迫切需要开发一种来源广泛、成本低廉、质量及面积比电容高且具备工业化潜力的超级电容器碳材料。
木质素是储量第二大的植物资源，占植物体干重约30％，其结构单元为苯丙烷，含有大量的苯环结构以及含氧官能团，碳含量高达60％，是理想的碳材料前驱体。通过热解可以转化为功能性碳材料，其作为储能电极材料成为近年来的研究热点。
木质素碳材料的微观结构特性是影响超级电容器性能的关键因素。有序的分级多孔结构能够提升碳材料的有效表面利用率，从而提升电容性能。二维碳纳米片具有开放的活性位点和良好的结构连续性，可以加速离子输运和电子传输。因此，二维碳纳米片受到了广泛的关注。中国专利申请CN109485029A公开了一种利用木质素制备多孔碳纳米片以及在超级电容器中的应用，该方法以水溶性磺化木质素作为碳前驱体和分散剂，弱腐蚀性的草酸盐作为活化剂，将二者溶于水溶剂中，然后滴加乙醇进行多次疏水自组装制备了木质素/草酸盐复合物，然后碳化制备了木质素多孔碳纳米片，该碳纳米片比表面积达到1069m 2/g，在1A/g电流密度下的比电容为320F/g，为得到纳米片层结构同时避免纳米片的堆叠，该工艺采用至少6次以上的自组装过程，操作工艺繁琐，难以规模化生产，此外直接采用草酸盐水溶性差，导致了木质素碳的结构无序。Fu等(Chemical Engineering Journal 392(2020)12372)以木质素磺酸钠作为碳源，硝酸锌与草酸钠生成的草酸锌为模板和活化剂，通过向木质素磺酸钠和硝酸锌的混合水溶液中加入草酸钠形成悬浮液，随后逐步滴加乙醇进行疏水自组装制备了木质素/草酸锌复合物，然后碳化制备了具有二维互连的木质素准纳米片碳材料。合成草酸锌作为模板相比直接采用草酸锌制备的木质素碳具有更为有序的片层结构，但纳米片堆叠严重，造成木质素碳片层较厚，降低了材料比表面积的有效利用率。Liu等(RSC Adv.,2017,7,48537)以碱木质素为原料，利用液氮中冷冻浇铸生成的冰晶为模板，直接碳化制备了木质素碳纳米片。该方法制备的碳纳米片在0.5A/g电流密度下的比电容为281F/g。
上述制备方法得到的二维碳纳米片整体结构无序，比表面积较高，且存在着片层无支撑、结构稳定性差和比表面积有效利用率低等问题，导致其面积比容量较低。因此，为了提升碳纳米片的结构稳定性，研究人员制备了由纳米片层组成的具有立体结构的碳材料。张宾朋(B.Zhang et al./Carbon 162(2020)256-266)将酶解木质素与二维片状的纳米MgO通过挥发诱导自组装过程得到花状结构的木质素/Mg(OH) 2复合物，随后将复合物碳化并且去除模板后得到直径为5μm的木质素基花状炭材料。该材料具有稳定的花状结构，与二维碳纳米片相比，增强了氧化锌光催化性能，但比表面积仅为827m 2/g，且花状碳的整体结构较大，作为电极材料活性位点不足，不适合作为电极材料。Wang等(F.Wang et al./Journal of Alloys and Compounds 812(2020)152109)以脲醛树脂为原料，采用直接碳化法合成了直径为3μm花状碳球，比表面积为611m 2/g，在2mV/s扫描速率下的比电容为276F/g。Liang等(J.Mater.Chem.A,2014,2, 16884–16891)以葡萄糖为碳源，花状Ni(OH) 2为模板，通过水热反应及高温碳化制备了直径为5μm，比表面积为796m 2/g的花状碳材料，在0.5A/g电流密度下的比电容为226F/g，在20A/g大电流密度下的比电容为185F/g，比电容保持率高达82％。相比于二维碳纳米片，花状碳材料具有更优的结构稳定性，表现出良好的倍率性能。然而花状结构密实的内核降低了碳纳米片的比表面积，导致电解质离子的活性位点减少，尤其在低电流密度下的质量比电容较低。
三维立方体碳材料具有稳定的框架结构，内部有充足的空间装载活性物质，作为储能电极材料具有显著的优势。如金属有机骨架材料(如ZIF-8、ZIF-67)衍生碳材料，具有三维纳米立方体结构，作为钠硫离子电池电极材料能显著提高多硫化物的固载率，且有效催化硫氧化还原反应(Small Methods 2021,2100455)。但目前仍未见木质素立方体碳材料的相关报道。
综上所述，目前现有的技术或者工艺所制备的木质素碳材料存在结构稳定性差、表面积有效利用率低，导致比电容低和倍率性能差等问题。需要解决以下关键问题：一是现有制备技术采用的活化剂或模板剂与木质素间的相互作用力弱，两者无法进行有效复合构建宏观有序的前驱物，导致木质素碳材料整体结构无序，显著降低了质量比容量和倍率性能；二是所采用的活化剂或模板剂对木质素碳骨架没有良好限域作用，导致所得木质素碳纳米片结构稳定性差且堆积严重，显著降低了有效比表面积，导致较低面积比容量。
发明内容
为解决现有技术的缺点和不足之处，本发明的首要目的在于提供一种手风琴状木质素立方体碳材料的制备方法。
本发明所述方法是采用蒸发组装炭化法制备手风琴状木质素立方体碳材料。首先将工业木质素进行碱溶，然后在弱酸下提纯木质素，以增强其在醇水混合溶剂中溶解性，进一步利用提纯木质素与嵌段共聚物的氢键作用，在醇水混合溶剂中形成木质素/嵌段共聚物混合胶束，然后依次加入可溶性锌盐和草酸盐，在中性条件下采用溶剂蒸发诱导使混合胶束和草酸锌共沉积，同时控制蒸发速率使木质素/嵌段共聚物混合胶束在草酸锌层间沉积，构建了结构有序的立方体状木质素/嵌段共聚物/草酸锌复合物。后续碳化得到结构有序、稳定性良好、内部片层支撑互连的手风琴状木质素立方体碳材料。
本发明的另一目的在于提供上述方法制得的一种手风琴状木质素立方体碳材料，该材料具有丰富的离子迁移空间，内部具有互连的支撑纳米片层，解决了碳纳米片易堆积的问题，提高了有效表面利用率，从而显著提升了超级电容器的质量和面积比电容以及倍率性能。
在本发明中，所述手风琴状木质素立方体碳材料的比表面积不低于1000m 2/g，尺寸不超过2μm，片层厚度小于20nm。
本发明的再一目的在于提供上述一种手风琴状木质素立方体碳材料在超级电容器中的应用。
本发明目的通过以下技术方案实现：
一种手风琴状木质素立方体碳材料的制备方法，包括以下步骤：
(1)将工业木质素溶于pH为12以上的碱溶液中，然后加酸调节溶液pH为5～7，过滤分离沉淀，将沉淀物干燥，得到纯化木质素；
(2)将纯化木质素和嵌段共聚物加入到乙醇水混合溶剂中，搅拌2～4h，静置3～6h，形成木质素/嵌段共聚物混合胶束，然后依次滴加可溶性锌盐溶液和草酸盐溶液，在70～90℃下蒸发4～8h，过滤，干燥，得到木质素/嵌段共聚物/草酸锌复合物；
(3)将木质素/嵌段共聚物/草酸锌复合物进行碳化，洗涤，离心，干燥，得到手风琴状木质素立方体碳材料。
优选的，步骤(2)所述纯化木质素、嵌段共聚物、可溶性锌盐、可溶性草酸盐和乙醇水混合溶剂的比例为100g：5～50g：20～100g：20～100g：2000～5000mL。
更优选的，步骤(2)所述纯化木质素、嵌段共聚物、可溶性锌盐、可溶性草酸盐和乙醇水混合溶剂的比例为100g：20～30g：50～80g：50～80g：2000～3000mL。
优选的，步骤(1)所述工业木质素选自木浆碱木质素、竹浆碱木质素、麦草浆碱木质素、蔗渣浆碱木质素、木浆黑液木质素、竹浆黑液木质素、麦草浆黑液木质素和蔗渣浆黑液木质素中的至少一种。
优选的，步骤(1)所述pH为12以上的碱溶液为氨水、氢氧化钠溶液和氢氧化钾溶液中的至少一种。
优选的，步骤(1)所述工业木质素在碱溶液中的质量浓度为10～30％；更优选为10～20％。
优选的，步骤(1)所述加酸调节溶液的pH为5～7，pH优选为6。所述酸为0.5～1.5mol/L的盐酸、硫酸和磷酸中的至少一种。
优选的，步骤(2)所述嵌段共聚物为聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯、星形聚乳酸-聚乙二醇、聚乙二醇单甲醚-聚苯乙烯-聚乙内酯、聚乙二醇-脂肪族聚酯-聚氨基酸和聚乳酸-生物素葡聚糖胺-DTMPDOL中的至少一种，更优选为聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯。
优选的，步骤(2)所述乙醇水混合溶剂中乙醇和水的体积比为1～4：1，更优选为2～3：1。
优选的，步骤(2)所述可溶性锌盐溶液和草酸盐溶液的滴加速率均为10～50mL/min；可溶性锌盐为硝酸锌、氯化锌、乙酸锌和柠檬酸锌中的至少一种；可溶性草酸盐为草酸钠、草酸钾和草酸铵中的至少一种。
优选的，步骤(2)所述可溶性锌盐溶液和草酸盐溶液的质量浓度均为2～10％，更优选为2～6％。
优选的，步骤(2)所述蒸发采用真空旋转蒸发，真空度为0.02～0.08MPa，更优选为0.04～0.06MPa。
优选的，步骤(3)所述碳化指在600～900℃碳化1～3h。
优选的，步骤(3)所述碳化在惰性气体或氮气气氛下进行。
优选的，步骤(3)所述洗涤是指将碳化产物在0.1～1.5mol/L的酸液中洗涤1～3h，然后水洗。
更优选的，所述0.1～1.5mol/L的酸液为盐酸、硫酸和硝酸中的至少一种。
优选的，步骤(3)所述干燥为冷冻干燥、鼓风干燥、真空干燥和红外干燥中的至少一种，更优选为冷冻干燥。
优选的，步骤(3)所述干燥温度为50～100℃，时间为2～8h；更优选的，干燥温度为60～80℃，时间为4～6h。
上述方法制得的一种一种手风琴状木质素立方体碳材料。
上述一种手风琴状木质素立方体碳材料在超级电容器中的应用。
下面将更加详细地描述本发明专利所述的制备方法。
(1)将工业木质素溶于pH为12以上的碱溶液中，然后加酸调节溶液pH为5～7，过滤分离沉淀，将沉淀物干燥，得到提纯木质素；
该步骤采用碱溶酸沉淀法目的是分离提纯木质素，同时需要满足步骤(2)中的乙醇/水混合体系对木质素的良好溶解度的要求，因此酸溶液的pH调节为5～7。
若pH＜5，则木质素在乙醇/水体系中的溶解度太大，在步骤(2)蒸发溶剂的过程中，木质素/嵌段共聚物混合胶束难以与草酸锌共沉积，且混合胶束之间容易发生团聚，无法发挥草酸锌对木质素的限域生长作用；若pH＞7，则木质素在乙醇/水体系中的溶解度太小，乙醇/水体系中形成的木质素/嵌段共聚物混合胶束数量较少，无法有效沉积在草酸锌的表面与层间，草酸锌片层之间容易发生团聚，不利于形成结构稳定的木质素/嵌段共聚物/草酸锌复合物。
(2)将一定量的步骤(1)提纯木质素与嵌段共聚物加入到乙醇水混合体系中，搅拌2～4小时静置3～6小时，依次缓慢滴加可溶性锌盐和草酸盐溶液，接着在70～90℃下以一定的蒸发速率进行蒸发4～8小时，而后过滤、干燥得到木质素/嵌段共聚物/草酸锌复合物；
该步骤是为了形成分散均匀的木质素/嵌段共聚物混合胶束，进而沉积在草酸锌的表面与层间，借助草酸锌对木质素的限域作用，形成结构稳定的木质素/嵌段共聚物/草酸锌复合物，有利于后续碳化过程中形成结构连续与稳定的立方体碳材料。
该步骤必须控制可溶性锌盐和草酸盐的滴加速度，若滴加速度太慢，大量木质素/嵌段共聚物混合胶束会在草酸锌的表面沉积出多层胶束球，草酸锌片层之间无法形成互连稳定的结构，无法发挥草酸锌的限域作用；若滴加速度太快，草酸锌短时间内大量生成进而发生团聚，片层之间堆积严重，不利于后续碳化过程。体系中的模板草酸锌是由两种可溶性盐反应生成，不能直接使用草酸锌，若直接使用草酸锌，木质素/嵌段共聚物混合胶束无法有效沉积在草酸锌片层之间，同时，草酸锌团聚严重，同样地，不利于后续碳化过程。
(3)将步骤(2)的木质素/嵌段共聚物/草酸锌复合物进行碳化，洗涤，离心，干燥后得到了手风琴状木质素立方体碳材料。
此步骤中碳化氛围为氮气、氩气或其他惰性气体。碳化温度要求在600～900℃范围内，时间在1～3h，若温度过低、时间过短，则会导致碳化不完全；若温度过高、时间过长，则不仅会提升生产成本，还造成立方体碳材料结构不稳定。
与现有技术相比，本发明具有以下优点及有益效果：
(1)本发明制备的手风琴状木质素立方体碳材料具有有序互连的片层结构和优良的结构稳定性，这不仅可以提高电解质离子的扩散速率，还可以提升碳材料比表面积的有效利用率。作为超级电容器电极材料，具有优异的质量和面积比电容以及倍率性能。
(2)本发明的手风琴状木质素立方体碳材料制备过程中，以工业碱木质素作为碳源，通过混合胶束结合蒸发自组装生成的草酸锌作为模板剂，实现了对木质素的限域生长，所得到的碳材料具有纳米片层结构且宏观结构有序，在储能材料中具有潜在的应用前景，此外其原料储量丰富、廉价易得、制备工艺简单环保，实现了木质素的高附加值利用。
附图说明
图1是本发明实施例1制备的手风琴状木质素立方体碳材料的扫描电镜图。
图2是本发明实施例1制备的手风琴状木质素立方体碳材料的透射电镜图(1×2微米)。
图3是本发明实施例1制备的手风琴状木质素立方体碳材料的氮气吸脱附曲线图和孔径分布图。
图4是本发明实施例1制备的手风琴状木质素立方体碳材料的循环伏安曲线图。
图5是本发明实施例1制备的手风琴状木质素立方体碳材料的恒直流充放电曲线图。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
本发明实施例中未注明具体条件者，按照常规条件或者制造商建议的条件进行。所用未注明生产厂商者的原料、试剂等，均为可以通过市售购买获得的常规产品。
实施例和对比例中用到的聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯、星形聚乳酸-聚乙二醇、聚乙二醇单甲醚-聚苯乙烯-聚乙内酯、聚乳酸-生物素葡聚糖胺-DTMPDOL均购买于Sigma Aldrich。
实施例1
将200g工业木浆碱木质素溶于2000mL pH为12的氢氧化钠碱溶液中，然后加0.5mol/L盐酸调节溶液pH为5，过滤分离沉淀，将沉淀物在80℃的鼓风烘箱中干燥6h，得到提纯木质 素；
取10g提纯后的木浆碱木质素和2g聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯依次加入到400mL乙醇/水(体积比为3：1)混合溶剂中，超声分散30min，搅拌2h，随后依次各加入含有5g纯硝酸锌的100g水溶液和含有5g纯草酸钠的100g水溶液，利用蠕动泵控制溶液的滴加速率为30mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在70℃、真空度为0.04MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在80℃的鼓风烘箱中干燥4h得到木质素/聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯/草酸锌复合物。
将上述复合物至于氮气氛围中，800℃碳化2h得到木质素碳/氧化锌复合物，将产物浸泡在0.5mol/L盐酸中洗涤1h，然后水洗、过滤和冷冻干燥后获得木质素立方体碳材料。
实施例2
将200g工业竹浆碱木质素溶于2000mL pH为12的氢氧化钾碱溶液中，然后加1.5mol/L盐酸调节溶液pH为6，过滤分离沉淀，将沉淀物在80℃的红外烘箱中干燥6h，得到提纯木质素；
取10g提纯后的竹浆碱木质素和5g聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯依次加入到500mL乙醇/水(体积比为4：1)混合溶剂中，超声分散30min，搅拌3h，随后依次各加入含有3g纯硝酸锌的100g水溶液和含有3g纯草酸钾的100g水溶液，利用蠕动泵控制溶液的滴加速率为40mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在80℃、真空度为0.05MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在60℃的红外烘箱中干燥5h得到木质素/聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯/草酸锌复合物。
将上述复合物至于氩气氛围中，700℃碳化1h得到木质素碳/氧化锌复合物，将产物浸泡在1mol/L硫酸中洗涤2h，然后水洗、过滤和红外干燥后获得木质素立方体碳材料。
实施例3
将200g工业麦草浆碱木质素溶于2000mL pH为12的氨水碱溶液中，然后加1.0mol/L盐酸调节溶液pH为7，过滤分离沉淀，将沉淀物在80℃的鼓风烘箱中干燥6h，得到提纯木质素；
取10g提纯后的麦草浆碱木质素和4g星形聚乳酸-聚乙二醇依次加入到500mL乙醇/水(体积比为2：1)混合溶剂中，超声分散30min，搅拌2h，随后依次各加入含有4g纯乙酸锌的100g水溶液和含有4g纯草酸铵的100g水溶液，利用蠕动泵控制溶液的滴加速率为35mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在70℃、真空度为0.06MPa条件下旋转蒸发6h，静置、过滤得到沉淀物，沉淀物在70℃的红外烘箱中干燥6h得到木质素/星形聚乳酸-聚乙二醇/草酸锌复合物。
将上述复合物至于氮气氛围中，900℃碳化3h得到木质素碳/氧化锌复合物，将产物浸泡在0.5mol/L硝酸中洗涤1.5h，然后水洗、过滤和真空干燥后获得木质素立方体碳材料。
实施例4
将200g工业蔗渣浆碱木质素溶于2000mL pH为12的氢氧化钠碱溶液中，然后加0.5mol/L盐酸调节溶液pH为5，过滤分离沉淀，将沉淀物在80℃的红外烘箱中干燥6h，得到提纯木质素；
取10g提纯后的蔗渣浆碱木质素和10g聚乙二醇单甲醚-聚苯乙烯-聚乙内酯依次加入到400mL乙醇/水(体积比为4：1)混合溶剂中，超声分散30min，搅拌3h，随后依次各加入含有6g纯柠檬酸锌的100g水溶液和含有6g纯草酸钠的100g水溶液，利用蠕动泵控制溶液的滴加速率为45mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在75℃、真空度为0.05MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在80℃的鼓风烘箱中干燥4h得到木质素/聚乙二醇单甲醚-聚苯乙烯-聚乙内酯/草酸锌复合物。
将上述复合物至于氮气氛围中，600℃碳化2.5h得到木质素碳/氧化锌复合物，将产物浸泡在1.5mol/L盐酸中洗涤3h，然后水洗、过滤和冷冻干燥后获得木质素立方体碳材料。
实施例5
将200g工业麦草浆碱木质素溶于2000mL pH为12的氢氧化钾碱溶液中，然后加0.5mol/L硫酸调节溶液pH为6，过滤分离沉淀，将沉淀物在80℃的真空烘箱中干燥6h，得到提纯木质素；
取10g提纯后的麦草浆碱木质素和5g聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯依次加入到300mL乙醇/水(体积比为4：1)混合溶剂中，超声分散30min，搅拌2h，随后依次各加入含有3g纯柠檬酸锌的100g水溶液和含有3g纯草酸钠的100g水溶液，利用蠕动泵控制溶液的滴加速率为45mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在85℃、真空度为0.05MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在80℃的真空烘箱中干燥4h得到木质素/聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯/草酸锌复合物。
将上述复合物至于氩气氛围中，850℃碳化3h得到木质素碳/氧化锌复合物，将产物浸泡在0.5mol/L盐酸中洗涤2h，然后水洗、过滤和红外干燥后获得木质素立方体碳材料。
实施例6
将200g工业竹浆碱木质素溶于2000mL pH为12的氢氧化钠碱溶液中，然后加0.5mol/L磷酸调节溶液pH为7，过滤分离沉淀，将沉淀物在80℃的鼓风烘箱中干燥6h，得到提纯木质素；
取10g提纯后的竹浆碱木质素和6g聚乳酸-生物素葡聚糖胺-DTMPDOL依次加入到450mL乙醇/水(体积比为3.5：1)混合溶剂中，超声分散30min，搅拌2h，随后依次各加入含有2g纯乙酸锌的100g水溶液和含有2g纯草酸铵的100g水溶液，利用蠕动泵控制溶液的滴加速率为35mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在70℃、真空度为0.04MPa条件下旋转蒸发6h，静置、过滤得到沉淀物，沉淀物在80℃的鼓风烘箱中干燥6h得到木质素/聚乳酸-生物素葡聚糖胺-DTMPDOL/草酸锌复合物。
将上述复合物至于氮气氛围中，650℃碳化2h得到木质素碳/氧化锌复合物，将产物浸泡在1.5mol/L硫酸中洗涤3h，然后水洗、过滤和冷冻干燥后获得木质素立方体碳材料。
实施例效果说明
对实施例1中制备得到的手风琴状木质素立方体碳材料应用于超级电容器电极材料中并进行材料表征和电化学测试，结果见表1及图1～图5。
样品的微观形貌和结构由扫描电子显微镜(SEM,Hitachi S-550)和高分辨场发射透射电子显微镜(HRTEM,JEOL JEM-2100F,200kV)来进行表征。样品的比表面积和孔道结构使用全自动比表面及孔隙度分析仪(Micromeritics ASAP 2020instrument)来进行测试。
电化学测试在电化学工作站(CHI660E，上海辰华)上进行，全部测试采用三电极体系。工作电极制备流程如下：将制备的木质素立方体碳材料、乙炔黑和聚四氟乙烯乳液(固含60wt％)以8:1:1的质量比分散在无水乙醇中，充分研磨，待乙醇完全挥发后将其涂覆到1cm×1cm的泡沫镍上，压片后获得工作电极。对电极采用铂片电极，参比电极采用饱和甘汞电极。循环伏安曲线测试在-1～0V的电压窗口以5～200mv/s的扫描速度完成。恒直流充放电曲线测试在-1～0V的电压窗口以0.5～20.0A/g的电流密度完成。
表1是上述实施例制备的手风琴状木质素立方体碳材料与下述对比例制备的样品在在电化学性能方面的比较。
对比例样品的制备工艺如下：
对比例1(采用疏水组装)
采用专利申请CN109485029 A及(Chemical Engineering Journal 392(2020)12372)中的工艺
将200g工业木浆碱木质素溶于2000mL pH为12的氢氧化钠碱溶液中，然后加0.5mol/L 盐酸调节溶液pH为5，过滤分离沉淀，将沉淀物在80℃的鼓风烘箱中干燥6h，得到提纯木质素；
取10g提纯木质素和2g聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯依次加入到100mL水中超声分散30min，搅拌2h，随后依次各加入含有5g纯硝酸锌的100g溶液和含有5g纯草酸钠的100g水溶液，利用蠕动泵控制溶液的滴加速率为30mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，再次利用蠕动泵往混合体系中滴加300mL乙醇，滴加速率为30mL/min，将混合溶液在70℃、真空度为0.04MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在80℃的鼓风烘箱中干燥4h得到木质素/聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯/草酸锌复合物。
将上述复合物至于氮气氛围中，800℃碳化2h得到木质素碳/氧化锌复合物，将产物浸泡在0.5mol/L盐酸中洗涤1h，然后水洗、过滤和冷冻干燥后获得木质素碳材料。
对比例2(水溶性磺化木质素)
采用专利申请CN109485029A及(Chemical Engineering Journal 392(2020)12372)中的水溶性磺化木质素
将200g水溶性磺化木质素溶于2000mL pH为12的氢氧化钠碱溶液中，然后加0.5mol/L盐酸调节溶液pH为5，过滤分离沉淀，将沉淀物在80℃的鼓风烘箱中干燥6h，得到提纯木质素；
取10g提纯后的水溶性磺化木质素和2g聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯依次加入到400mL乙醇/水(体积比为3：1)混合溶剂中，超声分散30min，搅拌2h，随后依次各加入含有5g纯硝酸锌的100g水溶液和含有5g纯草酸钠的100g水溶液，利用蠕动泵控制溶液的滴加速率为30mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在70℃、真空度为0.04MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在80℃的鼓风烘箱中干燥4h得到木质素/聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯/草酸锌复合物。
将上述复合物至于氮气氛围中，800℃碳化2h得到木质素碳/氧化锌复合物，将产物浸泡在0.5mol/L盐酸中洗涤1h，然后水洗、过滤和冷冻干燥后获得木质素碳材料。
对比例3(直接采用草酸锌)
将200g工业木浆碱木质素溶于2000mL pH为12的氢氧化钠碱溶液中，然后加0.5mol/L盐酸调节溶液pH为5，过滤分离沉淀，将沉淀物在80℃的鼓风烘箱中干燥6h，得到提纯木质素；
取10g提纯后的木浆碱木质素和2g聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯依次加入到400mL乙醇/水(体积比为3：1)混合溶剂中，超声分散30min，搅拌2h，随后加入含有10g纯草酸锌的100g水溶液，利用蠕动泵控制溶液的滴加速率为30mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在70℃、真空度为0.04MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在80℃的鼓风烘箱中干燥4h得到木质素/聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯/草酸锌复合物。
将上述复合物至于氮气氛围中，800℃碳化2h得到木质素碳/氧化锌复合物，将产物浸泡在0.5mol/L盐酸中洗涤1h，然后水洗、过滤和冷冻干燥后获得木质素碳材料。
对比例4(不加入嵌段共聚物)
将200g工业木浆碱木质素溶于2000mL pH为12的氢氧化钠碱溶液中，然后加0.5mol/L盐酸调节溶液pH为5，过滤分离沉淀，将沉淀物在80℃的鼓风烘箱中干燥6h，得到提纯木质素；
取10g提纯后的木浆碱木质素加入到400mL乙醇/水(体积比为3：1)混合溶剂中，超声分散30min，搅拌2h，随后依次各加入含有5g纯硝酸锌的100g水溶液和含有5g纯草酸钠的 100g水溶液，利用蠕动泵控制溶液的滴加速率为30mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在70℃、真空度为0.04MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在80℃的鼓风烘箱中干燥4h得到木质素/草酸锌复合物。
将上述复合物至于氮气氛围中，800℃碳化2h得到木质素碳/氧化锌复合物，将产物浸泡在0.5mol/L盐酸中洗涤1h，然后水洗、过滤和冷冻干燥后获得木质素碳材料。
对比例5(采用文献中聚氧丙烯聚氧乙烯共聚物F127)
将200g工业木浆碱木质素溶于2000mL pH为12的氢氧化钠碱溶液中，然后加0.5mol/L盐酸调节溶液pH为5，过滤分离沉淀，将沉淀物在80℃的鼓风烘箱中干燥6h，得到提纯木质素；
取10g提纯后的木浆碱木质素和2g F127依次加入到400mL乙醇/水(体积比为3：1)混合溶剂中，超声分散30min，搅拌2h，随后依次各加入含有5g纯硝酸锌的100g水溶液和含有5g纯草酸钠的100g溶液，利用蠕动泵控制溶液的滴加速率为30mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在70℃、真空度为0.04MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在80℃的鼓风烘箱中干燥4h得到木质素/聚氧丙烯聚氧乙烯共聚物F127/草酸锌复合物。
将上述复合物至于氮气氛围中，800℃碳化2h得到木质素碳/氧化锌复合物，将产物浸泡在0.5mol/L盐酸中洗涤1h，然后水洗、过滤和冷冻干燥后获得木质素立方体碳材料。
对比例6(提纯pH＜5的工业木浆碱木质素)
将200g工业木浆碱木质素溶于2000mL pH为12的氢氧化钠碱溶液中，然后加0.5mol/L盐酸调节溶液pH＝4，过滤分离沉淀，将沉淀物在80℃的鼓风烘箱中干燥6h，得到提纯木质素；
取10g提纯后的工业木浆碱木质素和2g聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯依次加入到400mL乙醇/水(体积比为3：1)混合溶剂中，超声分散30min，搅拌2h，随后依次各加入含有5g纯硝酸锌的100g水溶液和含有5g纯草酸钠的100g水溶液，利用蠕动泵控制溶液的滴加速率为30mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在70℃、真空度为0.04MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在80℃的鼓风烘箱中干燥4h得到木质素/聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯/草酸锌复合物。
对比例7(提纯pH＞7的工业木浆碱木质素)
将200g工业木浆碱木质素溶于2000mL pH为12的氢氧化钠碱溶液中，然后加0.5mol/L盐酸调节溶液pH＝8，过滤分离沉淀，将沉淀物在80℃的鼓风烘箱中干燥6h，得到提纯木质素；
取10g提纯后的工业木浆碱木质素和2g聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯依次加入到400mL乙醇/水(体积比为3：1)混合溶剂中，超声分散30min，搅拌2h，随后依次各加入含有5g纯硝酸锌的100g水溶液和含有5g纯草酸钠的100g水溶液，利用蠕动泵控制溶液的滴加速率为30mL/min，边滴加边搅拌使体系中各物料均匀分散。溶液滴加完毕后，将混合溶液在70℃、真空度为0.04MPa条件下旋转蒸发4h，静置、过滤得到沉淀物，沉淀物在80℃的鼓风烘箱中干燥4h得到木质素/聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯/草酸锌复合物。
将上述复合物至于氮气氛围中，800℃碳化2h得到木质素碳/氧化锌复合物，将产物浸泡在0.5mol/L盐酸中洗涤1h，然后水洗、过滤和冷冻干燥后获得木质素碳材料。
表1手风琴状木质素立方体碳材料与对比例1～5的结构特征及电化学性能
Figure PCTCN2022124434-appb-000001
表1说明：
实施例1所制备的手风琴状木质素立方体碳材料在0.5A/g电流密度下的质量和面积比电容为分别为358F/g和34.1μF/cm 2，当电流密度为20A/g时，碳材料的质量和面积比电容分别为255F/g和24.3μF/cm 2，比电容保持率即倍率性能高达71.2％。
所有实施例样品的质量比电容高于330F/g、面积比容量高于34.1μF/cm 2、倍率性能都高于71.2％，远远高于对比例样品，这主要得益于如下两点：(1)木质素立方体碳材料有序互连的片层结构，加快离子传输速率的同时提升了材料比表面积的有效利用率；(2)草酸锌对木质素的限域作用加强了立方体碳材料的结构稳定性。两者的协同作用使得木质素立方体碳材料兼具高质量和面积比电容以及倍率性能。因此本发明所制备的手风琴状木质素立方体碳材料不论 是比电容还是倍率性能，材料都表现出十分优异的电化学性能。
而表1中，(1)对比例1样品中未磺化的木质素在水溶液中溶解度较低，无法与嵌段共聚物形成足够二元混合胶束并沉积在草酸锌的表面与层间，草酸锌自身团聚严重，疏水自组装后得到无序沉淀物，碳化后产物虽呈现二维片层结构，但宏观结构无序，片层较厚，得不到手风琴状的立方体结构，质量及面积比电容分别为288F/g和23.0μF/cm 2，倍率性能仅为52.0％。(2)对比例2样品中，水溶性的磺化的木质素在乙醇/水体系中溶解度较低，草酸锌片层无法被二元混合胶束有效分散进而无序散乱堆积，制备的碳材料片层无序，片层之间无法有效支撑互连，质量及面积比电容为276F/g和21.6μF/cm 2，倍率性能仅有50.7％；(3)对比例3中由于直接使用草酸锌，导致木质素/嵌段共聚物二元混合胶束与草酸锌分散不均匀，胶束大量沉积在草酸锌的表面，无法发挥草酸锌对木质素的限域作用，碳化后的材料颗粒较大，结构无序且稳定性差，质量及面积比电容仅为128F/g和13.8μF/cm 2，比电容保持率为50.0％；(4)对比例4中没有加入嵌段共聚物，木质素自身团聚形成胶束，分散不均匀，无序沉积在草酸锌的表面与层间，碳化过程中无法形成互连的片层结构，碳材料片层散乱堆积，结构稳定性太差，质量和面积比电容为107F/g和14.5μF/cm 2，比电容保持率为49.5％。(5)对比例5中木质素与聚氧丙烯聚氧乙烯共聚物F127形成的二元混合胶束粒径分布宽，相互之间容易团聚，无法均匀沉积在草酸锌的表面与层间，造成草酸锌片层散乱堆积，大大降低了碳材料结构稳定性，比表面积为836m 2/g，质量和比电容仅为126F/g和15.1μF/cm 2；(6)对比例6中，pH＝4时提纯的木质素在乙醇/水体系中的溶解度太大，木质素/嵌段共聚物二元混合胶束之间容易发生团聚；对比例7中，pH＝8时提纯的木质素在乙醇/水体系中的溶解度太小，草酸锌片层之间容易发生堆叠，无论哪种情况胶束都难以与草酸锌共沉积，无法发挥草酸锌对木质素的限域生长作用，最终制备的木质素碳材料呈现大块状，对比例6中材料的质量和面积比电容仅为140F/g和14.8μF/cm 2；对比例7中材料的质量和面积比电容仅为138F/g和14.5μF/cm 2。
若pH＜5，则木质素在乙醇/水体系中的溶解度太大，在步骤(2)蒸发溶剂的过程中，木质素/嵌段共聚物混合胶束难以与草酸锌共沉积，且混合胶束之间容易发生团聚，无法发挥草酸锌对木质素的限域生长作用；若pH＞7，则木质素在乙醇/水体系中的溶解度太小，乙醇/水体系中形成的木质素/嵌段共聚物混合胶束数量较少，无法有效沉积在草酸锌的表面与层间，草酸锌片层之间容易发生团聚，不利于形成结构稳定的木质素/嵌段共聚物/草酸锌复合物。
图1是本发明实施例1制备的手风琴状木质素立方体碳材料的扫描电镜图。从图中可以看出，所制备的木质素立方体碳材料具有典型的手风琴状立方体结构，片层有序互连且结构稳定性良好。
图2是本发明实施例1制备的手风琴状木质素立方体碳材料的透射电镜图。从图中可以看出，木质素立方体碳材料的片层互连有序，片与片之间有丰富的孔道结构，这大大提升了碳立方体材料比表面积的有效利用率。
图3是本发明实施例1制备的手风琴状木质素立方体碳材料的氮气吸脱附曲线图和孔径分布图。从图中可以看出木质素立方体碳材料的吸脱附曲线属于Ⅳ型，且具有H3型回滞环。在相对压力较低的区域，氮气吸附量出现了迅速增加，表明其具有微孔结构，而在相对压力较高的区域出现的回滞环则表明其具有介孔结构。木质素多孔碳纳米片的总BET比表面积为1050m 2/g，其中微孔比表面积为647m 2/g，介孔比表面积为403m 2/g，总孔容积为0.918cm 3/g。其孔径分布非常宽，合理的孔道结构和丰富的孔径分布有利于电化学性能的提升。
图4是本发明实施例1制备的手风琴状木质素立方体碳材料的循环伏安曲线图。从图中可以看出，材料在不同扫速下的曲线都是准矩形状，这说明材料具有理想的双电层电容，即使在最高扫速下，曲线形状几乎不变，这说明材料的倍率性能优良。
图5是本发明实施例1制备的手风琴状木质素立方体碳材料的恒直流充放电曲线图。从图中可以看出，所制备的木质素立方体碳材料在不同电流密度下的曲线形状类似于等腰三角形， 这说明碳材料具有典型的双电层电容特性。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种手风琴状木质素立方体碳材料的制备方法，其特征在于，包括以下步骤：
    (1)将工业木质素溶于pH为12以上的碱溶液中，然后加酸调节溶液pH为5～7，过滤分离沉淀，将沉淀物干燥，得到纯化木质素；
    (2)将纯化木质素和嵌段共聚物加入到乙醇水混合溶剂中，搅拌2～4h，静置3～6h，形成木质素/嵌段共聚物混合胶束，然后依次滴加可溶性锌盐溶液和草酸盐溶液，在70～90℃下蒸发4～8h，过滤，干燥，得到木质素/嵌段共聚物/草酸锌复合物；
    (3)将木质素/嵌段共聚物/草酸锌复合物进行碳化，洗涤，离心，干燥，得到手风琴状木质素立方体碳材料；
    步骤(2)所述纯化木质素、嵌段共聚物、可溶性锌盐、可溶性草酸盐和乙醇水混合溶剂的比例为100g：5～50g：20～100g：20～100g：2000～5000mL。
  2. 根据权利要求1所述一种手风琴状木质素立方体碳材料的制备方法，其特征在于，步骤(2)所述嵌段共聚物为聚乙二醇-b-聚N-异丙基丙烯酰胺-b-聚乙内酯、星形聚乳酸-聚乙二醇、聚乙二醇单甲醚-聚苯乙烯-聚乙内酯、聚乙二醇-脂肪族聚酯-聚氨基酸和聚乳酸-生物素葡聚糖胺-DTMPDOL中的至少一种。
  3. 根据权利要求1所述一种手风琴状木质素立方体碳材料的制备方法，其特征在于，步骤(2)所述乙醇水混合溶剂中乙醇和水的体积比为1～4：1。
  4. 根据权利要求1所述一种手风琴状木质素立方体碳材料的制备方法，其特征在于，步骤(2)所述纯化木质素、嵌段共聚物、可溶性锌盐、可溶性草酸盐和乙醇水混合溶剂的比例为100g：20～30g：50～80g：50～80g：2000～3000mL。
  5. 根据权利要求1所述一种手风琴状木质素立方体碳材料的制备方法，其特征在于，步骤(2)所述可溶性锌盐溶液和草酸盐溶液的滴加速率均为10～50mL/min；所述可溶性锌盐溶液和草酸盐溶液的质量浓度均为2～10％；可溶性锌盐为硝酸锌、氯化锌、乙酸锌和柠檬酸锌中的至少一种；可溶性草酸盐为草酸钠、草酸钾和草酸铵中的至少一种。
  6. 根据权利要求1所述一种手风琴状木质素立方体碳材料的制备方法，其特征在于，步骤(2)所述蒸发采用真空旋转蒸发，真空度为0.02～0.08MPa。
  7. 根据权利要求1所述一种手风琴状木质素立方体碳材料的制备方法，其特征在于，步骤(3)所述碳化指在600～900℃碳化1～3h；所述碳化在惰性气体或氮气气氛下进行。
  8. 根据权利要求1所述一种手风琴状木质素立方体碳材料的制备方法，其特征在于，步骤(1)所述pH为12以上的碱溶液为氨水、氢氧化钠溶液和氢氧化钾溶液中的至少一种；所述工业木质素在碱溶液中的质量浓度为10～30％；所述酸为0.5～1.5mol/L的盐酸、硫酸和磷酸中的至少一种；
    步骤(1)所述工业木质素选自木浆碱木质素、竹浆碱木质素、麦草浆碱木质素、蔗渣浆碱木质素、木浆黑液木质素、竹浆黑液木质素、麦草浆黑液木质素和蔗渣浆黑液木质素中的至少一种；
    步骤(3)所述洗涤是指将碳化产物在0.1～1.5mol/L的酸液中洗涤1～3h，然后水洗。
  9. 权利要求1～8任一项所述方法制得的一种手风琴状木质素立方体碳材料。
  10. 权利要求9所述一种手风琴状木质素立方体碳材料在超级电容器中的应用。
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