WO2020103635A1 - 一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用 - Google Patents

一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用

Info

Publication number
WO2020103635A1
WO2020103635A1 PCT/CN2019/112879 CN2019112879W WO2020103635A1 WO 2020103635 A1 WO2020103635 A1 WO 2020103635A1 CN 2019112879 W CN2019112879 W CN 2019112879W WO 2020103635 A1 WO2020103635 A1 WO 2020103635A1
Authority
WO
WIPO (PCT)
Prior art keywords
lignin
oxalate
porous carbon
layer
composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/112879
Other languages
English (en)
French (fr)
Inventor
邱学青
杨东杰
钱勇
楼宏铭
方志强
刘伟峰
李致贤
黄锦浩
欧阳新平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to US17/261,693 priority Critical patent/US11952278B2/en
Publication of WO2020103635A1 publication Critical patent/WO2020103635A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • 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
    • H01G11/36—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
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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 particularly relates to a lignin porous carbon nanosheet, a preparation method thereof, and application in an electrode material of a supercapacitor.
  • Electrochemical energy storage devices play a very important role in the development of green and sustainable energy storage and conversion technologies.
  • supercapacitors As a new energy storage device between traditional physical capacitors and secondary batteries, supercapacitors have advantages in high power density, fast charge and discharge, long cycle life and wide applicable temperature range.
  • the automotive and other fields have attracted extensive attention.
  • the electrode materials of supercapacitors are the key factors that affect the performance of supercapacitors, mainly including carbon materials, metal oxides and conductive polymers. Among them, carbon materials have been extensively studied due to their advantages such as large specific surface area, controllable pore structure, superior conductivity, and stable chemical properties.
  • graphene has a very high theoretical specific surface area and electrical conductivity and is considered to be the most promising electrode material for supercapacitors.
  • graphene is not easy to prepare on a large scale, which greatly limits its industrial application. Therefore, there is an urgent need to develop a porous carbon material with high specific surface area and easy to be prepared on a large scale for supercapacitor electrode material research.
  • Lignin is the second largest organic polymer in natural plants and the only renewable aromatic polymer, with an annual output of 150 billion tons worldwide.
  • Lignin is a high molecular polymer with phenylpropane monomer as the hydrophobic framework.
  • Lignin in industry mainly includes: lignin sulfonate with good water solubility derived from acid-process pulping waste liquid and alkaline process pulping Alkali lignin in the paper industry and enzymatic hydrolysis lignin in the biorefinery industry.
  • Lignin has a wide range of sources, low cost, and a carbon element content of up to 60%, making it an ideal precursor for carbon materials.
  • the lignin sulfonate has good water solubility, and can be directly subjected to high-temperature carbonization to prepare porous carbon.
  • Chinese patent CN 102633525 uses lignin sulfonate derived from acid pulping waste liquid as a carbon source, directly in an inert atmosphere Porous carbon materials were prepared by high-temperature carbonization. Pang et al. Prepared lignin porous carbon by one-step pyrolysis of sodium lignosulfonate (Green Chemistry, 2017, 19 (16): 3916-3926).
  • chemical activation method and template method are often used in the preparation of lignin porous carbon.
  • the chemical activation method mainly utilizes the etching action of highly corrosive reagents (KOH, ZnCl 2 etc.) under high temperature conditions to obtain porous carbon dominated by micropore distribution.
  • KOH, ZnCl 2 etc. highly corrosive reagents
  • Chinese patent CN 1061855920A discloses a porous lignin carbon material and its preparation method and application.
  • the method uses alkaline lignin in alkaline papermaking black liquor containing KOH as a carbon precursor, which is obtained by pretreatment, carbonization and activation
  • the porous carbon material has a high specific surface area, but the resulting lignin porous carbon is an aggregate with severe agglomeration, and its preparation process needs to undergo secondary activation, and the energy consumption is large, which is not conducive to industrial production.
  • Zhang Guanzhong used alkali lignin as a carbon precursor, mixed it with ZnCl 2 solution and dried it, and then carried out high-temperature carbonization in an inert gas atmosphere to obtain alkali lignin-based activated carbon mainly distributed in micropores (forestry machinery and woodworking equipment, 2017,45 (02): 35-39), however, the ZnCl 2 used in this method is prone to volatilization at high temperature, which will cause environmental pollution while corroding production equipment.
  • the template method mainly utilizes the structure-directing effect of template agents (SiO 2 , Al 2 O 3 , ZnO and other oxides) to achieve precise control of the pore size of porous carbon materials.
  • template agents SiO 2 , Al 2 O 3 , ZnO and other oxides
  • Chinese Patent CN 106744793A discloses a porous carbon material for alkali lignin-based supercapacitors and its preparation method and application. The method uses the crudely purified alkali lignin in papermaking black liquor as a carbon precursor and uses a double template method to prepare A three-dimensional lignin porous carbon material. The preparation process of this method is more complicated, and the obtained porous carbon material has poor electrochemical performance.
  • Liu et al Used water-soluble alkali lignin as a carbon precursor, subjected to liquid nitrogen freezing pretreatment and high-temperature carbonization for 6 hours to obtain a lignin porous carbon nanosheet (RSC) with a thickness of about 100 nm Advances, 2017, 7 (77): 48537-48543).
  • RSC lignin porous carbon nanosheet
  • the process of this method has a longer carbonization time, higher energy consumption, and the liquid nitrogen freezing pretreatment process requires higher equipment and is more dangerous, which is not conducive to industrial large-scale production.
  • Guo et al Used enzymatically hydrolyzed lignin as a carbon precursor.
  • the method first uses silica microspheres as a template to prepare lignin activated carbon, and then mixes the resulting activated carbon with KOH for two Secondary activation to prepare three-dimensional lignin-based multi-stage porous activated carbon materials. This method is cumbersome and difficult to remove the silica template.
  • the lignin porous carbon produced by direct carbonization products has serious agglomeration and random microscopic pores. It is suitable for use as a supercapacitor electrode, and the existing chemical activation method or template method has the problems of complex process, serious corrosion of equipment, and high production cost.
  • the primary purpose of the present invention is to provide a method for preparing porous lignin carbon nanosheets.
  • the method of the present invention uses oxalate as an activator and water-soluble sulfonated lignin as a carbon precursor and dispersant to prepare a lignin porous carbon nanosheet.
  • the water-soluble sulfonated lignin is used as a carbon precursor and dispersant
  • the weakly corrosive oxalate is used as an activator.
  • the two are self-assembled in a selective solvent to prepare a uniformly dispersed compound, and then Then, carbonization is prepared to obtain a regular structured lignin porous carbon nanosheet.
  • the sulfonic acid group in the sulfonated lignin is beneficial to improve the dispersion of the precursor liquid and the activator, and the level of the lignin and the activator molecule are compounded during the layer-by-layer self-assembly process, which is beneficial to improve the activated carbonization effect Further increase the porosity and structural regularity of carbonized products, and apply it to the electrode materials of supercapacitors to improve the specific capacitance and rate performance of supercapacitors.
  • Another object of the present invention is to provide a lignin porous carbon nanosheet prepared by the above method.
  • Another object of the present invention is to provide the application of the above-mentioned lignin porous carbon nanosheets in electrode materials of supercapacitors.
  • the weight ratio of the sulfonated lignin to oxalate is preferably 100: (50-150).
  • the selective solvent is a combined water / ethanol solvent.
  • the layer-by-layer self-assembly refers to using the dispersion obtained from sulfonated lignin and oxalate dispersion water as a matrix solution to assemble the lignin / oxalate composite multiple times to obtain layer-by-layer self-assembled lignin / Oxalate complex.
  • the lignin / oxalate complex is obtained by adding ethanol to the matrix solution to separate out.
  • the assembly refers to adding the lignin / oxalate composite into the matrix solution and stirring it uniformly, and then adding ethanol to separate out to obtain the assembled lignin / oxalate composite.
  • the multiple assembly refers to repeating the above assembly steps multiple times. Specifically, the assembled lignin / oxalate composite is added to the matrix solution and stirred evenly, and then ethanol is added to separate out to obtain the lignin / oxalate composite after the second assembly, and repeated multiple times; preferably repeated 6 to 10 times, more preferably 6 times.
  • the total mass concentration of the sulfonated lignin and oxalate in the matrix solution is preferably 2-10%.
  • the volume ratio of the matrix solution and ethanol used each time is preferably 1: 1.
  • the uniform stirring is preferably 10-30 min.
  • the carbonization refers to carbonization at 550 to 850 ° C for 2 to 4 hours to obtain porous lignin carbon nanosheets.
  • the carbonization is preferably performed under an inert atmosphere.
  • the acid washing refers to washing the carbonized product in 0.5 to 2 mol / L acid solution for 1 to 3 hours, then washing with water, filtering and drying.
  • the acid solution may be hydrochloric acid or sulfuric acid.
  • the drying may include one of drying methods such as blast drying, vacuum drying, freeze drying, infrared drying, etc., preferably freeze drying.
  • the sulfonated lignin may be selected from sodium lignin sulfonate, calcium lignin sulfonate, magnesium lignin sulfonate in acid process pulping red liquor, alkali in alkali process pulping black liquor At least one of the sulfonation product of lignin, and the sulfonation product of enzymatic hydrolysis of lignin in the biorefinery industrial process.
  • the oxalate is preferably at least one of zinc oxalate, calcium oxalate, magnesium oxalate, ferrous oxalate and cobalt oxalate.
  • the preparation method of the present invention specifically includes the following steps:
  • step (3) Take the same A volume part of the matrix solution, add the lignin / oxalate composite obtained in step (2) to it, stir it evenly, then add the same B volume part of ethanol, and separate after standing to obtain the assembled Lignin / oxalate complex;
  • step (3) Repeat step (3) multiple times to obtain layer-by-layer self-assembled lignin / oxalate composites
  • the oxalate solid powder is dispersed by using the sulfonic acid group of sulfonated lignin to prepare a uniformly dispersed dispersion.
  • the dispersion of sulfonated lignin and oxalate is preferably formulated to a mass concentration of 2 to 10%. If the mass concentration of the dispersion is less than 2%, the subsequent yield of lignin / oxalate composite is low ; If the mass concentration of the dispersion is greater than 10%, lignin and oxalate tend to agglomerate themselves.
  • the weight ratio of sulfonated lignin: oxalate is 100: (50 ⁇ 150). If the weight ratio of oxalate is less than 50, the carbonization effect of the subsequent product is poor. The pores of the prepared lignin porous carbon nanosheets Less structure; if the weight ratio of oxalate is higher than 150, it will affect the dispersion effect of sulfonated lignin.
  • the sulfonated lignin has good water solubility and is insoluble in ethanol. It is self-assembled in the selective solvent ethanol-water, and the composite uniform wood is prepared by the interaction force between the metal cation of oxalate and the l bond of lignin molecule. This step is the key to the efficient and uniform compounding of oxalate and lignin.
  • step (3) Take a certain volume of the dispersion prepared in step (1), add the lignin / oxalate complex prepared in step (2), stir evenly, add a certain volume of ethanol, and separate the precipitate after standing to obtain Assembled lignin / oxalate complex;
  • step (2) the volume of the dispersion liquid and the ethanol added are the same as in step (2).
  • stirring is required. If the mixing is not uniform, the subsequent layer-by-layer self-assembly process is difficult to form Composite homogeneous lignin / oxalate composite.
  • step (3) Repeat step (3) N times to separate the precipitate to obtain layer-by-layer self-assembled composite lignin / oxalate composite;
  • repeating step (3) N times is preferably 6 to 10 times, and more preferably 6 times. If the number of self-assembly is less than 6, the yield of the layered self-assembled lignin / oxalate composite after carbonization is low; if the number of self-assembly is greater than 10, the preparation process takes a long time, affecting production efficiency.
  • step (4) Place the lignin / oxalate composite prepared in step (4) in an inert atmosphere, carbonize at 550 to 850 ° C for 2 to 4 hours, and pickle to obtain lignin porous carbon nanosheets.
  • the inert atmosphere in this step may be other inert gases such as nitrogen or argon.
  • the carbonization temperature should be in the range of 550 ⁇ 850 °C, and the carbonization time should be 2 ⁇ 4h. If the carbonization temperature or time is insufficient, the lignin carbonization effect will be poor, while the excessive carbonization temperature or time will cause excessive carbonization, and the product yield is low and the energy consumption is large.
  • the present invention provides the lignin porous carbon nanosheets prepared by the above method.
  • the specific surface area ranges from 200 to 1500 m 2 / g
  • the micropore specific surface area ranges from 100 to 500 m 2 / g
  • the mesoporous specific surface area ranges from 100 to 1000 m 2 / g
  • the pore size is 0.5 to 30 nm
  • the pore volume is 0.5 to 1.5 cm 3 / g. It can be used in super capacitor electrode materials.
  • the method of the present invention is based on the sulfonated lignin has good water solubility in aqueous solution and is insoluble in organic solvents, and has good dispersibility to oxalate, using metal cations and lignin molecules in oxalate in selective solvents
  • the interaction force between the ⁇ bonds prepares a homogeneous lignin / oxalate composite through layer-by-layer self-assembly process.
  • the composite is carbonized, and the metal oxide nanoparticles between the lignin carbon layers are removed by pickling to obtain a porous lignin carbon nanosheet with micropores and mesopores.
  • Oxalate has the dual functions of activation and template during carbonization.
  • the gas generated during the thermal decomposition of oxalate plays a role in activating pore formation of lignin, which is beneficial to the formation of microporous structure, and also has a stripping effect to prevent the polycondensation of lignin in the carbonization process.
  • the metal oxide nanoparticles generated by thermal decomposition of oxalate can be used as a template to etch and support the lignin carbon sheet framework, which is beneficial to the formation of carbon nanosheet structures with rich mesopores.
  • This porous carbon nanosheet structure not only significantly increases the adsorption active sites of electrolyte ions on lignin carbon, but also provides a channel for the rapid transmission and diffusion of electrolyte ions between the horizontal and vertical directions of the sheet, greatly improving the super Specific capacitance and rate performance of capacitor electrode materials.
  • the present invention has the following advantages and beneficial effects:
  • the lignin porous carbon nanosheet prepared by the present invention has a reasonable pore structure, a rich pore size distribution and a more regular two-dimensional carbon nanosheet structure . Applying it to the electrode material of supercapacitors can provide a good channel for the rapid diffusion and transmission of electrolyte ions in the electrochemical process, show higher specific capacitance and excellent rate performance, and have good potential application value.
  • FIG. 1 is a scanning electron micrograph of lignin porous carbon nanosheets prepared in Example 1 of the present invention.
  • Example 2 is a transmission electron micrograph of the lignin porous carbon nanosheet prepared in Example 1 of the present invention.
  • Example 3 is a graph of nitrogen adsorption and desorption curves and pore size distribution of lignin porous carbon nanosheets prepared in Example 1 of the present invention.
  • Example 4 is a cyclic voltammogram of a lignin porous carbon nanosheet prepared in Example 1 of the present invention.
  • Example 5 is a constant DC charge-discharge curve diagram of the lignin porous carbon nanosheet prepared in Example 1 of the present invention.
  • the materials involved in the following examples are all available from commercial sources.
  • the amount of each component is based on mass volume parts, g / mL.
  • lignin porous carbon nanosheets are obtained.
  • lignin / magnesium oxalate composite in an inert atmosphere, carbonize at 550 °C for 4h to obtain lignin carbon / magnesium oxide composite, soak the product in 0.5mol / L hydrochloric acid and wash for 3h, then wash and filter And freeze drying to obtain lignin porous carbon nanosheets.
  • lignin porous carbon nanosheets are obtained.
  • lignin porous carbon nanosheets are obtained.
  • lignin porous carbon nanosheets are obtained.
  • lignin porous carbon nanosheets are obtained.
  • the prepared lignin porous carbon nanosheets were used in supercapacitor electrode materials and material characterization and electrochemical tests were conducted. The results are shown in Table 1 and Figures 1 to 5.
  • the microscopic morphology and structure of the samples were characterized by scanning electron microscope (SEM, Hitachi S-550) and high resolution field emission transmission electron microscope (HRTEM, JEOL JEM-2100F, 200kV).
  • SEM scanning electron microscope
  • HRTEM high resolution field emission transmission electron microscope
  • the specific surface area and pore structure of the sample were tested using an automatic specific surface and porosity analyzer (Micromeritics ASAP 2020 instrument).
  • the electrochemical tests were conducted on an electrochemical workstation (CHI660E, Shanghai Chenhua), and all tests used a three-electrode system.
  • the working electrode preparation process is as follows: the prepared lignin porous carbon nanosheets, acetylene black and polytetrafluoroethylene emulsion (solid content 60wt%) are dispersed in absolute ethanol at a mass ratio of 8: 1: 1, and are fully ground until the After the ethanol is completely volatilized, it is coated on a foam nickel of 1 cm ⁇ 1 cm, and the working electrode is obtained after tableting.
  • the counter electrode uses a platinum electrode, and the reference electrode uses a saturated calomel electrode.
  • the cyclic voltammetry test is completed at a scanning speed of 10 to 200 mv / s in a voltage window of -1 to 0V.
  • the constant DC charge-discharge curve test is completed with a current density of 1.0-20.0A / g in a voltage window of -1 ⁇ 0V.
  • Table 1 compares the electrochemical properties of the lignin porous carbon nanosheets prepared in the above examples and the lignin carbon-1 prepared by KOH activation and the lignin carbon- 2 activated by ZnCl 2 .
  • lignin carbon-1 in Table 1 5 parts by mass of sodium lignosulfonate and 10 parts by mass of KOH are dissolved in 100 parts by volume of water, and heated and stirred at 80 ° C until the water is evaporated to dryness.
  • the obtained solid was fully ground, and then placed in an inert atmosphere at 800 ° C for 2h, and then the product was soaked in 1mol / L hydrochloric acid and washed for 2h, then washed with water, filtered and freeze-dried to obtain lignin carbon-1; lignin carbon- 2 Preparation steps: Weigh 5 parts by mass of sodium lignosulfonate and 10 parts by mass of ZnCl 2 dissolved in 100 parts by volume of water, heat and stir at 80 ° C until the water is evaporated to dryness. The obtained solid was fully ground, and then placed in an inert atmosphere at 700 ° C. for 2 h, and then the product was immersed in 1 mol / L hydrochloric acid and washed for 2 h, then washed with water, filtered and freeze-dried to obtain lignin carbon-2.
  • Example 1 The obtained lignin porous carbon nanosheets have specific capacitances of 320F / g and 240F / g at current densities of 1.0A / g and 20.0A / g, respectively, and the specific capacitance retention rate is 76.6%, with good rate performance , Has obvious performance advantages in lignin porous carbon materials.
  • the electrochemical properties of the lignin porous carbon nanosheets prepared in all the examples and the lignin carbon-1 activated by KOH and the lignin carbon- 2 activated by ZnCl 2 were compared.
  • the specific capacitance and rate performance of lignin carbon have been significantly improved, and the specific capacitance retention rate is higher than 75%, because the gas released by the thermal decomposition of oxalate has a stripping and activation effect on lignin, preventing During the carbonization process, the lignin is polycondensed, and the generated metal oxide nanoparticles act on the lignin carbon to etch and support the lignin carbon sheet frame, forming a porous lignin carbon nanosheet with a reasonable and rich pore structure.
  • the lignin carbon-1 prepared by KOH activation and the lignin carbon- 2 activated by ZnCl 2 have serious agglomeration and narrow pore size distribution, which increases the resistance of electrolyte ion diffusion during the electrochemical process, resulting in a serious decline in specific capacitance and rate performance. .
  • FIG. 1 is a scanning electron micrograph of lignin porous carbon nanosheets prepared in Example 1 of the present invention. It can be seen from the figure that the prepared lignin carbon is in the form of relatively regular two-dimensional carbon nanosheets, the structure is loose, and there are many pores of different sizes in the sheet.
  • Example 2 is a transmission electron micrograph of lignin porous carbon nanosheets prepared in Example 1 of the present invention. It can be seen from the figure that the lignin porous carbon nanosheets have graphene-like wrinkle lines, and the pore structure is very rich.
  • Example 3 is a graph of nitrogen adsorption and desorption curves and pore size distribution of lignin porous carbon nanosheets prepared in Example 1 of the present invention. It can be seen from the figure that the absorption and desorption curves of lignin porous carbon nanosheets belong to type IV and have a hysteresis loop of type H3. In the region with relatively low pressure, the nitrogen adsorption capacity increased rapidly, indicating that it has a microporous structure, while the hysteresis ring in the region with relatively high pressure indicates that it has a mesoporous structure.
  • Example 4 is a cyclic voltammogram of a lignin porous carbon nanosheet prepared in Example 1 of the present invention. It can be seen from the figure that the cyclic voltammetry curves of lignin porous carbon nanosheets are similar to rectangles at different scanning speeds, indicating that they have ideal electric double layer capacitance characteristics, and the curves at high scanning speed of 200mv / s The obvious deformation occurs, indicating that the lignin porous carbon nanosheets have good rate performance.
  • Example 5 is a constant DC charge-discharge curve diagram of the lignin porous carbon nanosheet prepared in Example 1 of the present invention. It can be seen from the figure that the charging and discharging curves of the lignin porous carbon nanosheets are similar to an isosceles triangle shape at different current densities, indicating that they have typical electric double layer capacitance characteristics, and the curve charging and discharging times are approximately equal, indicating that Plain porous carbon nanosheets have higher Coulomb efficiency.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用。通过磺化木质素和草酸盐在选择性溶剂中进行层层自组装，制备得到层层自组装的木质素/草酸盐复合物，经碳化，酸洗，得到木质素多孔碳纳米片。提供上述方法制备的木质素多孔碳纳米片，其比表面积范围200～1500m 2/g，微孔比表面积范围100～500m 2/g，介孔比表面积范围100～1000m 2/g，孔径大小0.5～30nm，孔容积0.5～1.5cm 3/g；可应用于超级电容器电极材料中，表现出更高的比电容和优异的倍率性能，具有良好的潜在应用价值。

Description

一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用 技术领域
本发明属于生物质碳材料技术领域，特别涉及一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用。
背景技术
传统化石能源的大量消耗和环境污染问题的日益严峻迫使世界各国将绿色环保新能源的开发提高到战略高度。电化学储能器件在发展绿色可持续能量储存与转化技术领域扮演着十分重要的角色。作为一种介于传统物理电容器与二次电池之间的新型储能器件，超级电容器由于具有功率密度高、可快速充放电、循环使用寿命长和适用温度范围宽等优点在便携式电子设备和电动汽车等领域引起了广泛的关注。超级电容器的电极材料是影响超级电容器性能的关键因素，主要包括碳材料、金属氧化物和导电聚合物三大类。其中，碳材料由于具有比表面积大、孔道结构可调控、导电性优越和化学性质稳定等优势被广泛地研究。在众多碳材料当中，石墨烯具有非常高的理论比表面积和电导率因而被认为是最有潜力的超级电容器电极材料，然而石墨烯不易大规模制备，极大地限制了它的工业化应用。因此迫切需要开发一种具有高比表面积且容易大规模制备的多孔碳材料用于超级电容器电极材料研究。
木质素是自然界植物中含量第二大的有机高分子聚合物，同时也是唯一的可再生芳香聚合物，全世界年产量高达1500亿吨。木质素是一种以苯丙烷单体为疏水骨架高分子聚合物，工业上木质素主要有：来源于酸法制浆废液中的具有良好水溶性的木质素磺酸盐、碱法制浆造纸工业的碱木质素和生物炼制工业的酶解木质素。木质素来源广，成本低，碳元素含量高达60％，是一种理想的碳材料前驱体。
木质素磺酸盐具有良好的水溶性，可直接经过高温碳化制备多孔碳，如中国专利CN 102633525以来源于酸法制浆废液中的木质素磺酸盐为碳源，直接在惰性气氛中进行高温碳化制备了多孔碳材料。Pang等通过一步高温热解木质素磺酸钠制备了木质素多孔碳(Green Chemistry,2017,19(16):3916-3926)，此外他们还通过预氧化直接碳化木质素磺酸钠制备了木质素多孔碳球(Carbon,2018,132:280-293)，然而由于制备过程没有添加活化剂或模板剂，因此制备的多孔碳材料的比表面积较小，孔道结构不够丰富，导致其比电容较低。而碱木质素直接碳化制备的碳材料比表面积更小，其比电容低于50F/g，无法满足超级电容器电极材料的要求(ChemSusChem,2015,8(3):428-432)。
为了增加其比表面积，调节其孔道结构，在制备木质素多孔碳时常采化学活化法和模板法。化学活化法主要利用高温条件下强腐蚀性试剂(KOH，ZnCl 2等)的刻蚀作用获得以微孔分布为主的多孔碳。如中国专利CN 1061855920A公开了一种木质素多孔碳材料及其制备方法和应用，该方法以含有KOH的碱法造纸黑液中的碱木质素为碳前驱体，经预处理、碳化和活化获得具有高比表面积的多孔碳材料，但所得木质素多孔碳是团聚严重的聚集体，且其制备工艺需要经过二次活化，能耗较大，不利于工业化生产。张冠中以碱木质素为碳前驱体，将其与ZnCl 2溶液进行混合后干燥，然后在惰性气体氛围中进行高温碳化获得以微孔分布为主的碱木质素基活性炭(林业机械与木工设备,2017,45(02):35-39)，然而该法使用的ZnCl 2在高温下容易大量挥发，腐蚀生产设备的同时还会产生环境污染。大量的研究表明，化学活化法可制备出高比表面积的木质素多孔碳，但其微观形貌依然表现出较为严重的聚集现象，且具有过多的无规微孔结构，这增加了电解质溶液在其内部的传输阻力，使其电化学性能难以提高。此外，高温碳化过程耗能较大，对设备损坏大且产物产率低。为了降低活化剂对设备的腐蚀，文献(傅凯放.造纸黑液木质素活性炭的制备、表征及吸附应用.山东大学，2018.)以草酸钾作为活化剂，通过与造纸黑液提取的木质素进行浸渍，经高温碳化制备了活性炭材料。文献(严明.胶原蛋白基掺氮多孔炭材料的制备与表征.北京化工大学，2016.)以草酸钙作为蛋白质的活化剂经一步碳化制备了多孔碳材料。草酸钾与草酸钙对生产设备的腐蚀较 弱，但活化温度仍然较高且活化效率较低。
模板法主要利用模板剂(SiO 2，Al 2O 3，ZnO等氧化物)的结构导向作用可实现对多孔碳材料孔径的精准调控。如中国专利CN 106744793A公开了一种碱木质素基超级电容器用多孔碳材料及其制备方法和应用，该方法以造纸黑液中粗提纯的碱木质素为碳前驱体，利用双模板法制备了一种三维木质素多孔碳材料。该方法制备流程较为复杂，且得到的多孔碳材料的电化学性能较差，在1A/g的电流密度下，比电容的最大值仅为141.4F/g；中国专利CN 106744789A公开了一种利用木质素制备多孔炭以及在超级电容器中的应用，该方法以酸沉淀法提取黑液的木质素为碳前驱体，将其溶于乙醇溶液，并与锌盐混合进行水热处理，利用锌盐水热生成的氧化锌作为模板，随后在惰性气体中进行碳化获得球形多孔炭。文献(时金金.木质素制备C-ZnO复合材料及其光催化性能研究.东北林业大学，2015.)报道了一种直接沉淀制备木质素碳/棒状氧化锌复合材料的方法，通过在乙酸锌与木质素磺酸钠的混合溶液中滴加乙醇，调节溶液pH至碱性以生成木质素磺酸钠/Zn(OH) 2复合物沉淀，将其置于惰性气体中碳化得到目标产物并应用于光催化剂领域。通过模板法可制备孔径分布集中的多孔碳材料，但所制备的多孔碳的孔道结构分布相对单一，且制备过程比较复杂，成本较高。
为了增加木质素多孔碳的孔道丰富程度，Liu等以水溶性的碱木质素为碳前驱体，经液氮冷冻预处理和高温碳化6h，得到厚度为100nm左右的木质素多孔碳纳米片(RSC Advances,2017,7(77):48537-48543)。该法流程碳化时间较长，耗能较高，且液氮冷冻预处理工艺对设备要求较高，且危险性较大，不利于工业化大规模生产。Guo等以酶解木质素作为碳前驱体，通过稀硫酸水热预处理以降低木质素的聚集后，再经KOH高温活化获得具有三维分级孔道的木质素多孔碳(Green Chemistry,2017,19(11):2595-2602)。该法得到的木质素碳具有良好的导电性，但水热预处理过程耗时较长，且活化剂KOH对设备腐蚀较为严重，不利于其工业化规模生产。中国专利CN 105817202A公开了一种三维木质素基多级孔活性炭材料的制备方法及其用途，该方法首先利用二氧化硅微球作为模板制备了木质素活性炭，随后将所得活性炭与KOH混合进行 二次活化制备三维木质素基多级孔活性炭材料。该法步骤繁琐，且不易去除二氧化硅模板。
综上所述，由于工业木质素如碱木质素或酶解木质素水溶性差，对固体颗粒的分散能力弱，导致了直接碳化产物制备的木质素多孔碳团聚严重、微观孔道无规等，不适用于作为超级电容器电极，而现有的化学活化法或模板法存在着工艺复杂、对设备腐蚀严重、生产成本高等问题。
发明内容
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种木质素多孔碳纳米片的制备方法。
本发明方法利用草酸盐作为活化剂，以水溶性磺化木质素作为碳前驱体和分散剂，制备得到木质素多孔碳纳米片。具体为以水溶性磺化木质素作为碳前驱体和分散剂，以弱腐蚀性的草酸盐作为活化剂，将二者在选择性溶剂中进行层层自组装制备分散均一的复合物，然后再进行碳化制备得到结构规整的木质素多孔碳纳米片。
本发明方法制备过程中，磺化木质素中的磺酸基有利于提高前驱液与活化剂的分散，层层自组装过程中实现木质素与活化剂分子水平复合，有利于提高活化碳化效果，进一步提高碳化产物的孔隙率及结构规整度，并将其应用于超级电容器电极材料，提高超级电容器的比电容和倍率性能。
本发明另一目的在于提供上述方法制备得到的木质素多孔碳纳米片。
本发明再一目的在于提供上述木质素多孔碳纳米片在超级电容器电极材料中的应用。
本发明的目的通过下述方案实现：
一种木质素多孔碳纳米片的制备方法，通过磺化木质素和草酸盐在选择性溶剂中进行层层自组装，制备得到层层自组装的木质素/草酸盐复合物，经碳化，酸洗，得到木质素多孔碳纳米片。
所述磺化木质素和草酸盐的重量比优选为100：(50～150)。
所述选择性溶剂为水/乙醇组合溶剂。
所述的层层自组装指以磺化木质素和草酸盐分散水中得到的分散液为基体溶液，对木质素/草酸盐复合物进行多次组装，得到层层自组装的木质素/草酸盐复合物。
所述的木质素/草酸盐复合物，通过向基体溶液中加入乙醇析出分离得到。
所述组装指将木质素/草酸盐复合物加入基体溶液中搅拌均匀，再加入乙醇析出分离，得到组装后的木质素/草酸盐复合物。
所述多次组装指重复多次上述组装的步骤。具体为将组装后的木质素/草酸盐复合物加入基体溶液中搅拌均匀，再加入乙醇析出分离，得到二次组装后的木质素/草酸盐复合物，并重复多次；优选为重复6～10次，更优选重复6次。
所述磺化木质素和草酸盐在基体溶液的总质量浓度优选为2～10％。
本发明方法中，每次取用基体溶液和乙醇的体积比均优选为1:1。
本发明方法中，所述的搅拌均匀均优选为搅拌10～30min。
本发明方法中，所述碳化指在550～850℃碳化2～4h，得到木质素多孔碳纳米片。
所述碳化优选在惰性气氛下进行。
所述的酸洗指将碳化后产物置于0.5～2mol/L酸液中洗涤1～3h，然后水洗、过滤和干燥。
所述的酸液可为盐酸或硫酸。
所述干燥可包括鼓风干燥、真空干燥、冷冻干燥、红外干燥等干燥方式中的一种，优选为冷冻干燥。
本发明方法中，所述的磺化木质素可选自酸法制浆红液中的木质素磺酸钠、木质素磺酸钙、木质素磺酸镁，碱法制浆黑液中的碱木质素的磺化产物，和生物炼制工业过程中的酶解木质素的磺化产物中的至少一种。
所述的草酸盐优选为草酸锌、草酸钙、草酸镁、草酸亚铁和草酸钴中的至少一种。
本发明制备方法具体包括以下步骤：
(1)把磺化木质素和草酸盐分散水中，得到基体溶液；
(2)取A体积份的基体溶液，搅拌下加入B体积份的乙醇，静置后分离，得到木质素/草酸盐复合物；
(3)取相同A体积份的基体溶液，将步骤(2)得到的木质素/草酸盐复合物加入其中，搅拌均匀，再加入相同B体积份的乙醇，静置后分离，得到组装的木质素/草酸盐复合物；
(4)重复步骤(3)多次，得到层层自组装的木质素/草酸盐复合物；
(5)将层层自组装的木质素/草酸盐复合物置于惰性气氛下，550～850℃碳化2～4h，酸洗，得到木质素多孔碳纳米片。
下面将更加详细地描述本发明制备方法：
(1)称取一定量的磺化木质素和草酸盐固体粉末，配制成一定质量浓度的分散液，作为基体溶液；
该步骤通过利用磺化木质素的磺酸基来分散草酸盐固体粉末以配制分散均匀的分散液。磺化木质素和草酸盐的分散液优选配制成质量浓度为2～10％，若分散液的质量浓度低于2％，则后续木质素/草酸盐复合物的产率较低；若分散液的质量浓度大于10％，则木质素与草酸盐容易自身团聚。
此步骤中，磺化木质素：草酸盐的重量比为100：(50～150)，若草酸盐重量比低于50，则后续产物碳化效果较差，制备的木质素多孔碳纳米片孔道结构较少；若草酸盐重量比高于150，则影响磺化木质素的分散效果。
(2)取一定体积的上述分散液，加入一定体积的乙醇，静置后分离出沉淀物，得到木质素/草酸盐复合物；
该步骤是利用磺化木质素具有良好水溶性而不溶于乙醇，在选择性溶剂乙醇-水中自组装，通过草酸盐的金属阳离子与木质素分子π键间的相互作用力制备复合均匀的木质素/草酸盐复合物，该步骤是草酸盐与木质素高效均匀复合的关键。
(3)取一定体积步骤(1)所配制的分散液，加入步骤(2)制备的木质素/草酸盐复合物，搅拌均匀后加入一定体积的乙醇，静置后分离出沉淀物，得到组装的木质素/草酸盐复合物；
该步骤中，所取分散液与所加乙醇的体积均与步骤(2)相同，加入木质 素/草酸盐复合物后需要进行搅拌，若不搅拌均匀，则后续层层自组装过程难以形成复合均匀的木质素/草酸盐复合物。
(4)重复步骤(3)N次，分离沉淀物得到层层自组装复合的木质素/草酸盐复合物；
该步骤中重复步骤(3)N次优选为6～10次，更优选为6次。若自组装次数少于6，则形成的层层自组装木质素/草酸盐复合物碳化后产率较低；若自组装次数大于10，则制备过程耗时长，影响生产效率。
(5)将步骤(4)制备的木质素/草酸盐复合物置于惰性气氛中，550～850℃碳化2～4h，酸洗，得到木质素多孔碳纳米片。
此步骤惰性气氛可为氮气或氩气等其他惰性气体。碳化温度要求在550～850℃区间，碳化时间为2～4h。若碳化温度或时间不足则会导致木质素碳化效果较差，而碳化温度或时间过高会导致过度碳化，产物的收率较低且耗能较大。
本发明提供上述方法制备的木质素多孔碳纳米片，其比表面积范围为200～1500m 2/g，微孔比表面积范围为100～500m 2/g，介孔比表面积范围为100～1000m 2/g，孔径大小为0.5～30nm，孔容积为0.5～1.5cm 3/g。可应用于超级电容器电极材料中。
本发明方法基于磺化木质素在水溶液中具有良好的水溶性而不溶于有机溶剂，且对草酸盐具有良好的分散性，在选择性溶剂中利用草酸盐中的金属阳离子与木质素分子π键之间的相互作用力，经层层自组装工艺制备复合均匀的木质素/草酸盐复合物。随后将复合物进行碳化，酸洗去除木质素碳层间的金属氧化物纳米颗粒即可得到微孔和介孔共存的木质素多孔碳纳米片。碳化过程中草酸盐具有活化与模板的双重作用。首先，草酸盐热分解过程中产生的气体对木质素起到活化造孔的作用，有利于形成微孔结构，同时还具有剥离效果防止碳化过程木质素的缩聚。其次，草酸盐热分解所生成的金属氧化物纳米颗粒可作为模板，起到刻蚀与支撑木质素碳片层框架的作用，有利于形成含有丰富介孔的碳纳米片结构。这种多孔碳纳米片结构不仅显著增加了电解液离子在木质素碳上的吸附活性位点，还提供了电解液离子在片层横向与纵向之间快速传 输与扩散的通道，大大提升了超级电容器电极材料的比电容和倍率性能。
本发明相对于现有技术，具有如下的优点及有益效果：
(1)本发明制备的木质素多孔碳纳米片与传统化学活化法和模板法制备的木质素多孔碳相比，具有合理的孔道结构、丰富的孔径分布以及更规整的二维碳纳米片结构。将其应用于超级电容器电极材料，可为电化学过程中电解质离子的快速扩散与传输提供良好的通道，表现出更高的比电容和优异的倍率性能，具有良好的潜在应用价值。
(2)本发明木质素多孔碳纳米片的制备过程中，以水溶性磺化木质素作为碳前驱体和分散剂，以弱腐蚀性的草酸盐为活化剂，原料来源广泛且廉价易得，制备流程简单环保，对设备腐蚀程度低，易实现大规模制备，实现了木质素的高附加值利用，有利于环境保护。
附图说明
图1是本发明实施例1制备的木质素多孔碳纳米片的扫描电镜图。
图2是本发明实施例1制备的木质素多孔碳纳米片的透射电镜图。
图3是本发明实施例1制备的木质素多孔碳纳米片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制备的木质素多孔碳纳米片的循环伏安曲线图。
图5是本发明实施例1制备的木质素多孔碳纳米片的恒直流充放电曲线图。
具体实施方式
下面结合实施例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。
下列实施例中涉及的物料均可从商业渠道获得。各组分用量以质量体积份计，g/mL。
实施例1
称取5质量份木质素磺酸钠和5质量份草酸锌固体粉末溶于500体积份 水中，搅拌均匀得到稳定的分散液A。取50体积份分散液A，在搅拌状态下，加入50体积份乙醇，静置后分离出沉淀物，得到木质素/草酸锌复合物。再取50体积份分散液A，加入上述制备的木质素/草酸锌复合物，搅拌20min后，加入50体积份乙醇，静置后分离出木质素/草酸锌复合物。重复上述操作6次，分离沉淀物得到层层自组装复合的木质素/草酸锌复合物。
将层层自组装复合的木质素/草酸锌复合物置于惰性气氛中，750℃碳化3h得到木质素碳/氧化锌复合物，将产物浸泡在1mol/L盐酸中洗涤2h，然后水洗、过滤和冷冻干燥后获得木质素多孔碳纳米片。
实施例2
称取10质量份木质素磺酸镁和5质量份草酸镁固体粉末溶于500体积份水中，搅拌均匀得到稳定的分散液A。取50体积份分散液A，在搅拌状态下，加入50体积份乙醇，静置后分离出沉淀物，得到木质素/草酸镁复合物。再取50体积份分散液A，加入上述制备的木质素/草酸镁复合物，搅拌20min后，加入50体积份乙醇，静置后分离出木质素/草酸镁复合物。重复上述操作8次，分离沉淀物得到层层自组装复合的木质素/草酸镁复合物。
将层层自组装复合的木质素/草酸镁复合物置于惰性气氛中，550℃碳化4h得到木质素碳/氧化镁复合物，将产物浸泡在0.5mol/L盐酸中洗涤3h，然后水洗、过滤和冷冻干燥后获得木质素多孔碳纳米片。
实施例3
称取5质量份木质素磺酸钙和7.5质量份草酸钙固体粉末溶于500体积份水中，搅拌均匀得到稳定的分散液A。取50体积份分散液A，在搅拌状态下，加入50体积份乙醇，静置后分离出沉淀物，得到木质素/草酸钙复合物。再取50体积份分散液A，加入上述制备的木质素/草酸钙复合物，搅拌20min后，加入50体积份乙醇，静置后分离出木质素/草酸钙复合物。重复上述操作6次，分离沉淀物得到层层自组装复合的木质素/草酸钙复合物。
将层层自组装复合的木质素/草酸钙复合物置于惰性气氛中，650℃碳化 3h得到木质素碳/氧化钙复合物，将产物浸泡在2mol/L盐酸中洗涤2h，然后水洗、过滤和冷冻干燥后获得木质素多孔碳纳米片。
实施例4
称取5质量份磺化碱木质素和5质量份草酸锌固体粉末溶于500体积份水中，搅拌均匀得到稳定的分散液A。取50体积份分散液A，在搅拌状态下，加入50体积份乙醇，静置后分离出沉淀物，得到木质素/草酸锌复合物。再取50体积份分散液A，加入上述制备的木质素/草酸锌复合物，搅拌20min后，加入50体积份乙醇，静置后分离出木质素/草酸锌复合物。重复上述操作6次，分离沉淀物得到层层自组装复合的木质素/草酸锌复合物。
将层层自组装复合的木质素/草酸锌复合物置于惰性气氛中，850℃碳化2h得到木质素碳/氧化锌复合物，将产物浸泡在2mol/L盐酸中洗涤2h，然后水洗、过滤和冷冻干燥后获得木质素多孔碳纳米片。
实施例5
称取10质量份磺化酶解木质素和10质量份草酸钴固体粉末溶于1000体积份水中，搅拌均匀得到稳定的分散液A。取100体积份分散液A，在搅拌状态下，加入100体积份乙醇，静置后分离出沉淀物，得到木质素/草酸钴复合物。再取100体积份分散液A，加入上述制备的木质素/草酸钴复合物，搅拌20min后，加入100体积份乙醇，静置后分离出木质素/草酸钴复合物。重复上述操作8次，分离沉淀物得到层层自组装复合的木质素/草酸钴复合物。
将层层自组装复合的木质素/草酸钴复合物置于惰性气氛中，750℃碳化2h得到木质素碳/氧化钴复合物，将产物浸泡在1mol/L盐酸中洗涤2h，然后水洗、过滤和冷冻干燥后获得木质素多孔碳纳米片。
实施例6
称取10质量份木质素磺酸钙和10质量份草酸锌固体粉末溶于500体积份水中，搅拌均匀得到稳定的分散液A。取50体积份分散液A，在搅拌状态 下，加入50体积份乙醇，静置后分离出沉淀物，得到木质素/草酸锌复合物。再取50体积份分散液A，加入上述制备的木质素/草酸锌复合物，搅拌20min后，加入50体积份乙醇，静置后分离出木质素/草酸锌复合物。重复上述操作7次，分离沉淀物得到层层自组装复合的木质素/草酸锌复合物。
将层层自组装复合的木质素/草酸锌复合物置于惰性气氛中，650℃碳化2h得到木质素碳/氧化锌复合物，将产物浸泡在1mol/L盐酸中洗涤2h，然后水洗、过滤和冷冻干燥后获得木质素多孔碳纳米片。
对制备得到的木质素多孔碳纳米片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 2020 instrument)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：将制备的木质素多孔碳纳米片、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10～200mv/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1.0～20.0A/g的电流密度完成。
表1是上述实施例制备的木质素多孔碳纳米片与KOH活化制备的木质素碳-1、ZnCl 2活化制备的木质素碳-2在电化学性能方面的比较。
表1中木质素碳-1制备步骤：称取5质量份的木质素磺酸钠和10质量份的KOH溶于100体积份水中，80℃加热搅拌直至水分蒸干。将所得固体进行充分研磨，随后置于惰性气氛中800℃碳化2h，再将产物浸泡在1mol/L盐酸中洗涤2h，然后水洗、过滤和冷冻干燥后获得木质素碳-1；木质素碳-2制备步骤：称取5质量份的木质素磺酸钠和10质量份的ZnCl 2溶于100体积份 水中，80℃加热搅拌直至水分蒸干。将所得固体进行充分研磨，随后置于惰性气氛中700℃碳化2h，再将产物浸泡在1mol/L盐酸中洗涤2h，然后水洗、过滤和冷冻干燥后获得木质素碳-2。
表1木质素多孔碳纳米片的电化学性能
Figure PCTCN2019112879-appb-000001
实施例1制备所得木质素多孔碳纳米片在1.0A/g和20.0A/g的电流密度下比电容分别为320F/g和240F/g，比电容保持率为76.6％，具有良好的倍率性能，在木质素多孔碳材料中具有明显的性能优势。
另外，将所有实施例制备所得木质素多孔碳纳米片与KOH活化制备的木质素碳-1、ZnCl 2活化制备的木质素碳-2的电化学性能进行对比，结果显示经草酸盐活化后木质素碳的比电容和倍率性能有了明显的提升，其比电容保持率均高于75％，这是因为草酸盐热分解过程所释放的气体对木质素具有剥离和活化的作用，防止碳化过程木质素的缩聚，且所生成的金属氧化物纳米颗粒对木质素碳起到刻蚀与支撑木质素碳片层框架的作用，形成了孔道结构合理丰富的木质素多孔碳纳米片，可促进电化学过程中电解质离子的快速传输与扩散，提升电化学性能。而KOH活化制备的木质素碳-1和ZnCl 2活化制备的木质素碳-2团聚严重，孔径分布狭窄，增大了电化学过程中电解质离子扩散的阻力，造成比电容和倍率性能的严重下降。
图1是本发明实例1制备的木质素多孔碳纳米片的扫描电镜图。从图中 可以看出，制备得到的木质素碳呈相对规整的二维碳纳米片状，结构疏松，且片层上具有许多大小不一的孔道。
图2是本发明实例1制备的木质素多孔碳纳米片的透射电镜图。从图中可以看出，木质素多孔碳纳米片具有类石墨烯的褶皱纹路，且孔道结构非常丰富。
图3是本发明实例1制备的木质素多孔碳纳米片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多孔碳纳米片的吸脱附曲线属于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1069m 2/g，其中微孔比表面积为406m 2/g，介孔比表面积为663m 2/g，总孔容积为1.4cm 3/g。其孔径分布集中在0.5～2nm的微孔和2～30nm的介孔，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是本发明实例1制备的木质素多孔碳纳米片的循环伏安曲线图。从图中可以看出，木质素多孔碳纳米片在不同扫描速度下循环伏安曲线都呈类似矩形状，表明其具有理想的双电层电容特性，且在高扫描速度200mv/s下曲线没有发生明显的变形，说明木质素多孔碳纳米片具有良好的倍率性能。
图5是本发明实例1制备的木质素多孔碳纳米片的恒直流充放电曲线图。从图中可以看出，木质素多孔碳纳米片在不同电流密度下充放电曲线都呈类似等腰三角形状，表明其具有典型的双电层电容特性，且曲线充放电时间近似相等，说明木质素多孔碳纳米片具有较高的库伦效率。
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 (6)

  1. 一种木质素多孔碳纳米片的制备方法，其特征在于通过磺化木质素和草酸盐在选择性溶剂中进行层层自组装，制备得到层层自组装的木质素/草酸盐复合物，经碳化，酸洗，得到木质素多孔碳纳米片；
    所述的磺化木质素选自酸法制浆红液中的木质素磺酸钠、木质素磺酸钙、木质素磺酸镁，碱法制浆黑液中的碱木质素的磺化产物，和生物炼制工业过程中的酶解木质素的磺化产物中的至少一种；所述的草酸盐为草酸锌、草酸钙、草酸镁、草酸亚铁和草酸钴中的至少一种；
    所述磺化木质素和草酸盐的重量比为100：50～150；
    所述选择性溶剂为水/乙醇组合溶剂；
    所述的层层自组装指以磺化木质素和草酸盐分散水中得到的分散液为基体溶液，对木质素/草酸盐复合物进行多次组装，得到层层自组装的木质素/草酸盐复合物；
    所述的木质素/草酸盐复合物，通过向基体溶液中加入乙醇析出分离得到；所述磺化木质素和草酸盐在基体溶液的总质量浓度为2～10％；每次取用基体溶液和乙醇的体积比均为1:1；所述的搅拌均匀均为搅拌10～30min。
  2. 根据权利要求1所述的木质素多孔碳纳米片的制备方法，其特征在于：所述组装指将木质素/草酸盐复合物加入基体溶液中搅拌均匀，再加入乙醇析出分离，得到组装后的木质素/草酸盐复合物；
    所述多次组装指重复多次上述组装的步骤，具体为将组装后的木质素/草酸盐复合物加入基体溶液中搅拌均匀，再加入乙醇析出分离，得到二次组装后的木质素/草酸盐复合物，并重复6～10次。
  3. 根据权利要求1所述的木质素多孔碳纳米片的制备方法，其特征在于：所述碳化指在550～850℃碳化2～4h，得到木质素多孔碳纳米片；
    所述的酸洗指将碳化后产物置于0.5～2mol/L酸液中洗涤1～3h，然后水洗、过滤和干燥；
  4. 根据权利要求1所述的木质素多孔碳纳米片的制备方法，其特征在于具体包括以下步骤：
    (1)把磺化木质素和草酸盐分散水中，得到基体溶液；
    (2)取A体积份的基体溶液，搅拌下加入B体积份的乙醇，静置后分离，得到木质素/草酸盐复合物；
    (3)取相同A体积份的基体溶液，将步骤(2)得到的木质素/草酸盐复合物加入其中，搅拌均匀，再加入相同B体积份的乙醇，静置后分离，得到组装的木质素/草酸盐复合物；
    (4)重复步骤(3)多次，得到层层自组装的木质素/草酸盐复合物；
    (5)将层层自组装的木质素/草酸盐复合物置于惰性气氛下，550～850℃碳化2～4h，酸洗，得到木质素多孔碳纳米片。
  5. 一种木质素多孔碳纳米片，其特征在于根据权利要求1～4任一项所述的制备方法得到。
  6. 权利要求5所述的木质素多孔碳纳米片在超级电容器电极材料中的应用。
PCT/CN2019/112879 2018-11-19 2019-10-23 一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用 Ceased WO2020103635A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/261,693 US11952278B2 (en) 2018-11-19 2019-10-23 Lignin porous carbon nanosheet, preparation method therefor, and application thereof in supercapacitor electrode materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811375772.8A CN109485029B (zh) 2018-11-19 2018-11-19 一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用
CN201811375772.8 2018-11-19

Publications (1)

Publication Number Publication Date
WO2020103635A1 true WO2020103635A1 (zh) 2020-05-28

Family

ID=65696878

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/112879 Ceased WO2020103635A1 (zh) 2018-11-19 2019-10-23 一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用

Country Status (3)

Country Link
US (1) US11952278B2 (zh)
CN (1) CN109485029B (zh)
WO (1) WO2020103635A1 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113096970A (zh) * 2021-03-03 2021-07-09 广东第二师范学院 一种二硒化钼/柚子皮碳复合材料的制备方法
CN113880073A (zh) * 2021-10-26 2022-01-04 华南理工大学 一种木质素基碳纳米管及其制备方法
CN113998697A (zh) * 2021-11-03 2022-02-01 中国矿业大学 一种树叶基氮掺杂多孔炭的制备方法及其在全pH范围内氧还原电催化中的应用
CN115231568A (zh) * 2022-05-27 2022-10-25 塔里木大学 类石墨烯碳纳米片大孔交联棉秆生物质碳电极材料及其制备方法
CN116161662A (zh) * 2022-12-09 2023-05-26 山西昆明烟草有限责任公司 一种用于烟碱检测的电极材料的制备方法

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109485029B (zh) 2018-11-19 2020-07-28 华南理工大学 一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用
CN110690449A (zh) * 2019-09-02 2020-01-14 广西大学 一种利用木质素制备碳电极的方法
CN110676066B (zh) * 2019-10-07 2021-07-09 东北林业大学 一种用于超级电容器电极的共轭木质素及其制备方法
CN111252763B (zh) * 2020-03-15 2022-03-15 福州大学 一种含磺酸基的木质素基高物化双性型生物炭及其制备方法
CN112441581B (zh) * 2020-11-25 2022-08-09 华南理工大学 一种紫根水葫芦基分级多孔炭材料及其制备方法与在超级电容器中的应用
CN113149005A (zh) * 2021-04-29 2021-07-23 长安大学 一种高比表面积生物质多孔碳材料及其制备方法和应用
CN113307250B (zh) * 2021-04-30 2022-08-26 齐鲁工业大学 有序木质素碳-碳纳米管复合材料的制备方法及其应用
CN113800500B (zh) * 2021-09-27 2023-06-09 华中科技大学 一种木质素制备硼掺杂碳纳米片的方法及产品
CN114408897A (zh) * 2022-01-14 2022-04-29 合肥工业大学 一种生物质基二维纳米碳材料及其制备方法
CN114524427B (zh) * 2022-02-22 2023-04-21 华南理工大学 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
CN114743808B (zh) * 2022-04-27 2023-09-26 大连工业大学 一种用于超级电容器的钨酸镍钴/酶解木质素炭电极材料的制备方法
CN114758900B (zh) * 2022-04-27 2024-09-03 深圳大学 一种生物质多孔碳材料及其制备方法和超级电容器
CN114864291B (zh) * 2022-06-10 2023-10-27 大连工业大学 一种用于超级电容器的NiCo2S4/酶解木质素炭电极材料的制备方法
CN115285991B (zh) * 2022-07-06 2023-11-28 浙江大学 基于生物质衍生物自组装生成分级多孔碳的方法及其应用
CN115403041B (zh) * 2022-09-15 2023-11-21 中国地质大学（北京） 一种半纤维素基中空多孔碳及其制备方法和其在锌离子储能器件中的应用
CN115893384B (zh) * 2022-11-28 2024-03-08 南开大学 一种以生物质为原料的多孔类石墨烯纳米片的合成方法
CN115832296B (zh) * 2022-12-16 2023-06-09 哈尔滨师范大学 一种柔性自支撑炭气凝胶电极材料的制备工艺
CN116332176B (zh) * 2023-03-28 2024-04-05 华南理工大学 一种高比表面积木质素介孔碳材料及其制备和应用
CN117160435B (zh) * 2023-08-09 2024-11-19 广东工业大学 一种木质素碳/氧化锌纳米复合材料及其制备与应用
CN117125740B (zh) * 2023-08-28 2024-07-09 湖北万润新能源科技股份有限公司 一种硫酸亚铁钠正极材料、其制备方法及应用
CN117101719B (zh) * 2023-09-25 2025-10-24 浙江师范大学 一种木质素基磺化碳催化剂及其制备方法和应用
CN118561278B (zh) * 2024-08-02 2024-11-15 成都锂能科技有限公司 木质素基硬碳材料及其制备方法、应用
CN118888350B (zh) * 2024-09-29 2025-02-25 西安科技大学 一种低阶煤基二维多孔纳米片、制备方法及应用
CN119601686A (zh) * 2024-11-27 2025-03-11 中国科学院广州能源研究所 一种生物质衍生分级多孔非对称配位单原子碳基电催化剂及其制备方法和应用
CN119898747A (zh) * 2024-12-16 2025-04-29 广东工业大学 一种高平台容量木质素基硬炭材料及其制备与在钠离子电池中的应用
CN120922955A (zh) * 2025-08-12 2025-11-11 浙江科技大学 一种木基太阳能界面蒸发器的制备方法及其应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103332677A (zh) * 2013-07-12 2013-10-02 天津工业大学 一种利用植物纤维制备生物质碳基复合储能材料的方法
WO2014207765A2 (en) * 2013-06-25 2014-12-31 Council Of Scientific And Industrial Research Synthesis of functionalized carbon microspheres and their catalyst activity in c-o and c-n bond formation reactions
CN106024423A (zh) * 2016-05-25 2016-10-12 华南理工大学 木质素基石墨烯/氧化锌杂化复合材料及制备方法和应用
US20160355402A1 (en) * 2014-07-25 2016-12-08 Farad Power, Inc., Method of making activated nano-porous carbon
CN107282030A (zh) * 2017-05-11 2017-10-24 华南理工大学 一种三维木质素多孔碳/氧化锌复合材料及其制备和在光催化领域中的应用
CN108751160A (zh) * 2018-06-15 2018-11-06 华南理工大学 一种孔道均匀的木质素多孔碳及其制备方法和在锂离子电池负极材料中的应用
CN109485029A (zh) * 2018-11-19 2019-03-19 华南理工大学 一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102633525B (zh) 2012-04-27 2013-10-23 同济大学 一种以脱硫石膏为主要胶凝材料的泡沫混凝土
US20170110259A1 (en) * 2015-10-16 2017-04-20 The Governors Of The University Of Alberta Electrical Energy Storage
CN105817202A (zh) 2016-05-26 2016-08-03 江苏大学 一种三维木质素基多级孔活性炭材料的制备方法及其用途
CN106185920B (zh) 2016-06-27 2018-05-18 农业部环境保护科研监测所 一种多孔碳材料及其制备方法和应用
CN106241780B (zh) * 2016-07-19 2018-02-27 华南理工大学 一种以木质素为原料制备石墨烯的方法
CN106564876B (zh) * 2016-10-24 2019-02-01 宁波工程学院 一种木质素基花状碳纳米材料及其制备方法和应用
CN106517179B (zh) * 2016-11-04 2018-11-20 中南大学 一种碳纳米片矩阵材料的制备方法及其在钠离子电池中的应用
CN106744789A (zh) 2016-11-14 2017-05-31 天津工业大学 一种利用木质素制备多孔炭以及在超级电容器中的应用
CN106744793B (zh) 2016-12-01 2019-04-05 中国林业科学研究院林产化学工业研究所 一种碱木质素基超级电容器用多孔炭材料及其制备方法和应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014207765A2 (en) * 2013-06-25 2014-12-31 Council Of Scientific And Industrial Research Synthesis of functionalized carbon microspheres and their catalyst activity in c-o and c-n bond formation reactions
CN103332677A (zh) * 2013-07-12 2013-10-02 天津工业大学 一种利用植物纤维制备生物质碳基复合储能材料的方法
US20160355402A1 (en) * 2014-07-25 2016-12-08 Farad Power, Inc., Method of making activated nano-porous carbon
CN106024423A (zh) * 2016-05-25 2016-10-12 华南理工大学 木质素基石墨烯/氧化锌杂化复合材料及制备方法和应用
CN107282030A (zh) * 2017-05-11 2017-10-24 华南理工大学 一种三维木质素多孔碳/氧化锌复合材料及其制备和在光催化领域中的应用
CN108751160A (zh) * 2018-06-15 2018-11-06 华南理工大学 一种孔道均匀的木质素多孔碳及其制备方法和在锂离子电池负极材料中的应用
CN109485029A (zh) * 2018-11-19 2019-03-19 华南理工大学 一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113096970A (zh) * 2021-03-03 2021-07-09 广东第二师范学院 一种二硒化钼/柚子皮碳复合材料的制备方法
CN113096970B (zh) * 2021-03-03 2022-09-27 广东第二师范学院 一种二硒化钼/柚子皮碳复合材料的制备方法
CN113880073A (zh) * 2021-10-26 2022-01-04 华南理工大学 一种木质素基碳纳米管及其制备方法
CN113880073B (zh) * 2021-10-26 2022-12-16 华南理工大学 一种木质素基碳纳米管及其制备方法
CN113998697A (zh) * 2021-11-03 2022-02-01 中国矿业大学 一种树叶基氮掺杂多孔炭的制备方法及其在全pH范围内氧还原电催化中的应用
CN113998697B (zh) * 2021-11-03 2023-09-29 中国矿业大学 一种树叶基氮掺杂多孔炭的制备方法及其在全pH范围内氧还原电催化中的应用
CN115231568A (zh) * 2022-05-27 2022-10-25 塔里木大学 类石墨烯碳纳米片大孔交联棉秆生物质碳电极材料及其制备方法
CN115231568B (zh) * 2022-05-27 2024-04-02 塔里木大学 类石墨烯碳纳米片大孔交联棉秆生物质碳电极材料及其制备方法
CN116161662A (zh) * 2022-12-09 2023-05-26 山西昆明烟草有限责任公司 一种用于烟碱检测的电极材料的制备方法

Also Published As

Publication number Publication date
CN109485029B (zh) 2020-07-28
CN109485029A (zh) 2019-03-19
US20210323825A1 (en) 2021-10-21
US11952278B2 (en) 2024-04-09

Similar Documents

Publication Publication Date Title
CN109485029B (zh) 一种木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用
CN110015660B (zh) 一种银掺杂木质素多孔碳纳米片及其制备方法和在超级电容器电极材料中的应用
CN111320172B (zh) 一种含微孔-介孔孔道的生物质活性炭基电极材料的定向合成方法及其应用
CN105776178B (zh) 一种利用煤直接液化重质有机分制备的氮硫共掺杂多孔炭及其制备方法和应用
CN107572523A (zh) 一种氮掺杂分级多孔碳微球及其制备方法和应用
Ma et al. ZIF-derived mesoporous carbon materials prepared by activation via Na2SiO3 for supercapacitor
CN112794324A (zh) 一种高介孔率木质素多级孔碳材料及其制备方法与应用
CN102951636A (zh) 氮掺杂壳聚糖基活性炭及其制备方法
CN108511204A (zh) 一种氧氮共掺杂多孔中空碳微球的制备方法
CN101281821A (zh) 纳米丝状二氧化锰负载炭气凝胶及其制备方法与应用
CN105692616A (zh) 一种用松针基活性炭材料制备超级电容器电极材料的方法
US20250197222A1 (en) Accordion-shaped lignin cubic carbon material, and preparation therefor and application thereof in supercapacitor
CN108892138A (zh) 一种基于生物质衍生氮/氧共掺杂多级孔结构碳材料及其制备方法
CN108584944A (zh) 一种超级电容器用高比表面积富氮分级多孔炭电极材料的制备方法
CN107285315A (zh) 一种可调孔径得到可溶性海藻酸盐基超级电容活性炭材料及其一步炭化制备方法
CN110707323A (zh) 一种阴离子扩层碳材料及其制备方法和应用
CN107445160A (zh) 一种可调孔径的不可溶性海藻酸盐基超级电容活性炭及其一步炭化制备方法
CN117524743A (zh) 一种用于超级电容器电极材料的木质素基硫掺杂活性炭及其制备方法和应用
CN109970045B (zh) 一种基于瓜环聚合物氮掺杂多孔碳材料、制备方法和应用
CN105776195B (zh) 一种超级电容器用富含微纳孔超结构多孔石墨烯的制备方法及产品
CN113979433B (zh) 一种基于直接碳化法的木质素基分级多孔炭的制备及应用
CN117012557A (zh) 一种木质素磺酸钠/壳聚糖高介孔的氮、硫共掺杂多孔碳基超级电容器电极材料的制备方法
CN109319762B (zh) 具有超高比表面积的生物质多孔碳材料的制备及作为电极材料的应用
CN108946695B (zh) 利用焦油废料制备超级电容器用多孔碳材料的方法
CN108428560B (zh) 高比表面积煤基氮掺杂活性炭球电极材料及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19887732

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 31.08.2021)

122 Ep: pct application non-entry in european phase

Ref document number: 19887732

Country of ref document: EP

Kind code of ref document: A1