CN115231550B - Preparation method and application of porous carbon material - Google Patents

Preparation method and application of porous carbon material Download PDF

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CN115231550B
CN115231550B CN202210935956.5A CN202210935956A CN115231550B CN 115231550 B CN115231550 B CN 115231550B CN 202210935956 A CN202210935956 A CN 202210935956A CN 115231550 B CN115231550 B CN 115231550B
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porous carbon
carbon material
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CN115231550A (en
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程华
应晓猛
黄蒙
陈龙明
俞新浩
田文龙
孙振国
解鹏洋
刘阳
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Zhejiang Provincial Building Materials Science Institute Co ltd
Cnbm Design & Research Institute Co ltd
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Cnbm Design & Research Institute Co ltd
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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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • H01G11/84—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

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Abstract

The invention discloses a preparation method of a porous carbon material, which is characterized in that the porous carbon material with different pore structures and surface oxygen contents is obtained by reacting materials for 1-24 hours under the conditions of 10Pa-300MPa and 300-1000 ℃; the material is a substance a; or the material is a mixture comprising a material a and a material b; according to the invention, oxalate, citrate, gluconate and lactate are used as carbon sources and self-templates, and porous carbon materials with different pore structures and surface oxygen contents can be prepared by adjusting pyrolysis pressure and adding carbon sources such as organic acid, sugar organic matters, alcohol organic matters, asphalt, resins and the like. The method has the characteristics of controllable reaction, simple process and recoverable template, the pore structure and the surface hetero atom content of the porous carbon are adjustable, and the porous carbon can be respectively used as the anode material and the cathode material of the alkali metal ion mixed capacitor, and has excellent electrochemical performance.

Description

Preparation method and application of porous carbon material
Technical Field
The invention relates to a porous carbon material, in particular to a preparation method and application of the porous carbon material.
Background
The porous carbon material has the advantages of developed pore structure, large specific surface area, excellent adsorption performance and wide application in the fields of sewage treatment, flue gas treatment, sea water desalination, capacitor electrodes and the like.
The current methods for preparing porous carbon mainly include a template method (soft/hard template), a chemical activation method (activation with potassium hydroxide, phosphoric acid, zinc oxide, etc.), a physical activation method (activation with water vapor, carbon dioxide, air, etc.), and the like. In general, the hard template method (using magnesium oxide, silica, etc. as a template) has further development advantages due to the advantages that the pore size can be determined by the template size, the template itself is inexpensive, the requirements for equipment are low, etc. However, the hard template method is used for preparing porous carbon, on one hand, the obtained porous carbon has limited specific surface area, usually 1000m 2 g -1 About, far lower than porous carbon prepared by chemical or physical activation method>2000m 2 g -1 ) On the other hand, the template needs to be washed off subsequently by strong acid or alkali, so that the cost is increased and the recovery is not facilitatedUtilization. In addition, porous carbon prepared by a template method or a chemical/physical activation method has abundant surface hetero atom content, and is unfavorable for compatibility with electrolyte under high voltage when being used as a positive electrode material of a hybrid ion capacitor. Therefore, in order to promote the development of the porous carbon material, a cheaper and easily-recovered preparation method is explored, and the synthesized porous carbon material has low surface hetero atom content and specific surface area of more than 2000m 2 g -1 Is of great significance for the development of high-voltage hybrid ion capacitors.
Disclosure of Invention
The invention aims to provide a preparation method and application of a porous carbon material. The invention has the characteristics of low production cost and easy recovery of organic salt substances. .
The technical scheme of the invention is as follows: a preparation method and application of a porous carbon material,
compared with the prior art, the preparation method of the invention is that the materials react for 1-24 hours under the conditions of 10Pa-300MPa and 300-1000 ℃, the materials are a substance a or a mixture of a substance a and a substance b, the substance a comprises oxalate, citrate, gluconate, lactate and other organic salts, the substance b comprises at least one of organic acid, saccharide organic matters, alcohol organic matters, asphalt and resin, and thus porous carbon with different pore structures can be obtained. According to the invention, oxalate, citrate, gluconate and lactate are used as carbon sources and self-templates, and porous carbon materials with different pore structures and surface oxygen contents can be prepared by adjusting pyrolysis pressure and adding carbon sources such as organic acid, sugar organic matters, alcohol organic matters, asphalt, resins and the like. The method has the characteristics of controllable reaction and simple process, and the pore structure and the surface hetero atom content of the porous carbon can be adjusted to be up to 2383.6m 2 g -1 And the surface oxygen content is as low as 1.88at.%. The method can realize closed-loop preparation, and can react corresponding organic acid with the reaction product to generate corresponding organic acid salt again, thereby being environment-friendly and low in cost. The pore structure and the surface hetero atom content of the controllable porous carbon material can be respectively obtained to obtain the anode and cathode materials of the alkali metal ion hybrid capacitor, and the anode and cathode materials exhibitThe porous carbon with excellent electrochemical performance and superhigh specific surface has wide application prospect as a catalyst carrier.
Drawings
FIG. 1 is an XRD pattern of magnesium citrate recovered from example 3 and magnesium citrate as a starting material;
FIG. 2 is a graph showing isothermal adsorption and desorption of nitrogen gas of the porous carbon material prepared in example 3;
FIG. 3 is a STEM chart of the porous carbon material produced in example 3;
FIG. 4 is a graph showing isothermal adsorption and desorption of nitrogen gas of the porous carbon material prepared in example 4;
FIG. 5 is a graph showing isothermal adsorption and desorption of nitrogen gas of the porous carbon material prepared in example 5;
FIG. 6 is a graph showing isothermal adsorption/desorption of nitrogen gas of the porous carbon material prepared in example 7;
FIG. 7 is an SEM image of a porous carbon material obtained in example 7;
FIG. 8 is a graph showing isothermal adsorption/desorption of nitrogen gas of the porous carbon material prepared in comparative example 1;
FIG. 9 is an SEM image of a porous carbon material obtained in comparative example 1;
FIG. 10 is an SEM image of a porous carbon material obtained in comparative example 2;
fig. 11 is an SEM image of the porous carbon material produced in comparative example 3.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not intended to be limiting.
Examples. A method for preparing a porous carbon material, comprising the steps of:
reacting the materials at the temperature of between 300 and 1000 ℃ under the pressure of between 10 and 300MPa for 1 to 24 hours to obtain porous carbon with different pore structures and surface oxygen contents;
the material is a substance a; or the material is a mixture comprising a substance a and a substance b;
the substance a comprises organic salts such as oxalate, citrate, gluconate, lactate and the like;
the substance b comprises at least one of organic acid, sugar organic matter, alcohol organic matter, asphalt and resin.
The mixed solution containing the substances a and b is prepared by the following method:
grinding or ball milling or preparing the substance a and the substance b into a solution, and evaporating to dryness to obtain a solid mixture.
The grinding or ball milling is carried out at room temperature.
The preparation of the solution is carried out under the condition of stirring, and the drying by distillation is carried out under the condition of 50-100 ℃ and stirring.
The oxalate comprises at least one of lithium oxalate, sodium oxalate, potassium oxalate, magnesium oxalate, calcium oxalate, manganese oxalate, iron oxalate, nickel oxalate, cobalt oxalate and zinc oxalate.
The citrate comprises at least one of lithium citrate, sodium citrate, potassium citrate, magnesium citrate, calcium citrate, manganese citrate, ferric citrate, nickel citrate, cobalt citrate and zinc citrate;
the gluconate comprises at least one of lithium gluconate, sodium gluconate, potassium gluconate, magnesium gluconate, calcium gluconate, manganese gluconate, iron gluconate, nickel gluconate, cobalt gluconate and zinc gluconate;
the lactate comprises at least one of lithium lactate, sodium lactate, potassium lactate, magnesium lactate, calcium lactate, manganese lactate, ferric lactate, nickel lactate, cobalt lactate and zinc lactate;
the organic acid comprises at least one of oxalic acid, citric acid, gluconic acid and lactic acid.
The saccharide organic matter comprises at least one of glucose, fructose, maltose, sucrose, lactose, starch and cellulose;
the alcohol organic matter comprises at least one of polyvinyl alcohol, polyethylene glycol, sunflower glycol, stearyl alcohol and behenyl alcohol;
the asphalt comprises at least one of high-temperature asphalt, medium-temperature asphalt, low-temperature asphalt, modified asphalt, petroleum asphalt, coal asphalt, petroleum coke, asphalt coke and needle coke;
the resin comprises at least one of epoxy resin, phenolic resin, polyester resin, polyethylene, polypropylene, polyether-ether-ketone, polystyrene, polyoxymethylene and nylon;
the dosage ratio of the substance a to the substance b is 5g to 0-5g.
Preferably, the ratio of the amount of the substance a to the amount of the substance b is 5g to 0g, 1g, 2g, 3g, 4g and 5g.
After the materials are prepared, the materials are reacted for 1 to 24 hours at the temperature of between 300 and 1000 ℃ under the pressure of between 10 and 300MPa, and the porous carbon with different pore structures and surface oxygen contents is obtained.
The pressure of the reaction is 10Pa,101325Pa (standard atmospheric pressure, in a tube furnace) and 10MPa, and the reaction temperature is 600 ℃ or 700 ℃ or 800 ℃.
The reaction time was 5h.
The reaction is carried out in a high temperature stainless steel kettle or a tube furnace.
The pressure is regulated by a vacuum pump, temperature and material quantity.
After the reaction, the method further comprises: naturally cooling the reacted product to room temperature, removing impurities with the organic acid, washing, drying and recovering.
The selected organic acid for removing impurities comprises at least one of oxalic acid, citric acid, gluconic acid and lactic acid.
The impurity removal and recovery process also comprises the following steps:
adding corresponding organic acid at 50-100deg.C, reacting for 1-24 hr, filtering while hot to obtain filtrate, and evaporating at 50-100deg.C to obtain corresponding organic salt.
The washing includes: and (5) filtering and cleaning with deionized water to remove impurities. The times of suction filtration and cleaning are 3 times.
The drying method is not particularly limited in the present invention, and a drying method well known to those skilled in the art may be used.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
The invention also provides porous carbon with high specific surface and low surface hetero atom content, which is prepared by the preparation method.
The porous carbon with different pore structures and surface oxygen contents provided by the invention can be carbon micro-particles or carbon nano-structures.
The prepared carbon microparticles have ultrahigh specific surface area and lower surface oxygen content, and have excellent electrochemical performance as a positive electrode material of the mixed ion capacitor.
The prepared carbon nano structure has moderate specific surface area and higher surface oxygen content, and has excellent electrochemical performance as a negative electrode material of the mixed ion capacitor.
The prepared carbon microparticles have a size of about 1-10 μm, uniformly distributed 1-3nm nanopores therein, and a surface oxygen content as low as 1.8at.%.
The prepared carbon nano structure consists of carbon nano particles and carbon nano sheets, wherein the diameter of the carbon nano particles is 5-20nm, and the carbon nano particles are mutually crosslinked and loaded on the carbon nano sheets.
The invention also provides an alkali metal mixed ion capacitor which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the positive electrode and the negative electrode comprise the porous carbon material.
The alkali metal ion battery may be a lithium ion hybrid capacitor, a sodium ion hybrid capacitor, or a potassium ion hybrid capacitor.
The alkali metal ion hybrid capacitor is assembled according to the following method:
the porous carbon materials with different pore structures and surface oxygen contents are adopted, and the mass ratio of the binder (CMC) to the conductive agent (Super-P) is 8:1:1, mixing, adding water to prepare slurry, uniformly coating the slurry on a copper foil current collector, and carrying out vacuum drying and rolling to prepare an alkali metal ion mixed capacitor negative plate; the mass ratio of binder (PCDF) to conductive agent (Super-P) is 8:1:1, mixing, adding NMP to prepare slurry, uniformly coating on an aluminum foil current collector, and carrying out vacuum drying and rolling to prepare the positive plate of the alkali metal ion mixed capacitor. When the half battery is assembled, the electrode plate is adopted as the positive electrode, a lithium foil (sodium plate or potassium plate) is adopted as the counter electrode, celgard2500 is adopted as a lithium ion battery diaphragm, glass fiber is adopted as a sodium/potassium ion battery diaphragm, 1.0mol/L lithium hexafluorophosphate/sodium/potassium solution (the solvent is ethylene carbonate and propylene carbonate with the volume ratio of 1:1) is adopted as electrolyte, the CR2016 button type alkali metal ion battery is obtained through assembly, and the assembly process is completed in an argon glove box. When the alkali metal ion mixed capacitor is assembled, the cathode plate after pre-lithium/sodium/potassium treatment and the electrode prepared by coating on the aluminum foil are used as the anode, other components are the same as the half battery, the CR2016 button type alkali metal ion mixed capacitor is assembled, and the assembling process is completed in an argon glove box.
The pre-potassium negative electrode sheet is prepared by using alkali metal as a counter electrode at a concentration of 50-100mA g -1 The current density of (2) was cycled 10 times and the cutoff voltage was 1.5V.
In order to further illustrate the present invention, the following examples are provided to illustrate porous carbon materials with different pore structures and surface oxygen contents, and the preparation method and application thereof, but should not be construed as limiting the scope of the present invention.
Example 1
Placing 5g of calcium oxalate into a high-temperature stainless steel kettle, reacting for 5 hours at 10MPa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with equimolar oxalic acid, filtering while hot, evaporating and recovering the filtrate to obtain calcium oxalate, repeatedly pumping, filtering and washing the filter residue with deionized water for 3 times, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
Example 2 of the embodiment
Placing 5g of magnesium gluconate into a high-temperature stainless steel kettle, reacting for 5 hours at 10MPa and 700 ℃, naturally cooling to room temperature, soaking with equimolar gluconic acid at 80 ℃ for 12 hours, filtering while hot, evaporating and recovering the filtrate to obtain magnesium gluconate, repeatedly pumping and filtering the filter residue with deionized water for 3 times, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
Example 3
Placing 5g of magnesium citrate in a high-temperature stainless steel kettle, reacting for 5 hours at 10MPa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with equimolar citric acid, filtering while hot, evaporating and recovering the filtrate to obtain magnesium citrate, repeatedly pumping and filtering the filter residue with deionized water for 3 times, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
FIG. 1 shows XRD patterns of magnesium citrate recovered in example 3 of the present invention and magnesium citrate as a raw material.
FIG. 2 is a graph showing isothermal adsorption/desorption of nitrogen gas of the porous carbon material prepared in example 3. The specific surface area was 201.32m2/g and the average pore diameter was 8.4nm.
FIG. 3 is a STEM chart of the porous carbon material obtained in example 3. The morphology of the nano-particle-based carbon nano-sheet composite material consists of carbon nano-particles and carbon nano-sheets.
Example 4
Placing 5g of calcium citrate in a high-temperature stainless steel kettle, reacting for 5 hours at 10MPa and 700 ℃, then naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with equimolar citric acid, filtering while hot, evaporating and recovering filtrate to obtain the calcium citrate, repeatedly pumping and filtering the filter residue with deionized water for 3 times, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
Fig. 4 is a nitrogen isothermal adsorption/desorption curve of the porous carbon material prepared in example 4. Its specific surface area is 214.05m 2 And/g, average pore diameter of 7.4nm.
Example 5
Placing 5g of ferric citrate in a high-temperature stainless steel kettle, reacting for 5 hours at 10MPa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with equimolar citric acid, filtering while hot, evaporating and recovering the filtrate to obtain ferric citrate, repeatedly pumping and filtering the filter residue with deionized water for 3 times, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
Fig. 5 is a nitrogen isothermal adsorption/desorption curve of the porous carbon material prepared in embodiment 5 of the present invention. Its specific surface area is 242.05m 2 And/g, the average pore diameter is 11.1nm.
Example 6
Placing 5g of magnesium oxalate into a high-temperature stainless steel kettle, reacting for 5 hours at 10MPa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with equimolar oxalic acid, filtering while hot, evaporating and recovering the filtrate to obtain magnesium oxalate, repeatedly pumping, filtering and washing the filter residue with deionized water for 3 times, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
Example 7
Placing 5g of magnesium citrate in a high-temperature stainless steel kettle, reacting for 5 hours at 10Pa and 700 ℃, then naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with equimolar citric acid, filtering while hot, evaporating and recovering the filtrate to obtain magnesium citrate, repeatedly pumping and filtering the filter residue with deionized water for 3 times, and drying to obtain carbon microparticles with the size of 1-20 mu m.
Fig. 6 is a nitrogen isothermal adsorption/desorption curve of the porous carbon material prepared in example 7. The specific surface area was 2383.63m2/g and the average pore diameter was 2.2nm.
Fig. 7 is an SEM image of the porous carbon material prepared in example 7. The morphology exhibited carbon microparticles of 1-20 μm size.
Example 8
Placing 5g of magnesium gluconate into a high-temperature stainless steel kettle, reacting for 5 hours at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with equimolar gluconic acid, filtering while the magnesium gluconate is hot, evaporating and recovering the filtrate to obtain magnesium gluconate, repeatedly pumping and filtering the filter residue with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 mu m.
Example 9
Placing 5g of magnesium citrate and 1g of citric acid mixture into a high-temperature stainless steel kettle, reacting for 5 hours at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with citric acid with the same mol as magnesium citrate, filtering while hot, evaporating and recovering filtrate to obtain magnesium citrate, repeatedly pumping and filtering filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 mu m.
Example 10
Placing 5g of magnesium citrate and 1g of medium-temperature asphalt mixture into a high-temperature stainless steel kettle, reacting for 5 hours at 10Pa and 700 ℃, then naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with citric acid which is equimolar to the magnesium citrate, filtering while hot, evaporating and recovering filtrate to obtain magnesium citrate, repeatedly pumping and filtering and washing filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 mu m.
Example 11
Placing 5g of magnesium citrate and 2g of polyvinyl alcohol mixture into a high-temperature stainless steel kettle, reacting for 5 hours at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with citric acid with the same mol as magnesium citrate, filtering while hot, evaporating and recovering filtrate to obtain magnesium citrate, repeatedly pumping and filtering filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 mu m.
Example 12
Placing 5g of magnesium citrate and 3g of glucose mixture into a high-temperature stainless steel kettle, reacting for 5 hours at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with citric acid with the same mol as magnesium citrate, filtering while hot, evaporating and recovering filtrate to obtain magnesium citrate, repeatedly pumping and filtering filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 mu m.
Example 13
Placing 5g of magnesium citrate and 1g of phenolic resin mixture into a high-temperature stainless steel kettle, reacting for 5 hours at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with citric acid with the same mol as magnesium citrate, filtering while hot, evaporating and recovering filtrate to obtain magnesium citrate, repeatedly pumping and filtering filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 mu m.
Example 14
Placing 5g of zinc oxalate and 1g of oxalic acid mixture into a high-temperature stainless steel kettle, reacting for 5 hours at 10Pa and 700 ℃, then naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with oxalic acid with the same mole as magnesium oxalate, filtering while hot, evaporating and recovering filtrate to obtain magnesium oxalate, repeatedly pumping and filtering filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 mu m.
Comparative example 1
Placing 5g of magnesium citrate into a corundum magnetic boat, calcining and reacting for 5 hours in a tubular furnace protected by argon at 700 ℃, then naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with equimolar citric acid, filtering while hot, evaporating and recovering filtrate to obtain magnesium citrate, repeatedly pumping and filtering filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 mu m.
FIG. 8 is a graph showing isothermal adsorption/desorption of nitrogen gas of the porous carbon material prepared in comparative example 1. Its specific surface area is 1825.43m 2 And/g, average pore diameter of 3.7nm.
Fig. 9 is an SEM image of the porous carbon material produced in comparative example 1. The morphology exhibited carbon microparticles of 1-20 μm in diameter.
Comparative example 2
Placing 5g of citric acid into a high-temperature stainless steel kettle, reacting for 5 hours at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with dilute hydrochloric acid, repeatedly pumping, filtering and washing with deionized water for 3 times, and drying to obtain block granular materials with different sizes.
Fig. 10 is an SEM image of the porous carbon material produced in comparative example 2. The morphology exhibited bulk particulate material of varying sizes.
Comparative example 3
Placing 5g of citric acid into a high-temperature stainless steel kettle, reacting for 5 hours at 10MPa and 700 ℃, naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with dilute hydrochloric acid, repeatedly pumping, filtering and washing with deionized water for 3 times, and drying to obtain the carbon microsphere with the size of 1-20 mu m.
Fig. 11 is an SEM image of the porous carbon material produced in comparative example 3. The morphology of the carbon microsphere shows a diameter of 1-20 μm.
The surface oxygen content of the porous carbon material prepared by the invention is determined by XPS test, and the test results are shown in Table 1.
TABLE 1 oxygen content test results on porous carbon surfaces
Example 3 Example 7 Comparative example 1
Surface oxygen content (at.) 6.65 1.88 4.94
Example 15
The potassium ion hybrid capacitor and half cells thereof are assembled according to the following method:
the porous carbon materials with different pore structures and surface oxygen contents are adopted, and the mass ratio of the binder (CMC) to the conductive agent (Super P) is 8:1:1, mixing, adding water to prepare slurry, uniformly coating the slurry on a copper foil current collector, and carrying out vacuum drying and rolling to prepare a negative plate of the potassium ion mixed capacitor; the mass ratio of binder (PCDF) to conductive agent (SuperP) is 8:1:1, mixing, adding NMP to prepare slurry, uniformly coating on an aluminum foil current collector, and carrying out vacuum drying and rolling to prepare the positive plate of the potassium ion mixed capacitor. When the half battery is assembled, the electrode plate is adopted as the positive electrode, the potassium plate is adopted as the counter electrode, the glass fiber is adopted as the battery diaphragm, 1.0mol/L potassium hexafluorophosphate solution (the solvent is ethylene carbonate and propylene carbonate with the volume ratio of 1:1) is adopted as the electrolyte, the CR2016 button type potassium ion battery is obtained through assembly, and the assembly process is completed in an argon glove box. When the mixed potassium ion capacitor is assembled, the pre-potassium-treated negative plate and the electrode coated on the aluminum foil are used as the positive electrode, other components are the same as the half battery, the CR2016 button type potassium ion mixed capacitor is obtained through assembly, and the assembly process is completed in an argon glove box.
Conditions for electrochemical performance testing: the model of the electrochemical performance testing instrument is as follows: LANDCT2001A, test temperature is 25 ℃, the test voltage range of the negative electrode plate is 0.01-2.5V, the test voltage range of the positive electrode plate is 1.2-4.2V, the test voltage range of the hybrid capacitor is 0.01-4.0V, and the current density is 0.5A/g and 1.0A/g.
The test results are shown in Table 2.
TABLE 2 results of electrochemical Performance test of Potassium ion hybrid capacitors

Claims (3)

1. A preparation method of a porous carbon material is characterized by comprising the following steps: placing 5g of magnesium citrate in a high-temperature stainless steel kettle, reacting for 5 hours at 10Pa and 700 ℃, then naturally cooling to room temperature, soaking for 12 hours at 80 ℃ with equimolar citric acid, filtering while hot, evaporating and recovering the filtrate to obtain magnesium citrate, repeatedly pumping and filtering the filter residue with deionized water for 3 times, and drying to obtain carbon microparticles with the size of 1-20 mu m.
2. A porous carbon material of different pore structure and surface oxygen content, characterized in that: which is prepared by the preparation method of the porous carbon material as claimed in claim 1.
3. An alkali metal ion hybrid capacitor, includes positive pole, negative pole, diaphragm and electrolyte, its characterized in that: the anode and the cathode adopt porous carbon materials with different pore structures and surface oxygen contents prepared by the preparation method of the porous carbon material as claimed in claim 1.
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