CN115231550A - Preparation method and application of porous carbon material - Google Patents

Preparation method and application of porous carbon material Download PDF

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CN115231550A
CN115231550A CN202210935956.5A CN202210935956A CN115231550A CN 115231550 A CN115231550 A CN 115231550A CN 202210935956 A CN202210935956 A CN 202210935956A CN 115231550 A CN115231550 A CN 115231550A
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porous carbon
citrate
oxalate
gluconate
substance
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CN115231550B (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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Zhejiang Provincial Building Materials Science Institute Co ltd
Cnbm Design & Research Institute Co ltd
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    • 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
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    • 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a preparation method of a porous carbon material, which comprises the steps of reacting materials for 1-24 hours at 300-1000 ℃ under 10Pa-300MPa to obtain the porous carbon materials 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; according to the method, oxalate, citrate, gluconate and lactate are used as carbon sources and self-templates, and the porous carbon materials with different pore structures and surface oxygen contents can be prepared by adjusting pyrolysis pressure and adding organic acids, carbohydrate organic matters, alcohol organic matters, asphalt, resins and other carbon sources. The method has the characteristics of controllable reaction, simple process and recoverable template, the pore structure and the surface heterogeneous 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 hybrid capacitor and shows 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 a developed pore structure, a large specific surface area and excellent adsorption performance, and is widely applied to the fields of sewage treatment, flue gas treatment, seawater desalination, capacitor electrodes and the like.
The methods for producing porous carbon at present mainly include a template method (soft/hard template), a chemical activation method (activation with potassium hydroxide, phosphoric acid, zinc oxide, or the like), a physical activation method (activation with steam, carbon dioxide, air, or the like), and the like. In general, the hard template method (using magnesium oxide, silicon dioxide, etc. as a template) has a further advantage in that the pore size can be determined by the size of the template, the template itself is inexpensive, the requirements for equipment are low, and the like. However, in the preparation of porous carbon by the hard template method, on one hand, the obtained porous carbon has limited specific surface area, usually 1000m 2 g -1 About, far lower than that prepared by chemical or physical activationPorous carbon (C)>2000m 2 g -1 ) On the other hand, strong acid or strong base is needed to be used for washing off the template subsequently, so that the cost is increased and the recycling is not facilitated. In addition, the porous carbon prepared by the template method or the chemical/physical activation method has rich surface heterogeneous atom content, and is not favorable for the compatibility with the electrolyte at high voltage when being used as the anode material of the mixed ion capacitor. Therefore, in order to promote the development of the porous carbon material, a preparation method which is cheaper and easy to recover is explored, and the synthesized porous carbon material has low surface heterogeneous atom content and specific surface area of more than 2000m 2 g -1 The porous carbon has important significance for the development of high-voltage mixed 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 comprises the step of reacting materials for 1-24 hours at 300-1000 ℃ under 10Pa-300MPa, wherein the materials are substance a or a mixture of substance a and substance b, substance a comprises oxalate, citrate, gluconate, lactate and other organic salts, and substance b comprises at least one of organic acid, carbohydrate organic matters, alcohol organic matters, asphalt and resin, so that porous carbon with different pore structures can be obtained. According to the method, oxalate, citrate, gluconate and lactate are used as carbon sources and self-templates, and the porous carbon materials with different pore structures and surface oxygen contents can be prepared by adjusting pyrolysis pressure and adding organic acids, carbohydrate organic matters, alcohol organic matters, asphalt, resins and other carbon sources. The method has the characteristics of controllable reaction and simple process, and the pore structure and the surface heterogeneous atom content of the porous carbon can be adjusted to reach 2383.6m at most 2 g -1 And the surface oxygen content is as low as 1.88at.%. The method can realize closed-loop preparation, can use the corresponding organic acid to react with the reaction product to generate the corresponding organic acid salt again, and is environment-friendly and low in price. The inventionThe pore structure and the surface heterogeneous atom content of the porous carbon material can be controlled to respectively obtain the anode material and the cathode material of the alkali metal ion hybrid capacitor, so that the electrochemical performance is excellent, and the porous carbon with the ultrahigh specific surface area as a catalyst carrier has wide application prospect.
Drawings
FIG. 1 is an XRD pattern of magnesium citrate recovered and a starting material magnesium citrate for example 3;
FIG. 2 is a nitrogen isothermal adsorption/desorption curve of the porous carbon material obtained in example 3;
FIG. 3 is a STEM chart of a porous carbon material obtained in example 3;
FIG. 4 is a nitrogen isothermal adsorption and desorption curve of the porous carbon material obtained in example 4;
FIG. 5 is a nitrogen isothermal adsorption and desorption curve of the porous carbon material obtained in example 5;
FIG. 6 is a nitrogen isothermal adsorption/desorption curve of the porous carbon material obtained in example 7;
FIG. 7 is an SEM photograph of a porous carbon material obtained in example 7;
FIG. 8 is a nitrogen isothermal adsorption/desorption curve of the porous carbon material produced in comparative example 1;
FIG. 9 is an SEM photograph of a porous carbon material obtained in comparative example 1;
FIG. 10 is an SEM photograph of a porous carbon material obtained in comparative example 2;
FIG. 11 is an SEM photograph of a porous carbon material obtained in comparative example 3.
Detailed Description
The invention is further described with reference to the following figures and examples, which are not to be construed as limiting the invention.
Examples are given. A method for producing a porous carbon material, comprising the steps of:
reacting the material for 1-24h under 10Pa-300MPa and at 300-1000 ℃ 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 oxalate, citrate, gluconate, lactate and other organic salts;
the substance b comprises at least one of organic acid, saccharide organic substance, alcohol organic substance, asphalt and resin.
The mixed solution containing the substance a and the substance b is prepared by the following method:
and grinding or ball-milling the substance a and the substance b or preparing a solution and then evaporating to obtain a solid mixture.
The grinding or ball milling is carried out at room temperature.
The solution preparation is carried out under the condition of stirring, and the evaporation is carried out at the temperature of 50-100 ℃ under the condition of 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, ferric 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, iron 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 carbohydrate 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, sebacic glycol, octadecanol and eicosanol;
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, polyformaldehyde and nylon;
the dosage ratio of the substance a to the substance b is 5g.
Preferably, the dosage ratio of the substance a to the substance b is 5g.
After preparing the materials, reacting the materials for 1 to 24 hours at the temperature of between 300 and 1000 ℃ under the pressure of between 10 and 300MPa to obtain porous carbon with different pore structures and surface oxygen contents.
The pressure of the reaction is 10Pa,101325Pa (a standard atmospheric pressure, a tubular 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 tubular furnace.
The pressure is adjusted by a vacuum pump, the temperature and the amount of the material.
After the reaction, the method further comprises the following steps: and naturally cooling the reacted product to room temperature, removing impurities by using impurity-removed organic acid, washing, drying and recovering.
The impurity-removed organic acid comprises at least one of oxalic acid, citric acid, gluconic acid and lactic acid.
The impurity removal and recovery process further comprises:
adding corresponding organic acid at 50-100 deg.C, reacting for 1-24 hr, filtering while hot to obtain filtrate, and evaporating at 50-100 deg.C to obtain corresponding organic salt.
The washing comprises the following steps: and (4) carrying out suction filtration and washing by using deionized water to remove impurities. The times of suction filtration and cleaning are 3 times.
The method of drying is not particularly limited in the present invention, and a method of drying known to those skilled in the art may be used.
The present invention is not particularly limited in the source of the above-used raw materials, and may be generally commercially available.
The invention also provides the porous carbon with high specific surface and low surface heterogeneous 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 microparticles or carbon nanostructures.
The prepared carbon micron particles have ultrahigh specific surface area and lower surface oxygen content, and have excellent electrochemical performance when being used as a cathode material of a mixed ion capacitor.
The prepared carbon nano structure has moderate specific surface area and higher surface oxygen content, and has excellent electrochemical performance when being used as a cathode material of a mixed ion capacitor.
The prepared carbon micron particle has size of 1-10 μm, uniformly distributed 1-3nm nanometer pores inside, and surface oxygen content as low as 1.8at.%.
The prepared carbon nano structure is composed of carbon nano particles and carbon nano sheets, the diameter of the carbon nano particles is 5-20nm, and the carbon nano particles are mutually cross-linked 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 performing vacuum drying and rolling to prepare an alkali metal ion mixed capacitor negative plate; and (2) mixing a binder (PCDF) and a conductive agent (Super-P) according to a mass ratio of 8:1:1, adding NMP to prepare slurry, uniformly coating the slurry on an aluminum foil current collector, and performing vacuum drying and rolling to prepare the alkali metal ion mixed capacitor positive plate. When a half cell is assembled, the electrode plate is used as a positive electrode, lithium foil (sodium sheet or potassium sheet) is used as a counter electrode, celgard2500 is used as a lithium ion battery diaphragm, glass fiber is used as a sodium/potassium ion battery diaphragm, 1.0mol/L lithium hexafluorophosphate/sodium/potassium solution (solvent is ethylene carbonate and propylene carbonate with the volume ratio of 1). When the alkali metal ion hybrid capacitor is assembled, the pre-lithium/sodium/potassium-treated negative plate and an electrode coated on an aluminum foil are used as a positive electrode, other components are the same as the half cell, the CR2016 button type alkali metal ion hybrid capacitor is obtained by assembly, and the assembly process is completed in an argon glove box.
The pre-potassized negative plate is prepared by taking alkali metal as a counter electrode and 50-100mA g -1 The current density of (2) was cycled 10 times, and the cut-off voltage was 1.5V.
In order to further illustrate the present invention, the following examples are provided to describe the porous carbon material with different pore structures and surface oxygen contents, its preparation method and application in detail, but it should not be construed as limiting the scope of the present invention.
Examples 1
Placing 5g of calcium oxalate in a high-temperature stainless steel kettle, reacting for 5h at the temperature of 700 ℃ under 10MPa, naturally cooling to room temperature, soaking for 12h at the temperature of 80 ℃ by using equimolar oxalic acid, filtering while the solution is hot, evaporating and recovering filtrate to obtain the calcium oxalate, repeatedly filtering and washing filter residues for 3 times by using deionized water, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
EXAMPLES example 2
Placing 5g of magnesium gluconate in a high-temperature stainless steel kettle, reacting for 5h at the temperature of 700 ℃ under 10MPa, naturally cooling to room temperature, soaking for 12h at the temperature of 80 ℃ by using equimolar gluconic acid, filtering while hot, evaporating and recovering filtrate to obtain magnesium gluconate, repeatedly filtering and washing filter residues for 3 times by using deionized water, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
Embodiment example 3
Placing 5g of magnesium citrate into a high-temperature stainless steel kettle, reacting for 5h at the temperature of 700 ℃ under 10MPa, naturally cooling to room temperature, soaking for 12h at the temperature of 80 ℃ by using equimolar citric acid, filtering while hot, evaporating and recovering filtrate to obtain magnesium citrate, repeatedly filtering and washing filter residues for 3 times by using deionized water, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
Fig. 1 is an XRD pattern of the recovered magnesium citrate and the raw magnesium citrate of example 3 of the present invention.
FIG. 2 is a nitrogen isothermal adsorption and desorption curve of the porous carbon material obtained in example 3. The specific surface area was 201.32m2/g, and the average pore diameter was 8.4nm.
FIG. 3 is a STEM of a porous carbon material obtained in example 3. The morphology of the nano-carbon film 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 5h at 10MPa and 700 ℃, then naturally cooling to room temperature, soaking for 12h at 80 ℃ by using equimolar citric acid, filtering while hot, evaporating and recovering filtrate to obtain calcium citrate, repeatedly filtering and washing filter residues for 3 times by using deionized water, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
FIG. 4 is a nitrogen isothermal adsorption and desorption curve of the porous carbon material obtained in example 4. The specific surface area is 214.05m 2 In terms of/g, the mean pore diameter is 7.4nm.
EXAMPLE 5
Placing 5g of ferric citrate in a high-temperature stainless steel kettle, reacting for 5h at 10MPa and 700 ℃, then naturally cooling to room temperature, soaking for 12h at 80 ℃ by using equimolar citric acid, filtering while hot, evaporating and recovering filtrate to obtain ferric citrate, repeatedly filtering and washing filter residues for 3 times by using deionized water, 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 produced in example 5 of the present invention. The specific surface area of the powder is 242.05m 2 In terms of/g, the mean pore diameter is 11.1nm.
EXAMPLE 6
Placing 5g of magnesium oxalate in a high-temperature stainless steel kettle, reacting for 5h at the temperature of 700 ℃ under 10MPa, naturally cooling to room temperature, soaking for 12h at the temperature of 80 ℃ by using equimolar oxalic acid, filtering while the solution is hot, evaporating and recovering filtrate to obtain magnesium oxalate, repeatedly filtering and washing filter residues for 3 times by using deionized water, and drying to obtain the carbon nano structure consisting of carbon nano particles and carbon nano sheets.
EXAMPLES example 7
Placing 5g of magnesium citrate in a high-temperature stainless steel kettle, reacting for 5h at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12h at 80 ℃ with equimolar citric acid, filtering while hot, evaporating and recovering filtrate to obtain magnesium citrate, repeatedly filtering and washing filter residue with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 microns.
FIG. 6 is a nitrogen isothermal adsorption and desorption curve of the porous carbon material obtained in example 7. The specific surface area of the composite material is 2383.63m2/g, and the average pore diameter is 2.2nm.
FIG. 7 is an SEM photograph of a porous carbon material obtained in example 7. The morphology exhibits carbon microparticles of size 1-20 μm.
EXAMPLES example 8
Placing 5g of magnesium gluconate in a high-temperature stainless steel kettle, reacting for 5h at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12h at 80 ℃ with equimolar gluconic acid, filtering while hot, evaporating and recovering filtrate to obtain magnesium gluconate, repeatedly filtering and washing filter residues for 3 times by using deionized water, and drying to obtain carbon micron particles with the size of 1-20 mu m.
EXAMPLES example 9
Placing a mixture of 5g of magnesium citrate and 1g of citric acid in a high-temperature stainless steel kettle, reacting for 5h at 10Pa and 700 ℃, naturally cooling to room temperature, soaking in citric acid with the same mole as the magnesium citrate at 80 ℃ for 12h, filtering while hot, evaporating and recovering filtrate to obtain magnesium citrate, repeatedly filtering and washing filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 microns.
EXAMPLES example 10
Placing a mixture of 5g of magnesium citrate and 1g of medium-temperature asphalt in a high-temperature stainless steel kettle, reacting for 5h at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12h at 80 ℃ with citric acid with the same mole as the magnesium citrate, filtering while hot, evaporating and recovering filtrate to obtain the magnesium citrate, repeatedly filtering and washing filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 microns.
EXAMPLES example 11
Placing a mixture of 5g of magnesium citrate and 2g of polyvinyl alcohol in a high-temperature stainless steel kettle, reacting for 5h at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12h at 80 ℃ with citric acid with the same mole as the magnesium citrate, filtering while hot, evaporating and recovering filtrate to obtain the magnesium citrate, repeatedly filtering and washing filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 microns.
EXAMPLE 12
Placing a mixture of 5g of magnesium citrate and 3g of glucose in a high-temperature stainless steel kettle, reacting for 5h at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12h at 80 ℃ with citric acid with the same mole as the magnesium citrate, filtering while hot, evaporating and recovering filtrate to obtain the magnesium citrate, repeatedly filtering and washing filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 microns.
EXAMPLES example 13
Placing a mixture of 5g of magnesium citrate and 1g of phenolic resin in a high-temperature stainless steel kettle, reacting for 5h at 10Pa and 700 ℃, then naturally cooling to room temperature, soaking for 12h at 80 ℃ by using citric acid with the same mole as the magnesium citrate, filtering while hot, evaporating and recovering filtrate to obtain the magnesium citrate, repeatedly filtering and washing filter residues by using deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 microns.
EXAMPLES example 14
Placing a mixture of 5g of zinc oxalate and 1g of oxalic acid in a high-temperature stainless steel kettle, reacting for 5h at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12h at 80 ℃ with oxalic acid with the same mole as magnesium oxalate, filtering while hot, evaporating and recovering filtrate to obtain magnesium oxalate, repeatedly carrying out suction filtration and cleaning on filter residues for 3 times by using deionized water, and drying to obtain carbon micron particles with the size of 1-20 microns.
Comparative example 1
Placing 5g of magnesium citrate in a corundum magnet boat, calcining in a tube furnace under the protection of argon at 700 ℃ for 5h, naturally cooling to room temperature, soaking in equimolar citric acid at 80 ℃ for 12h, filtering while hot, evaporating and recovering filtrate to obtain magnesium citrate, repeatedly filtering and washing filter residues with deionized water for 3 times, and drying to obtain carbon micron particles with the size of 1-20 microns.
FIG. 8 is a nitrogen isothermal adsorption/desorption curve of the porous carbon material obtained in comparative example 1. The specific surface area is 1825.43m 2 In terms of/g, the mean pore diameter is 3.7nm.
FIG. 9 is an SEM photograph of the porous carbon material obtained in comparative example 1. The morphology exhibits carbon microparticles of size 1-20 μm in diameter.
Comparative example 2
Placing 5g of citric acid in a high-temperature stainless steel kettle, reacting for 5h at 10Pa and 700 ℃, naturally cooling to room temperature, soaking for 12h at 80 ℃ with dilute hydrochloric acid, repeatedly performing suction filtration and cleaning for 3 times with deionized water, and drying to obtain block granular materials with different sizes.
FIG. 10 is an SEM photograph of the porous carbon material obtained in comparative example 2. The morphology of the material shows bulk granular materials with different sizes.
Comparative example 3
Placing 5g of citric acid in a high-temperature stainless steel kettle, reacting at 10MPa and 700 ℃ for 5h, naturally cooling to room temperature, soaking with dilute hydrochloric acid at 80 ℃ for 12h, repeatedly performing suction filtration and cleaning with deionized water for 3 times, and drying to obtain the carbon microspheres with the size of 1-20 microns.
FIG. 11 is an SEM photograph of a porous carbon material obtained in comparative example 3. The morphology shows carbon microspheres with a diameter of 1-20 μm.
The surface oxygen content of the porous carbon material prepared by the present invention was 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 EXAMPLES example 7 Comparative example 1
Surface oxygen content (at.%) 6.65 1.88 4.94
Example 15
The potassium ion hybrid capacitor and its half-cell were assembled as follows:
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 performing vacuum drying and rolling to prepare a potassium ion mixed capacitor negative plate; and (2) mixing a binder (PCDF) and a conductive agent (SuperP) according to a mass ratio of 8:1:1, adding NMP to prepare slurry, uniformly coating the slurry on an aluminum foil current collector, and performing vacuum drying and rolling to prepare the positive plate of the potassium ion hybrid capacitor. When a half cell is assembled, the electrode plate is used as a positive electrode, the potassium plate is used as a counter electrode, the glass fiber is used as a cell diaphragm, 1.0mol/L potassium hexafluorophosphate solution (the solvent is ethylene carbonate and propylene carbonate with the volume ratio of 1. When the mixed potassium ion capacitor is assembled, the pre-potassized negative plate and an electrode prepared by coating on an aluminum foil are used as a positive electrode, other components are the same as the half battery, the CR2016 button type potassium ion mixed capacitor is obtained by assembly, and the assembly process is completed in an argon glove box.
Conditions for electrochemical performance testing: the electrochemical performance test instrument has the following types: LANDCT2001A, the testing temperature is 25 ℃, the testing voltage range of the negative plate is 0.01-2.5V, the testing voltage range of the positive plate is 1.2-4.2V, the testing 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 electrochemical Performance test results of Potassium ion hybrid capacitor
Figure BDA0003783388510000141

Claims (10)

1. A method for producing a porous carbon material, characterized by comprising: reacting the material at 300-1000 ℃ under 10Pa-300MPa for 1-24h, naturally cooling the reacted product to room temperature, removing impurities with impurity-removing organic acid, washing, drying and recovering to obtain the porous carbon material;
the material is a substance a or a mixture of the substance a and a substance b;
the substance a is an organic salt substance;
the substance b is one or more of organic acid, saccharide organic matter, alcohol organic matter, asphalt and resin.
2. The method according to claim 1, wherein: the dosage ratio of the substance a to the substance b is 5 (0-5).
3. The method for producing a porous carbon material according to claim 1, wherein: the organic salt substance comprises one or more of oxalate, citrate, gluconate or lactate.
4. The method according to claim 3, wherein: 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, ferric 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, iron lactate, nickel lactate, cobalt lactate, and zinc lactate.
5. The method according to claim 1, wherein: the organic acid comprises at least one of oxalic acid, citric acid, gluconic acid and lactic acid;
the saccharide organic substance 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, sebacic alcohol, octadecanol and eicosanol;
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, polyetheretherketone, polystyrene, polyformaldehyde and nylon.
6. The method for producing a porous carbon material according to claim 1, wherein: the organic acid for removing impurities comprises at least one of oxalic acid, citric acid, gluconic acid and lactic acid.
7. The method according to claim 1, wherein: the specific process of removing impurities is as follows:
adding corresponding organic acid for removing impurities at 50-100 deg.C, reacting for 1-24 hr, and filtering while hot to obtain filtrate and residue; then evaporating the filtrate at 50-100 ℃ to obtain corresponding organic salt; and the filter residue is subjected to subsequent washing, drying and recovery to obtain the porous carbon material.
8. The method for producing a porous carbon material according to claim 1, wherein: the temperature rise rate of the materials during the reaction is 0.5-5 ℃/min.
9. A porous carbon material with different pore structures and surface oxygen contents is characterized in that: which is produced by the method for producing a porous carbon material according to any one of claims 1 to 8.
10. An alkali metal ion hybrid capacitor, includes positive pole, negative pole, diaphragm and electrolyte, its characterized in that: the positive and negative electrodes adopt porous carbon materials with different pore structures and surface oxygen contents prepared by the preparation method of the porous carbon material in any one of claims 1 to 8.
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