CN113942995A - Heteroatom-doped porous carbon material and preparation method and application thereof - Google Patents
Heteroatom-doped porous carbon material and preparation method and application thereof Download PDFInfo
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- CN113942995A CN113942995A CN202111350398.8A CN202111350398A CN113942995A CN 113942995 A CN113942995 A CN 113942995A CN 202111350398 A CN202111350398 A CN 202111350398A CN 113942995 A CN113942995 A CN 113942995A
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- porous carbon
- heteroatom
- carbon material
- doped porous
- biomass
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Links
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- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 10
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
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- 239000007788 liquid Substances 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
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- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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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
- C01B32/05—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 OR LIGHT-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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
Abstract
The application discloses a heteroatom-doped porous carbon material and a preparation method and application thereof. The porous carbon takes biomass or biomass hydrolysate as a precursor, the biomass is treated by water-soluble oxysalt aqueous solution to obtain biomass hydrolysate/oxysalt mixed solution, or the biomass hydrolysate is directly added into the oxysalt aqueous solution, then a solution drying product is subjected to pyrolysis and water washing, and the porous carbon is prepared by the aid of the actions of activation, template, doping, catalysis and the like of the water-soluble oxysalt. The heteroatom-doped porous carbon material has unique microscopic morphology and hierarchical pore structure, and contains two or more heteroatoms (such as nitrogen, oxygen, sulfur, phosphorus, boron and the like); the material shows good electrochemical performance when being applied to electrode materials of hybrid ion capacitors, alkali metal ion batteries, super capacitors and fuel cells.
Description
Technical Field
The application relates to heteroatom-doped biomass-based porous carbon and a preparation technology thereof, and a mixed type ion capacitor, an alkali metal ion battery, a super capacitor and a fuel cell which are constructed by using the material as an electrode active material, belonging to the field of porous carbon electrode materials.
Background
The efficient utilization of clean energy can effectively solve the problems of energy and environment, and has important significance for the sustainable development of human society. The development of high-performance electrochemical energy storage and conversion devices (such as lithium ion batteries, supercapacitors, fuel cells, etc.) is one of the most effective ways to achieve efficient utilization of clean energy. Electrode materials are important components of electrochemical energy storage and conversion devices, and determine the electrochemical performance of the devices. The development of high-performance and low-cost electrode materials is an effective strategy for improving the performance of electrochemical energy storage and conversion devices and promoting the large-scale application of the electrochemical energy storage and conversion devices.
The porous carbon has the advantages of high conductivity, stable chemical performance, easily-controlled structural composition, wide precursor source and the like, and is considered to be the electrode material of the electrochemical energy storage and conversion device with the most development potential. Among them, porous carbon having an open pore structure, rich defects, and heteroatom doping tends to exhibit excellent electrochemical properties when used as an electrode material for electrochemical energy storage and conversion devices. However, the preparation of porous carbon usually requires complicated preparation conditions and additional activators, templates, dopants, etc., and has problems of high cost, environmental unfriendliness, etc.: (1) most of porous carbon precursors have single structural composition and higher cost; (2) the design of the open pore structure is often realized by a template method or an activation method, the template and activation effect depends on the dispersibility of a template agent or an activating agent in a precursor, and the residual template agent or the activating agent is generally removed by an acidic or alkaline reagent after carbonization; (3) the introduction of heteroatoms generally requires additional dopants, and the doping effect depends on the degree of dispersion of the dopants in the precursor and the strict control of the doping conditions. Therefore, the selection of the precursor and the auxiliary agent and the design of the preparation scheme are one of the difficulties in the preparation of the high-performance and low-cost porous carbon.
The biomass (such as bones, skins, shells and phosphorus widely existing in animals and roots, stems, leaves, flowers and fruits of plants) and hydrolysate of the biomass (such as chitosan, alginic acid, sucrose, glucose and phytic acid) have the characteristics of rich resources and low cost, and can reduce the preparation cost of the carbon material and realize the effective utilization of the resources as the carbon precursor. In addition, the biomass is rich in various elements such as carbon, nitrogen, oxygen and the like, and the heteroatom-doped carbon material can be directly obtained through pyrolysis. Therefore, the biomass can be used as an ideal precursor for preparing the porous carbon. However, the porous carbon prepared by using biomass as a precursor usually has the problems of single morphology structure and chemical composition, low utilization rate of the pore structure and the like, so that the porous carbon has poor electrochemical performance when used as an electrode material, and is difficult to meet the use requirements of high-performance electrochemical energy storage and conversion devices.
Therefore, how to design a simple and efficient scheme, the biomass is taken as a porous carbon precursor to accurately regulate and control the morphology structure and chemical composition of the porous carbon, and the preparation of the porous carbon electrode material with low cost and high performance is of great significance in promoting the development and application of electrochemical energy storage and conversion devices.
Disclosure of Invention
The invention provides a simple, efficient and low-cost method for preparing heteroatom-doped biomass porous carbon, and the material has unique microscopic morphology, hierarchical pore structure, heteroatom doping, rich defects and high specific surface area. The material shows good electrochemical performance when being used as an electrode material of a hybrid ion capacitor, an alkali metal battery, a super capacitor and a fuel battery.
The specific scheme of the invention is as follows: biomass or biomass hydrolysate is used as a precursor, and water-soluble oxysalt is used as an auxiliary agent. Because of the good water solubility of the assistant, the invention uses the aqueous solution of oxyacid salt to process the biomass to obtain the mixed solution of biomass hydrolysate/oxyacid salt, or directly adds the biomass hydrolysate into the aqueous solution of oxyacid salt, and after the solution is freeze-dried or thermally dried, the solution isAnd (3) carrying out pyrolysis water washing on the dried product, and preparing the porous carbon by virtue of the actions of activation, template, doping, catalysis and the like of the water-soluble oxysalt. The material has an open one-dimensional tubular shape, a two-dimensional sheet shape or a three-dimensional honeycomb shape, and the specific surface area is 100-3000m2 g-1Pore diameter range of 0.5 nm-50 μm, pore volume of 0.1-3.0 cm3 g-1The length-diameter ratio of the nano tube is 5-1000, the thickness of a lamella of the nano sheet is about 1-100 nm, the size of a honeycomb-shaped hole is 0.5-50 μm, and the nano sheet is doped with two or more heteroatoms selected from nitrogen (1.0-20.0 at.%), oxygen (5-20.0 at.%), sulfur (0.2-15.0 at.%), phosphorus (0.5-20.0 at.%), and boron (0.5-10.0 at.%).
According to a first aspect of the present application, a heteroatom-doped porous carbon material is provided.
A heteroatom-doped porous carbon material having a hierarchical porous structure;
the shape of the heteroatom-doped porous carbon material is a one-dimensional tubular shape, a two-dimensional sheet shape or a three-dimensional honeycomb shape.
Optionally, the specific surface area of the heteroatom-doped porous carbon material is 100-3000m2 g-1The pore diameter is 0.5 nm-50 μm, and the pore volume is 0.1-3.0 cm3 g-1。
Optionally, when the shape of the heteroatom-doped porous carbon material is a one-dimensional tubular shape, the length-diameter ratio of the nanotube is 5-1000.
Optionally, when the shape of the heteroatom-doped porous carbon material is a two-dimensional sheet, the thickness of the nanosheet sheet is 1-100 nm.
Optionally, when the morphology of the heteroatom-doped porous carbon material is a three-dimensional honeycomb, the size of the honeycomb pores is 0.5 nm-50 μm.
Optionally, the heteroatom is doped in the porous carbon material, and the doped heteroatom is selected from at least two of nitrogen, oxygen, sulfur, phosphorus and boron.
Optionally, the heteroatom-doped porous carbon material has a specific surface area independently selected from 100m2 g-1、300m2 g-1、500m2 g-1、700m2 g-1、1000m2 g-1、1300m2 g-1、1500m2 g-1、1700m2 g-1、2000m2 g-1、2300m2 g-1、2500m2 g-1、2700m2 g-1、3000m2 g-1Or any value in the range between any two.
Optionally, the pore size of the heteroatom-doped porous carbon material is independently selected from any value of 0.5nm, 1nm, 5nm, 10nm, 50nm, 100nm, 500nm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 30 μm, 40 μm, 50 μm, or a range value between any two.
Optionally, the pore volume of the heteroatom-doped porous carbon material is independently selected from 0.1cm3 g-1、0.2cm3 g-1、0.5cm3 g-1、1cm3 g-1、2cm3 g-1、3cm3 g-1、4cm3 g-1、5cm3 g-1Or any value in the range between any two.
Optionally, the doping amount of nitrogen is 1.0-20.0 at.%.
Optionally, the amount of oxygen doped is 5.0 to 20.0 at.%.
Optionally, the doping amount of the sulfur is 0.2 to 15.0 at.%.
Optionally, the doping amount of the phosphorus is 0.5 to 20.0 at.%.
Optionally, the doping amount of boron is 0.5 to 10.0 at.%.
Optionally, the doping amount of nitrogen is independently selected from any of 1.0 at.%, 2.0 at.%, 5.0 at.%, 7.0 at.%, 10.0 at.%, 12.0 at.%, 15.0 at.%, 17.0 at.%, 20.0 at.%, or a range value therebetween.
Optionally, the doping amount of oxygen is independently selected from any of 5.0 at.%, 7.0 at.%, 10.0 at.%, 12.0 at.%, 15.0 at.%, 17.0 at.%, 20.0 at.%, or a range value therebetween.
Optionally, the doping amount of sulfur is independently selected from any of 0.2 at.%, 0.5 at.%, 1.0 at.%, 2.0 at.%, 5.0 at.%, 7.0 at.%, 10.0 at.%, 12.0 at.%, 15.0 at.%, or a range between any two thereof.
Optionally, the doping amount of the phosphorus is independently selected from any of 0.5 at.%, 1.0 at.%, 2.0 at.%, 5.0 at.%, 7.0 at.%, 10.0 at.%, 12.0 at.%, 15.0 at.%, 17.0 at.%, 20.0 at.%, or a range between any two.
Optionally, the doping amount of boron is independently selected from any of 0.5 at.%, 1.0 at.%, 2.0 at.%, 5.0 at.%, 7.0 at.%, 10.0 at.%, or a range between any two thereof.
According to a second aspect of the present application, a method for preparing a heteroatom-doped porous carbon material is provided. The heteroatom-doped porous carbon material is prepared by adopting the method.
A preparation method of a heteroatom-doped porous carbon material comprises the following steps:
reacting a mixed solution containing a biomass precursor, water-soluble oxysalt and water, removing impurities from the obtained mixture, freeze-drying to obtain a solid, carbonizing the solid, and washing off non-carbon substances to obtain the heteroatom-doped porous carbon material;
the biomass precursor is biomass and/or a biomass hydrolysate.
Optionally, the water-soluble oxysalt is selected from at least one of phosphate, sulfate, nitrate, carbonate, borate, chlorate.
Alternatively, phosphates, sulfates, nitrates, carbonates, borates, chlorates are their corresponding alkali metal salts.
Optionally, the water-soluble oxysalt is selected from at least one of a phosphate, a sulfate, a nitrate, a carbonate, a borate, and an alkali metal salt corresponding to a chlorate.
Optionally, the water soluble oxo acid salt is selected from alkali metal phosphates.
The phosphate, sulfate, nitrate, carbonate, borate, chlorate may be selected from their corresponding potassium salts, sodium salts, etc., such as potassium phosphate, sodium phosphate, potassium sulfate, sodium sulfate, potassium nitrate, sodium nitrate, potassium carbonate, sodium carbonate, potassium borate, sodium borate, potassium chlorate, sodium chlorate.
In the application, the heteroatom-doped porous carbon material is prepared by virtue of the actions of activation, template, doping, catalysis and the like of the water-soluble oxysalt, the one-dimensional tubular or two-dimensional sheet or three-dimensional honeycomb shape can be obtained by virtue of the template action of the water-soluble oxysalt, and the heteroatom contained in the water-soluble oxysalt can be doped into the porous carbon material, such as sulfur atom can be doped into the porous carbon material when potassium sulfate is selected.
The invention adopts water-soluble oxysalt as an auxiliary agent, which is beneficial to the precise regulation and control of the morphology structure and the chemical composition of the porous carbon for the following reasons: (i) the good water solubility enables the oxysalt to be rapidly mixed with the biomass in the aqueous solution, avoids the use of expensive and toxic organic reagents, can be complexed with organic functional groups in the biomass to form an organic-inorganic composite material with certain mechanical strength, and maintains the structure of the biomass charcoal during subsequent pyrolysis; (ii) during pyrolysis, the oxysalt and the biomass charcoal can generate oxidation-reduction reaction in situ, and the oxysalt and the biomass charcoal can generate micropores and mesopores in situ as an activating agent, so that defects are introduced and the carbon layer spacing is increased; part of non-metal elements in the oxygen-containing acid radical can be reduced and doped into the biomass charcoal in the form of heteroatoms; in addition, the oxysalt and the reduction product thereof can be used as a template to regulate and control the microstructure of the biomass charcoal; some transition metal oxysalts also have the function of catalyzing carbon formation at high temperature, and the defects and the graphitization degree of the biomass carbon are regulated and controlled.
Optionally, the biomass comprises a plant tissue organ and/or an animal tissue organ. Plant tissue organs, such as roots, stems, leaves, flowers, fruits, etc., of plants; animal tissue and organs, such as animal bone, skin, scales, and shell.
Optionally, the biomass hydrolysate comprises at least one of gelatin, chitosan, alginic acid, sucrose, glucose, phytic acid.
The biomass material adopted by the invention contains rich elements such as carbon, nitrogen, oxygen and the like, and can realize in-situ heteroatom doping of the porous carbon.
Optionally, the mass ratio of the biomass precursor to the water-soluble oxysalt is 10: 1-1: 100.
Preferably, the mass ratio of the biomass precursor to the water-soluble oxysalt is 5: 1-1: 5.
Optionally, the mass ratio of the biomass precursor to the water-soluble oxysalt is independently selected from any value of 10:1, 9:1, 7:1, 5:1, 1:1.25, 1:3, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, or a range between any two.
Optionally, the concentration of the water-soluble oxysalt is 0.1-10M.
Preferably, the concentration of the water-soluble oxysalt is 0.5-2.0M.
Optionally, the concentration of the water-soluble oxoacid salt is independently selected from any of 0.1M, 0.2M, 0.5M, 0.7M, 1M, 2M, 3M, 4M, 5M, 6M, 7M, 8M, 9M, 10M, or a range between any two.
Optionally, the reaction conditions are:
the reaction temperature is 20-120 ℃, and the reaction time is 0.5-48 h.
Preferably, the reaction temperature is 60-100 ℃, and the reaction time is 6-24 h.
Optionally, the temperature of the reaction is independently selected from any value of 20 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃, 100 ℃, 110 ℃, 120 ℃ or a range value between any two.
Alternatively, the time of the reaction is independently selected from any of 0.5h, 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 24h, 28h, 30h, 34h, 38h, 42h, 48h, or a range between any two.
Optionally, the reaction is carried out under stirring, and the stirring speed is 50-2000 rpm. The reaction may be carried out in a reaction vessel or a glass vessel.
Optionally, the rotational speed of the agitation is independently selected from any of 500rpm, 800rpm, 1000rpm, 1200rpm, 1500rpm, 1700rpm, 2000rpm, or a range between any two.
Optionally, the carbonization conditions are: heating the mixture from room temperature to 500-1200 ℃ at a heating rate of 1-20 ℃/min, and then preserving the heat for 0.5-4 h.
Preferably, the temperature is raised from room temperature to 600-1000 ℃ at the temperature raising rate of 2-10 ℃/min, and then the temperature is maintained for 0.5-2 h.
Optionally, the rate of temperature increase is independently selected from any of 1 ℃/min, 2 ℃/min, 5 ℃/min, 7 ℃/min, 20 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min, 17 ℃/min, 20 ℃/min, or a range of values therebetween.
Optionally, the temperature to which heating is applied is independently selected from any value of 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1100 ℃, 1200 ℃ or a range value between any two.
As a preferred embodiment, comprising:
(1) adding biomass or a biomass hydrolysate and a water-soluble oxysalt into an aqueous solution according to a mass ratio of 10: 1-1: 100, wherein the salt concentration of the solution is 0.1-10M, then stirring at 20-120 ℃ for 0.5-48 h, filtering out precipitates in the solution, and drying the filtrate.
(2) Placing the dried solid in a carbonization furnace, heating the solid to 500-1200 ℃ from room temperature at a heating rate of 1-20 ℃/min, and then preserving heat for 0.5-4 h;
(3) and after the carbonization furnace is cooled to room temperature, taking out the carbonized product, washing off non-carbon substances, and drying to obtain the porous carbon.
Preferably, the drying method of the mixed solution is freeze drying.
According to a third aspect of the present application, there is provided a use of a heteroatom-doped porous carbon material.
The heteroatom-doped porous carbon material and/or the heteroatom-doped porous carbon material prepared by the preparation method is applied to a hybrid ion capacitor, an alkali metal ion battery, a super capacitor and a fuel cell as an active material.
The heteroatom-doped porous carbon material is used as an active material to be applied to electrode materials of hybrid ion capacitors, alkali metal batteries, super capacitors and fuel cells, and the material has good electrochemical performance.
The beneficial effects that this application can produce include:
1) the heteroatom-doped porous carbon material provided by the application has various microscopic appearances, an open pore structure and abundant heteroatoms and defects. The heteroatom-doped porous carbon material has wide application fields, provides a new idea for low-cost and large-scale preparation of high-performance hybrid ionic capacitor, alkali metal battery, super capacitor and fuel cell electrode materials, and promotes the development of electrochemical energy storage and converter.
2) According to the preparation method of the heteroatom-doped porous carbon material, biomass with rich resources and low cost is used as a precursor, so that the preparation cost of the porous carbon is reduced, and the sustainable development concept is met. The biomass material adopted by the invention contains rich elements such as carbon, nitrogen, oxygen and the like, and can realize in-situ heteroatom doping of porous carbon; the water-soluble oxysalt is adopted as an auxiliary agent, so that the precise regulation and control of the morphology structure and the chemical composition of the porous carbon are facilitated. Different from the traditional activation method, the method fully utilizes the physical and chemical characteristics of the raw materials, develops a simple and efficient preparation technology with low cost, and avoids the problems of uneven distribution of the active agent, single shape and structure of the porous carbon and the like.
Drawings
FIG. 1 is a scanning electron microscope (fig. a, 1 μm), a transmission electron microscope (fig. b, 200nm), an element distribution surface scanning (fig. c), a nitrogen absorption and desorption curve (fig. d) and an X-ray photoelectron energy spectrum (fig. e) of the nitrogen and oxygen atom co-doped porous carbon block material prepared in example 1 of the present invention;
FIG. 2 shows constant current charge and discharge test (fig. a and b) and long cycle test (fig. c) in a button-type half cell when the nitrogen and oxygen atom co-doped porous carbon block material prepared in example 1 of the present invention is used as a negative electrode material of a potassium ion cell or a potassium ion capacitor;
FIG. 3 is a scanning electron micrograph (fig. a, 1 μm), a transmission electron micrograph (fig. b, 200nm), an element distribution surface micrograph (fig. c), a nitrogen absorption and desorption curve chart (fig. d) and an X-ray photoelectron energy spectrum (fig. e) of the nitrogen, oxygen and phosphorus three-atom co-doped porous carbon block material prepared in example 2 of the present invention;
FIG. 4 shows a constant current charge and discharge test (FIG. a) and a long cycle test (FIG. b) in a button-type half cell when the nitrogen, oxygen and phosphorus three-atom co-doped porous carbon block material prepared in example 2 of the present invention is used as a positive electrode material of a potassium ion capacitor;
fig. 5 is a constant current charge and discharge test (fig. a and b) and a long cycle test (fig. c) of a potassium ion capacitor constructed when the nitrogen-oxygen atom co-doped porous carbon nanosheet material prepared in example 1 of the present invention and the nitrogen-oxygen-phosphorus atom co-doped porous carbon block material prepared in example 2 of the present invention are used as a negative electrode material and a positive electrode material of the potassium ion capacitor, respectively;
fig. 6 is a scanning electron micrograph (fig. a, 1 μm), a transmission electron micrograph (fig. b, 200nm), an element distribution surface scanning micrograph (fig. c), a nitrogen absorption and desorption curve chart (fig. d) and an X-ray photoelectron energy spectrum (fig. e) of the nitrogen, oxygen and sulfur triple-atom co-doped porous carbon nanosheet material prepared in example 4 of the present invention;
fig. 7 is a constant current charge and discharge test (fig. a and b) and a long cycle test chart (fig. c) in a button-type half cell when the nitrogen, oxygen and sulfur three-atom co-doped porous carbon nanosheet material prepared in example 4 of the present invention is used as a negative electrode material of a potassium ion battery or a potassium ion capacitor;
fig. 8 is a constant current charge and discharge test (fig. a and b) and a long cycle test (fig. c) of a potassium ion capacitor constructed when the nitrogen, oxygen and sulfur triatomic-co-doped porous carbon nanosheet material prepared in example 4 of the present invention and the nitrogen, oxygen and phosphorus triatomic-co-doped porous carbon block material prepared in example 2 of the present invention are used as a negative electrode material and a positive electrode material of the potassium ion capacitor, respectively.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
If not stated, the test method adopts the conventional method, and the instrument setting adopts the setting recommended by the manufacturer.
The analysis method in the examples of the present application is as follows:
the selected instrument for testing the scanning electron microscope image is a JSM-6701F type cold field emission scanning electron microscope of JEOL company, and the accelerating voltage is 5 kV.
The instrument selected for the transmission electron microscope image test is a JSM-2100 transmission electron microscope of JEOL company, and the accelerating voltage is 200 kV.
The instruments selected for the element distribution test are a JEOL JEM-ARM200F transmission electron microscope and an energy dispersion X-ray spectrometer.
The instrument selected for the nitrogen adsorption and desorption curve test is a Quantachrome AUTOSORB-1 type tester manufactured by Quanta, and the test temperature is 77K (liquid nitrogen temperature).
The instrument selected for X-ray photoelectron spectroscopy is ESCALB 250 model instrument from Thermo Fisher.
Example 1
The invention provides a nitrogen and oxygen atom co-doped porous carbon block material, a preparation technology and electrochemical application thereof, and the specific preparation method comprises the following steps:
60mL of deionized water were first poured into the 100mL hydrothermal kettle liner and 2.5g of potassium phosphate was dissolved in the aqueous solution. Then 2g of washed and dried herring scales are added into the solution. The mixture was stirred continuously at 80 ℃ for 24h, at 1000 rpm. After the reaction is finished, removing solid impurities in a vacuum filtration mode, and transferring the obtained solution to a freeze dryer for freeze drying. Then carbonizing the freeze-dried solid in argon atmosphere, wherein the heating rate is 2.5 ℃ for min-1The carbonization temperature is 600 ℃, and the heat preservation time is 1 h. The carbonized product is used with the concentration of 1mol L-1Washing with hydrochloric acid for 12h, washing with deionized water, and drying in a forced air drying oven to obtain porous carbon block. The porous carbon block is named CDC600, as shown in figure 1, wherein a is a scanning electron microscope image with the scale of 1 mu m, and b is a scanning electron microscope image with the scale of 200nmThe specific surface area of the material is 682m, which can be obtained by scanning the elemental distribution surface of the material with a transmission electron microscope, wherein the figure c is a scanning figure of the elemental distribution surface, the figure d is a nitrogen absorption and desorption curve chart of the elemental distribution surface, and the figure e is an X-ray photoelectron energy spectrum chart of the elemental distribution surface2 g-1Pore volume of 0.39cm3 g-1Nitrogen content was 10.9 at.%, oxygen content was 13.0 at.%. As can be seen from the graphs (a) and (b), the morphology of the CDC600 is three-dimensional honeycomb, and the size of the honeycomb pores is 0.6 nm-50 μm.
In order to evaluate the electrochemical performance of the CDC600 as a negative electrode material of a potassium ion battery or a potassium ion capacitor, the CDC600 is prepared into an electrode as an active material and assembled into a button-type half cell for electrochemical performance testing. The preparation method of the electrode comprises the following steps: mixing CDC600 with acetylene black and polyvinylidene fluoride according to the mass ratio of 7:1.5:1.5, and dropwise adding a proper amount of solvent NMP to grind into slurry. And uniformly coating the slurry on the surface of a circular copper foil with the radius of 7mm, and then placing the circular copper foil in a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃ to obtain the CDC600 negative electrode. The CDC600 negative electrode was then assembled into a coin-type half cell with potassium metal plates as the counter and reference electrodes and 1M KFSI/EC + DEC electrolyte (1:1 Vol%). The battery is respectively subjected to cyclic volt-ampere test, constant current charge and discharge test and long cycle test, and the voltage range is as follows: 0.01-3V. The constant current charge and discharge test results of the CDC600 negative electrode are shown in FIG. 2(a, b), and are at 0.05A g-1Reversible capacity at current density of 311.2mA hr g-1Even at 10A g-1At high current density, the current density of the alloy still maintains 134.6mA h g-1The reversible capacity of the material shows higher reversible specific capacity and good rate capability. FIG. 2(c) shows the long cycle stability of CDC600 negative electrodes at 1A g-1After 3000 times of circulation under the current density, the CDC600 cathode can still maintain 164.5mA h g-1Indicating a good long cycle stability of the CDC600 negative electrode.
Example 2
The invention provides a nitrogen, oxygen and phosphorus atom co-doped porous carbon block material, a preparation technology and electrochemical application thereof. The preparation method of the porous carbon block material is the same as that of example 1, except that the carbonization temperature is 1000 ℃, and the finally prepared porous carbon block materialMaterial is named CDC 1000. As shown in FIG. 3, a is a scanning electron micrograph at a scale of 1 μm, b is a transmission electron micrograph at a scale of 200nm, c is a scanning electron micrograph of an element distribution surface thereof, d is a nitrogen absorption/desorption graph thereof, and e is an X-ray photoelectron spectrum thereof, and the CDC1000 has a specific surface area of 1776m2 g-1Pore volume of 0.94cm3 g-1The oxygen content was 12.4 at.%, the nitrogen content was 1.4 at.%, and the phosphorus content was 2.4 at.%. As can be seen from the graphs (a) and (b), the morphology of the CDC1000 is three-dimensional honeycomb, and the size of the honeycomb pores is 0.5 nm-20 μm.
Electrochemical performance of CDC1000 as a positive electrode material of a potassium ion capacitor was evaluated by the same electrochemical test method as example 1, except that aluminum foil was used as a current collector of the CDC1000 positive electrode, and the electrolyte of the assembled button-type half cell was KPF of 0.85M6The volume ratio of the/EC + DEC is 1:1, and the voltage range of electrochemical test is 1.5-4.05V. The result of the constant current charge/discharge test of the CDC1000 positive electrode was 0.05A g as shown in fig. 4(a)-1The specific capacity under the current density is 88.6mA h g-1Even at 5A g-1At a high current density of 53.6mA h g-1The specific capacity shows higher reversible specific capacity and good rate capability. FIG. 4(b) shows the long cycle stability of the CDC1000 positive electrode at 1A g-1After 3000 times of circulation under current density, the capacity retention rate is 90%, which shows that the CDC1000 positive electrode has good long-cycle stability.
In order to evaluate the practical application potential of the CDC1000 and CDC600 in example 1 as the positive electrode and negative electrode materials of the potassium ion capacitor, respectively, the potassium ion capacitor was assembled with the CDC1000 positive electrode and the CDC600 negative electrode, and the electrochemical performance test was performed. As shown in FIG. 5, the assembled potassium ion capacitor was at 40.05W kg-1Has a mass specific power of 107W h kg-1The mass specific energy of (2) is 7.9kW kg-1The high mass specific power of the reactor still keeps 29.3W h kg-1The specific mass energy of (c). In addition, potassium ion capacitors are at 1A g-1The capacity retention rate after 6000 long cycles at the current density was 93%, indicating good cycle stability.
Example 3
The operating conditions were the same as in example 1 except that the mass of potassium phosphate was 6 g. Obtaining the nitrogen and oxygen atom co-doped porous carbon block material. The specific surface area is 926m2 g-1Pore volume of 0.60cm3g-1The oxygen content was 11.13 at.%, and the nitrogen content was 4.97 at.%.
Electrochemical tests were carried out in the same manner as in example 1, and the results showed that it was 0.05A g-1Reversible capacity at current density of 290.8mA hr g-1Even at 10A g-1At high current density, the current density of the alloy still maintains 100.2mA h g-1The reversible capacity of the material shows higher reversible specific capacity and good rate capability. At 1A g-1After 1000 times of circulation under the current density, the current density can still maintain 114.5mA h g-1Indicating that it has good long cycle stability.
Example 4
The invention provides a nitrogen, oxygen and sulfur atom co-doped porous carbon nanosheet material, a preparation technology and electrochemical application thereof. The preparation method of the porous carbon block material is the same as that in example 3, except that the oxysalt is potassium sulfate, the carbonization temperature is 700 ℃, and the final porous carbon nanosheet is named as N/S-C700, as shown in FIG. 6, a is a scanning electron microscope image of the porous carbon nanosheet at the scale of 1 mu m, b is a transmission electron microscope image of the porous carbon nanosheet at the scale of 200nm, C is a scanning image of an element distribution surface of the porous carbon block material, d is a nitrogen absorption and desorption curve diagram of the porous carbon block material, and e is an X-ray photoelectron energy spectrum diagram of the porous carbon block material, the specific surface area of the material is 929m2 g-1Pore volume of 0.62cm2 g-1Nitrogen content was 8.6 at.%, oxygen content was 9.9 at.%, and sulfur content was 8.6 at.%. As can be seen from the graphs (a) and (b), the morphology of the N/S-C700 is two-dimensional sheet shape, and the thickness of the sheet layer is about 5 nm.
In order to evaluate the electrochemical performance of N/S-C700 as a negative electrode material of a potassium ion battery or a potassium ion capacitor, the invention prepares N/S-C700 as an active material into an electrode, and assembles the electrode into a button type half cell for electrochemical performance test. Electrode preparation method, button cell assembly and electrochemical performance testing method thereofThe procedure was as in example 1. The results of the constant current charge/discharge test of the N/S-C700 negative electrode are shown in FIG. 7(a, b), and are at 0.05A g-1Reversible capacity at current density of 434mA hr g-1Even at 5A g-1At high current density of (2), still maintained 107mA h g-1The reversible capacity of the material shows higher reversible specific capacity and good rate capability. FIG. 7(C) shows the long cycle stability of the N/S-C700 negative electrode at 0.5A g-1The capacity of the cathode is not obviously attenuated after the cathode is cycled for 1000 times, which shows that the N/S-C700 cathode has good long-cycle stability.
In order to evaluate the practical application potential of N/S-C700 as the cathode material of the potassium ion capacitor, the potassium ion capacitor is assembled by using the porous carbon CDC1000 prepared in example 2 as the anode and the N/S-C700 cathode, and electrochemical performance tests are carried out. As shown in FIG. 8, the assembled potassium ion capacitor is at 26.7W kg-1Has a mass specific power of 129W h kg-1The mass specific energy of (2.3 kW kg)-1Still maintains 46W-h kg under high mass specific power-1The specific mass energy of (c). In addition, potassium ion capacitors are at 2A g-1The capacity retention rate after more than 4000 long cycles under the current density is 75 percent, and the good cycle stability is shown.
Example 5
The invention provides a nitrogen and oxygen atom co-doped porous carbon block material, a preparation technology and electrochemical application thereof, and the specific preparation method comprises the following steps:
1g of gelatin and 2.5g of potassium phosphate were dissolved in 60mL of deionized water at 80 ℃ with stirring at 1000rpm for 24h to form a clear solution. The solution was then transferred to a lyophilizer for freeze drying. The conditions were then the same as in example 1. Obtaining the nitrogen and oxygen atom co-doped porous carbon block material. The specific surface area is 1011m2 g-1Pore volume of 0.70cm3 g-1The oxygen content was 12.31 at.%, and the nitrogen content was 8.93 at.%.
Electrochemical tests were carried out in the same manner as in example 1, and the results showed that it was 0.05A g-1Reversible capacity at current density of 315.6mA h g-1Even at 10A g-1At high current density, 124.2mA h g is still maintained-1The reversible capacity of the material shows higher reversible specific capacity and good rate capability. At 1A g-1After 1000 times of circulation under the current density, the current density can still keep 123.6mA h g-1Indicating that it has good long cycle stability.
Example 6
Porous carbon block material was prepared as in example 2, except that CDC1000 was applied to the fuel cell catalyst. To evaluate the electrochemical performance of CDC1000 as a fuel cell oxygen reduction catalyst, the present invention added 5mg of CDC1000 catalyst to 1mL of ethanol solution containing 5 wt.% Nafion and sonicated for 0.5h to mix them uniformly. The catalyst slurry was then dropped onto the polished glassy carbon electrode and dried at room temperature (catalyst loading 0.8mg cm)-2) And obtaining the working electrode. Electrochemical tests were performed at room temperature using a standard three-electrode system, mainly performed in 0.1M KOH solution by rotating a circular disc device, with the counter electrode being a graphite rod and the reference electrode being a saturated calomel electrode. The results showed that the half-wave potential of CDC1000 was 0.853V and the kinetic current density at 0.8V was 38.2mA cm-2The hydrogen peroxide yield was 2.8%, and the electrochemical performance was close to that of the platinum-carbon catalyst. And tested for durability of CDC1000, which was only 1.74% of activity decay after 10000s of test, much higher than commercial platinum carbon.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A heteroatom-doped porous carbon material is characterized in that the heteroatom-doped porous carbon material has a hierarchical porous structure;
the shape of the heteroatom-doped porous carbon material is a one-dimensional tubular shape, a two-dimensional sheet shape or a three-dimensional honeycomb shape.
2. The heteroatom-doped porous carbon material as claimed in claim 1, wherein the specific surface area of the heteroatom-doped porous carbon material is 100-3000m2g-1The pore diameter is 0.5 nm-50 μm, and the pore volume is 0.1-3.0 cm3g-1；
Preferably, when the shape of the heteroatom-doped porous carbon material is a one-dimensional tubular shape, the length-diameter ratio of the nanotube is 5-1000;
when the appearance of the heteroatom-doped porous carbon material is a two-dimensional sheet, the thickness of the sheet layer of the nano sheet is 1-100 nm;
when the appearance of the heteroatom-doped porous carbon material is three-dimensional honeycomb, the size of the honeycomb pores is 0.5 nm-50 μm.
3. The heteroatom-doped porous carbon material of claim 1, wherein the heteroatom-doped porous carbon material is doped with heteroatoms selected from at least two of nitrogen, oxygen, sulfur, phosphorus, and boron;
preferably, the doping amount of the nitrogen is 1.0-20.0 at.%;
the doping amount of the oxygen is 5.0-20.0 at.%;
the doping amount of the sulfur is 0.2-15.0 at.%;
the doping amount of the phosphorus is 0.5-20.0 at.%;
the doping amount of the boron is 0.5 to 10.0 at.%.
4. A preparation method of a heteroatom-doped porous carbon material is characterized by comprising the following steps:
reacting a mixed solution containing a biomass precursor, water-soluble oxysalt and water, removing impurities from the obtained mixture, freeze-drying to obtain a solid, carbonizing the solid, and washing off non-carbon substances to obtain the heteroatom-doped porous carbon material;
the biomass precursor is biomass and/or a biomass hydrolysate.
5. The method according to claim 4, wherein the water-soluble salt of an oxyacid is at least one selected from the group consisting of a phosphate, a sulfate, a nitrate, a carbonate, a borate, and a chlorate;
preferably, the water-soluble oxysalt is selected from at least one of phosphates, sulfates, nitrates, carbonates, borates, alkali metal salts corresponding to chlorates.
6. The method of claim 4, wherein the biomass comprises a plant tissue organ and/or an animal tissue organ;
the biomass hydrolysate comprises at least one of gelatin, chitosan, alginic acid, sucrose, glucose and phytic acid.
7. The preparation method according to claim 4, wherein the mass ratio of the biomass precursor to the water-soluble oxysalt is 10:1 to 1: 100;
preferably, the concentration of the water-soluble oxysalt is 0.01-10M;
preferably, the mass ratio of the biomass precursor to the water-soluble oxysalt is 5: 1-1: 5;
preferably, the concentration of the water-soluble oxysalt is 0.5-2.0M.
8. The method according to claim 4, wherein the reaction conditions are as follows:
the reaction temperature is 20-120 ℃, and the reaction time is 0.5-48 h;
preferably, the reaction temperature is 60-100 ℃, and the reaction time is 6-24 h;
preferably, the reaction is carried out under stirring, and the stirring speed is 50-2000 rpm.
9. The method according to claim 4, wherein the carbonization conditions are as follows: heating the mixture from room temperature to 500-1200 ℃ at a heating rate of 1-20 ℃/min, and then preserving heat for 0.5-4 h;
preferably, the temperature is raised from room temperature to 600-1000 ℃ at the temperature raising rate of 2-10 ℃/min, and then the temperature is maintained for 0.5-2 h.
10. Use of the heteroatom-doped porous carbon material according to any one of claims 1 to 3 and/or the heteroatom-doped porous carbon material prepared by the preparation method according to any one of claims 4 to 9 as an active material in hybrid ion capacitors, alkali metal ion batteries, supercapacitors and fuel cells.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114300274A (en) * | 2022-01-24 | 2022-04-08 | 西北民族大学 | Boron-sulfur co-doped porous carbon material and preparation method and application thereof |
| CN114583137A (en) * | 2022-03-17 | 2022-06-03 | 华中科技大学 | Method for modifying carbon surface by doping sulfur with phosphorus and application thereof |
| CN114956268A (en) * | 2022-05-16 | 2022-08-30 | 河南师范大学 | Preparation method and application of nitrogen-boron double-doped porous carbon-based electrode material |
| CN115078492A (en) * | 2022-06-22 | 2022-09-20 | 江苏大学 | Preparation method and application of BiOX/N-doped biomass charcoal nanocomposite |
| CN115424870A (en) * | 2022-08-30 | 2022-12-02 | 南昌工程学院 | Biomass-derived carbon material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105575673A (en) * | 2016-03-11 | 2016-05-11 | 北京化工大学 | Preparation method of nitrogen and oxygen in-situ doped porous carbon electrode material and application thereof |
| WO2017083825A1 (en) * | 2015-11-13 | 2017-05-18 | David Mitlin | Activated carbons from dairy products |
| WO2018103386A1 (en) * | 2016-12-07 | 2018-06-14 | 温州大学 | Sheet-shaped nitrogen-phosphorus co-doped porous carbon material and method for preparation thereof and use thereof |
| CN109553098A (en) * | 2018-09-04 | 2019-04-02 | 四川大学 | A kind of method and application preparing the foramen magnum-mesoporous carbon of high-specific surface area using salt template |
| CN110697714A (en) * | 2019-10-17 | 2020-01-17 | 北京化工大学 | Radish-derived nitrogen-doped graded porous carbon and preparation method and application thereof |
| CN112374485A (en) * | 2020-11-12 | 2021-02-19 | 滁州学院 | Preparation method of nitrogen-phosphorus double-doped foamy carbon for zinc ion hybrid capacitor |
-
2021
- 2021-11-15 CN CN202111350398.8A patent/CN113942995B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017083825A1 (en) * | 2015-11-13 | 2017-05-18 | David Mitlin | Activated carbons from dairy products |
| CN105575673A (en) * | 2016-03-11 | 2016-05-11 | 北京化工大学 | Preparation method of nitrogen and oxygen in-situ doped porous carbon electrode material and application thereof |
| WO2018103386A1 (en) * | 2016-12-07 | 2018-06-14 | 温州大学 | Sheet-shaped nitrogen-phosphorus co-doped porous carbon material and method for preparation thereof and use thereof |
| CN109553098A (en) * | 2018-09-04 | 2019-04-02 | 四川大学 | A kind of method and application preparing the foramen magnum-mesoporous carbon of high-specific surface area using salt template |
| CN110697714A (en) * | 2019-10-17 | 2020-01-17 | 北京化工大学 | Radish-derived nitrogen-doped graded porous carbon and preparation method and application thereof |
| CN112374485A (en) * | 2020-11-12 | 2021-02-19 | 滁州学院 | Preparation method of nitrogen-phosphorus double-doped foamy carbon for zinc ion hybrid capacitor |
Non-Patent Citations (4)
| Title |
|---|
| LIU, MY ET AL.: "Potassium compound-assistant synthesis of multi-heteroatom doped ultrathin porous carbon nanosheets for high performance supercapacitors", 《NANO ENERGY》 * |
| LIU, MY ET AL.: "Potassium compound-assistant synthesis of multi-heteroatom doped ultrathin porous carbon nanosheets for high performance supercapacitors", 《NANO ENERGY》, vol. 51, 7 September 2018 (2018-09-07), pages 366 - 372 * |
| 刘梦月: "基于钾化合物辅助法的生物质多孔炭的制备及电化学储能应用研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
| 刘梦月: "基于钾化合物辅助法的生物质多孔炭的制备及电化学储能应用研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》, 15 January 2021 (2021-01-15), pages 1 - 9 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114300274A (en) * | 2022-01-24 | 2022-04-08 | 西北民族大学 | Boron-sulfur co-doped porous carbon material and preparation method and application thereof |
| CN114300274B (en) * | 2022-01-24 | 2023-07-14 | 西北民族大学 | Boron-sulfur co-doped porous carbon material and preparation method and application thereof |
| CN114583137A (en) * | 2022-03-17 | 2022-06-03 | 华中科技大学 | Method for modifying carbon surface by doping sulfur with phosphorus and application thereof |
| CN114583137B (en) * | 2022-03-17 | 2023-10-24 | 华中科技大学 | Method for modifying carbon surface by sulfur doped phosphorus and application thereof |
| CN114956268A (en) * | 2022-05-16 | 2022-08-30 | 河南师范大学 | Preparation method and application of nitrogen-boron double-doped porous carbon-based electrode material |
| CN115078492A (en) * | 2022-06-22 | 2022-09-20 | 江苏大学 | Preparation method and application of BiOX/N-doped biomass charcoal nanocomposite |
| CN115424870A (en) * | 2022-08-30 | 2022-12-02 | 南昌工程学院 | Biomass-derived carbon material and preparation method and application thereof |
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