CN106602013B - Preparation method of sulfur-activated carbon/graphene composite material - Google Patents

Preparation method of sulfur-activated carbon/graphene composite material Download PDF

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CN106602013B
CN106602013B CN201611178237.4A CN201611178237A CN106602013B CN 106602013 B CN106602013 B CN 106602013B CN 201611178237 A CN201611178237 A CN 201611178237A CN 106602013 B CN106602013 B CN 106602013B
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sulfur
activated carbon
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王俊中
刘勇志
王俊英
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Shanxi Institute of Coal Chemistry of CAS
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    • 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
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    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
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Abstract

The invention discloses a preparation method of a sulfur-activated carbon/graphene composite material, which comprises the following steps: (1) pretreating a biomass raw material; (2) mixing the pretreated biomass raw material with graphene and an activating agent to form a solid mixed material; (3) activating, washing, carrying out solid-liquid separation and drying on the solid mixed material to obtain an activated carbon/graphene composite material; (4) and compounding the activated carbon/graphene composite material with sulfur to obtain the sulfur-activated carbon/graphene composite material. The process for preparing the composite material provided by the invention has the advantages of simple steps, high efficiency and low energy consumption, and can realize large-scale production.

Description

Preparation method of sulfur-activated carbon/graphene composite material
Technical Field
The invention relates to a preparation method of a sulfur-activated carbon/graphene composite material, and belongs to the field of electrochemical energy storage.
Background
With the rapid development of the fields of space technology, mobile communication, missile, aerospace, etc., and the increasing concern of modern people about energy crisis and environmental protection problems, research and development of lithium secondary batteries with high energy density has attracted much interest (inorg. chem. front., 2015, 2, 1059). Lithium sulfur batteries are considered to be one of the most promising new multi-electron reactive secondary battery systems. The theoretical specific capacity of the reaction of elemental sulfur and lithium is 1675 mAh g-1, the mass specific energy reaches 2600 Wh kg-1, and the material is far higher than the existing traditional lithium ion secondary battery material. Meanwhile, the sulfur has the advantages of rich source, environmental friendliness and the like. Although the energy density of the lithium-sulfur battery is far higher than that of the commercial secondary battery, the lithium-sulfur secondary battery has various problems of low utilization rate of active materials, poor rate performance, short battery life and the like in the practical process, so that the wide popularization and application of the lithium-sulfur secondary battery are restricted (adv. funct. mater. 2016, 26, 6351).
The graphene is a compound of having sp2The single-layer sheet-shaped structure material formed by the carbon atoms of the hybrid orbit is the thinnest and the hardest nano material at present, has special physical properties, and provides a good way for modifying the lithium-sulfur battery by the carbon material. Despite the good conductivity of grapheneThe utilization rate of elemental sulfur is effectively improved, but the sulfur is directly contacted with the electrolyte due to the large specific surface area of the elemental sulfur, so that the active substances are dissolved. Thereby creating a shuttle effect that affects the cycle life of the battery. The special pore structure of the activated carbon material not only provides a loading place for elemental sulfur, but also has strong capillary adsorption effect to effectively inhibit the dissolution of polysulfide (Journal of Energy Chemistry 2013, 22, 214, CN201310659172.5, CN201410476466.9, CN 201180036690.0).
Under the large background of energy crisis, the conventional activated carbon raw materials such as wood and coal gradually quit the historical stage, and are replaced by biomass materials with the characteristics of low price, rich resources, safety, renewability and the like. The biomass resource is used as the raw material to prepare the activated carbon, so that the cost of the activated carbon is reduced to a great extent; on the other hand, the crop residues are recycled, and the environmental problem caused by unorganized burning is avoided. Therefore, the preparation and application of biomass activated carbon have been receiving wide attention in recent years (CN 201410729808.3, CN 201610373129.6).
The preparation method of the active carbon is divided into three types: physical activation methods, chemical activation methods, and combined physical-chemical activation methods. The physical activation method is that the material is carbonized, then the furnace carrying carbonized product is filled with oxidizing gas such as carbon dioxide, water vapor, air or the mixture gas, and then the activated carbon product is obtained after activation at higher temperature. From the practical production point of view, the chemical activation method has an irreplaceable position, the carbonization and the activation are simultaneously carried out in the chemical activation method, and the activating agent is usually KOH, NaOH and ZnCl2、K2CO3And H3PO4And the like. If the activated carbon/graphene composite material can be prepared by taking agricultural and forestry wastes which are rich in sources, low in price and renewable as raw materials and then compounded with sulfur to obtain the sulfur-activated carbon/graphene composite material for the lithium-sulfur battery, large-scale commercial production and application of the sulfur-activated carbon/graphene composite material can be realized (CN 201410729808.3).
Disclosure of Invention
The invention aims to provide a preparation method of a sulfur-activated carbon/graphene composite material, which is simple, easy to operate and control, low in cost, high in efficiency and good in quality. The method has the advantages of cheap and easily-obtained raw materials, abundant sources and reproducibility, and meets the requirements of industrial production.
The sulfur-activated carbon/graphene composite material comprises the following components: a sulfur content of 10 wt% to 90 wt% (10-90 wt%), an activated carbon/graphene composite content of 10 wt% to 90 wt% (10-90 wt%);
the sulfur-activated carbon/graphene composite material is characterized in that the mass fraction of activated carbon in the activated carbon/graphene composite material is 0-100% (0-100%), and the mass fraction of graphene is 0-100% (0-100%); the content of the heteroatom in the activated carbon is 0 wt% to 90 wt% (0-90 wt%); the content of heteroatoms in the graphene is 0 wt% to 90 wt% (0-90 wt%);
the graphene as described above includes but is not limited to one of graphene and heteroatom doped graphene;
the heteroatom-doped graphene described above includes, but is not limited to, nitrogen-doped graphene, phosphorus-doped graphene, sulfur-doped graphene, boron-doped graphene, nitrogen-phosphorus-codoped graphene, nitrogen-sulfur-codoped graphene, nitrogen-boron-codoped graphene, phosphorus-sulfur-codoped graphene, phosphorus-boron-codoped graphene, sulfur-boron-codoped graphene, nitrogen-phosphorus-sulfur-codoped graphene, nitrogen-phosphorus-boron-codoped graphene, nitrogen-sulfur-boron-codoped graphene, phosphorus-sulfur-boron-codoped graphene, nitrogen-phosphorus-sulfur-boron-codoped graphene, and the like.
The activated carbon as described above includes but is not limited to one of activated carbon, heteroatom-doped activated carbon;
the heteroatom-doped activated carbon includes, but is not limited to, nitrogen-doped activated carbon, phosphorus-doped activated carbon, sulfur-doped activated carbon, boron-doped activated carbon, nitrogen-phosphorus-codoped activated carbon, nitrogen-sulfur-codoped activated carbon, nitrogen-boron-codoped activated carbon, phosphorus-sulfur-codoped activated carbon, phosphorus-boron-codoped activated carbon, sulfur-boron-codoped activated carbon, nitrogen-phosphorus-sulfur-codoped activated carbon, nitrogen-phosphorus-boron-codoped activated carbon, phosphorus-sulfur-boron-codoped activated carbon, nitrogen-phosphorus-sulfur-boron-codoped activated carbon, and the like.
The invention also provides a preparation method of the sulfur-activated carbon/graphene composite material; the method comprises the following steps:
1. pretreating a biomass raw material; 2. mixing the pretreated biomass raw material with graphene and an activating agent; 3. activating, washing, carrying out solid-liquid separation and drying on the solid mixed material; 4. compounding the composite material with sulfur to obtain a sulfur-activated carbon/graphene composite material;
the specific process of the step 1 comprises the following steps:
the pretreatment of the biomass raw material in the step 1 includes, but is not limited to, one or more than two steps of pre-drying, crushing, screening, washing, solid-liquid separation, drying and the like;
the biomass raw material in the step 1 includes but is not limited to one or more of agriculture and forestry resources and wastes, light industrial resources and wastes;
the agriculture and forestry resources and wastes include, but are not limited to, rice hulls, shaddock peels, durian peels, lotus leaves, wheat stalks, corn cobs, jute stalks, hemp stalks, lotus flower stalks, catkins, spartina alterniflora, plant ash, orange peels, bean stalks, melon seed peels, wood sawdust, cotton stalks, cattail wool, droughhairweed, lotus flower stalks, poplar wood chips, grain husks, bean pods, straw, cedar wood chips, rape stalks, bamboo powder, pine wood chips, red wood chips, juniper wood chips, birch wood chips, cedar wood chips, coconut trees and wastes thereof, cassava stalks, small eucalyptus wastes, cashew shells, olive tree wastes, mulberry branches, bamboo and processing residues, switchgrass, kenaf stalk cores, wheat stalks, poplar and wastes thereof, willow and wastes thereof, elm and wastes thereof, peach trees and wastes thereof, apricot trees and wastes thereof, pear trees and wastes thereof, bamboo and wastes thereof, corn cobs and wastes thereof, jute stalk cores, wheat stalks, rice straw, albizzia julibrissin and its waste, bamboo shoot shell, palm wood and its waste, jujube wood and its waste, grapevine, chinese wolfberry stem, sorghum stalk, cypress and its waste, ryegrass, violet, eggplant, papaya, reed, water weed, sorghum shell, aegilops tauschii, tobacco stem, walnut shell, apricot kernel, coconut shell, pistachio shell, palm shell, hawthorn kernel, oak shell, peanut shell, water chestnut shell, olive kernel, jujube kernel, mixed southern hardwood after hydrolysis of plum kernel, chestnut wood, carbonized apricot kernel, hazelnut shell, chestnut shell, wheat shell, oak sawdust, walnut shell, waste tea leaf, beet root, cotton shell, banana shell, cherry kernel, orange peel, coffee bean pod, cassava peel, chestnut bud, oil palm shell, larch wood chip, eucalyptus wood, sawdust, peanut straw, rubber shell, corn cob, Chinese chestnut shell, silvery gum, waste pepper, oil tea-oil camellia shell, rapeseed shell, rape seed shell, etc, One or more of erythrina wood chips, bean stalks, rice hulls, date palm kernels, rice bran, beet leaves, oat stalks, sunflower stalks, pine needles, olive branch tamarind, fir trees and their wastes, teak sawdust, oil palm trees, cotton linters, wheat straws, hemp, mulberry bark, paper mulberry bark, grape seeds, oat hulls, vine sawdust, oak sawdust, algae, sesame stalks, potatoes, hemp, chick pea hulls, tobacco stems, vine chips, plum kernels, palm hulls, foot woods, switch grass, and the like;
the light industrial byproducts include but are not limited to one or more of alcohol lees, oil meal, white spirit lees, beer lees, vinegar lees, traditional Chinese medicine residues, sweet potato residues, tea/coffee residues, coconut shell residues, furfural residues, sisal residues, antibiotic bacteria residues, papermaking black liquor, bagasse, fermentation bacteria residues, papermaking leftover materials, black liquor soluble residues, fruit and vegetable processing residues, olive residue filter cakes, oil palm shell filter cakes, end product biomass charcoal of refined biomass oil, biomass cracking residual charcoal and the like;
the pre-drying of the biomass raw material includes but is not limited to one of natural drying, forced air drying, vacuum drying and the like;
the natural drying time is 1 hour to 30 days (1 h-30 days);
the temperature of the forced air drying or vacuum drying is 70-120 ℃ (70-120 ℃), and the drying time is 2-96 hours (2-96 hours);
the crushing of the biomass raw material includes, but is not limited to, mechanical crushing, ultrasonic crushing; the particle size of the crushed biomass raw material is 20 meshes to 100 meshes;
the mechanical crushing comprises but is not limited to ball milling, crushing by a crusher and the like; the ball milling ball can be one of stainless steel ball, agate ball, zirconia ball, alumina ball or silicon carbide ball; the diameter of the ball is 1 mm to 15 mm (1-15 mm); the ball milling tank can be made of stainless steel, agate or zirconia; the ball-material ratio (mass ratio) is 15-150: 1; the ball milling speed is as follows: 50 rpm to 580 rpm (50-580 rpm); the gas is more than one of air, nitrogen, argon or helium; the ball milling time is 0.5 to 72 hours (0.5 to 72 hours);
the ultrasonic crushing is carried out at the frequency of 20 kHz to 30 kHz (20-30 kHz), the power density of 500W to 1000W (500-;
screening the crushed biomass raw material by adopting one of a three-dimensional vibrating screen, a swinging screen, a mine screen, a linear vibrating screen, an ultrasonic vibrating screen, an airflow screen, a drum screen, a direct discharge filter screen, a checking screen and a high-frequency vibrating screen;
the washing of the biomass raw material comprises using inorganic acid (concentrated or diluted), water;
the mineral acid (concentrated or dilute) includes but is not limited to H2SO4、H3PO4、HNO3、HClO4、HClO3And (5) one of S. The mass percentage of the effective components in the inorganic acid (concentrated or diluted) is between 1 percent and 98 percent (1-98 percent).
The solid-liquid separation uses porous polymeric (e.g., polypropylene, polyethylene, polystyrene, polyester, and cellulose) bags or membranes including, but not limited to, having an average pore size between 0.2 microns and 20 microns (0.2-20 μm). The porous polymeric bag facilitates liquid-solid separation, with solids remaining in the bag and liquids being thrown, squeezed, pressed or run off.
The drying of the biomass raw material comprises but is not limited to one of forced air drying and vacuum drying;
the temperature of the forced air drying or vacuum drying is 70-120 ℃ (70-120 ℃), and the drying time is 2-96 hours (2-96 hours);
step 2, the concrete steps include the following:
the mixing of the biomass feedstock with graphene and activating agent as described above uses one of, but not limited to, impregnation, stirring, ultrasound, high speed shearing, ball milling;
the graphene in step 2 as described above includes but is not limited to one of graphene and heteroatom-doped graphene;
the heteroatom-doped graphene described above includes, but is not limited to, nitrogen-doped graphene, phosphorus-doped graphene, sulfur-doped graphene, boron-doped graphene, nitrogen-phosphorus-codoped graphene, nitrogen-sulfur-codoped graphene, nitrogen-boron-codoped graphene, phosphorus-sulfur-codoped graphene, phosphorus-boron-codoped graphene, sulfur-boron-codoped graphene, nitrogen-phosphorus-sulfur-codoped graphene, nitrogen-phosphorus-boron-codoped graphene, nitrogen-sulfur-boron-codoped graphene, phosphorus-sulfur-boron-codoped graphene, nitrogen-phosphorus-sulfur-boron-codoped graphene, and the like.
The above-mentioned mixing of the biomass raw material, the graphene and the activating agent can be carried out with or without adding a dispersing agent;
the dispersant includes, but is not limited to, water, organic solvents, inorganic acids (concentrated or dilute), aqueous solutions of soluble inorganic bases, organic solutions or aqueous solutions of soluble inorganic salts. The ratio of dispersant (volume, ml) to solid material (mass, g) is controlled between 1 ml/g and 100ml/g (1-100 ml/g).
The organic solvent may include, but is not limited to, one of liquid alcohol, acetone, diethyl ether, and other liquid oxygen-containing organic solvents.
The inorganic acid (concentrated or diluted) is H3PO4(ii) a The mass percentage of the effective components in the inorganic acid (concentrated or diluted) is between 1 percent and 85 percent (1-85 percent).
The soluble inorganic base includes but is not limited to NaOH, KOH, Na2CO3、K2CO3One of (1); the mass percentage of the inorganic base in the soluble inorganic base aqueous solution is between 0.5 percent and 100 percent (0.5-100 percent);
the soluble inorganic salt is ZnCl2(ii) a The mass fraction of inorganic salt in the soluble inorganic salt water solution is between 0.01% and 432% (0.01-432%). The mass fraction of the inorganic salt in the soluble inorganic salt organic solution is between 0.01 percent and 40 percent (0.01-40 percent);
activators as described above include, but are not limited to, KOH, NaOH, ZnCl2、K2CO3、Na2CO3、H3PO4、H2SO4One of (1); wherein the mass percentage of the effective components in the inorganic acid (concentrated or diluted) is between 1 percent and 98 percent (1-98 percent).
The mass ratio of the biomass raw material to the graphene is 0:10 to 10:0 (0: 10-10: 0);
the mass ratio of the solid material to the activating agent is 1 (0.1-10);
the frequency of the ultrasound as described above is 20 kHz to 30 kHz (20-30 kHz), the power density is 500W to 1000W (500-.
The stirring is carried out magnetically or/and mechanically for 3-60 hours (3-60 hours) at 20-60 deg.C (20-60 deg.C).
The working temperature of the high-speed shearing machine is adjustable from 20 ℃ to 60 ℃ (20-60 ℃); the rotating speed is 50 to 3000 revolutions per minute (50 to 3000 rpm) and can be adjusted; the shearing time is adjustable from 0.5 h to 72 h (0.5-72 h); the dispersant added in the shearing can be water;
the dipping time is adjustable from 2 hours to 144 hours (2-144 hours); the dipping temperature is 20 ℃ to 60 ℃ (20 ℃ to 60 ℃);
the ball-milling ball can be one of stainless steel ball, agate ball, zirconia ball, alumina ball or silicon carbide ball; the diameter of the ball is 1 mm to 15 mm (1-15 mm); the ball milling tank can be made of stainless steel, agate or zirconia; the ball-material ratio (mass ratio) is 15-150: 1; the ball milling speed is as follows: 50 rpm to 580 rpm (50-580 rpm); the gas is more than one of air, nitrogen, argon or helium; the ball milling time is 0.5 to 72 hours (0.5 to 72 hours);
when mixed with the addition of a dispersant as described above, the solid-liquid separation uses porous polymer (e.g., polypropylene, polyethylene, polystyrene, polyester, and cellulose) bags or membranes including, but not limited to, those having an average pore size between 0.2 microns and 20 microns (0.2-20 μm). The porous polymeric bag facilitates liquid-solid separation, with solids remaining in the bag and liquids being thrown, squeezed, pressed or run off.
Step three, the concrete steps in step 3 include the following:
the activation temperature of the solid material is 350-1050 ℃ (350-1050 ℃); the activation time is 20 minutes to 96 hours (20 min to 96 hours); the gas introduced during the activation is one of nitrogen, argon, helium and ammonia;
the ammonia gas can be pure ammonia gas or a mixed gas of the ammonia gas and one of inert gases such as nitrogen, argon, helium and the like; the volume fraction of ammonia in the ammonia gas mixture is between 1% and 99% (1-99%);
the washing of the activated material is one of water, water-soluble inorganic acid, water-soluble organic acid, water-soluble inorganic base and water-soluble organic base;
the water-soluble inorganic acid (concentrated or dilute) includes but is not limited to H2SO4、H3PO4、HCl、HNO3、HClO4、HClO3One of S; the mass percentage of the effective components in the water-soluble inorganic acid (concentrated or diluted) is between 1 percent and 98 percent (1-98 percent). The water-soluble inorganic base includes but is not limited to NaOH, KOH, Na2CO3、NH3•H2O、K2CO3One of (1); the above-mentionedThe mass percentage of the inorganic base in the water-soluble inorganic base water solution is between 0.5 percent and 50 percent (0.5-50 percent). The water-soluble organic acid (concentrated or diluted) comprises one of water-soluble carboxylic acid and derivatives thereof, water-soluble sulfonic acid and derivatives thereof, water-soluble sulfinic acid and derivatives thereof, water-soluble thiocarboxylic acid and derivatives thereof; the mass percentage of the effective components in the water-soluble organic acid (concentrated or diluted) is between 1 percent and 60 percent (1-60 percent); the water-soluble organic base (concentrated or diluted) comprises one of, but is not limited to, water-soluble amine compounds, water-soluble alkali metal salts of alcohols, water-soluble alkaloids and pyridine; the mass percentage of the effective components in the water-soluble organic alkali is 1.5-65%.
Solid-liquid separation as described above uses porous polymeric (e.g., polypropylene, polyethylene, polystyrene, polyester, and cellulose) bags or membranes including, but not limited to, having an average pore size between 0.2 microns and 20 microns (0.2-20 μm). The porous polymeric bag facilitates liquid-solid separation, with solids remaining in the bag and liquids being thrown, squeezed, pressed or run off.
The active carbon/graphene composite material solid obtained by the method can be freeze-dried at-50 ℃ (50 ℃) for 10 hours to 96 hours (10 hours to 96 hours) to obtain active carbon/graphene composite material powder; drying by blowing or vacuum at 70-120 deg.C (70-120 deg.C) for 2-96 hr (2-96 hr); active carbon/graphene composite material powder can be obtained.
Fourthly, the specific steps of the step 4 comprise the following steps:
the method for compounding sulfur with the activated carbon/graphene composite material as described above includes, but is not limited to, one of a liquid phase impregnation method, a heating and melting method, a high-energy ball milling method, a solvothermal method, and a precipitation method;
the liquid phase impregnation method comprises the following specific steps: (1) dispersing a sulfur source; (2) mixing a sulfur source with the activated carbon/graphene composite material, carrying out solid-liquid separation, and drying to obtain a sulfur-activated carbon/graphene composite material;
the sulfur content of the sulfur-activated carbon/graphene composite material prepared by the liquid phase impregnation method is between 10% and 90% (10-90%) by mass;
the sulfur source in the liquid phase impregnation method as described above includes, but is not limited to, sulfur powder, thiourea, (NH)4)2S、(NH4)2S2O8、H2S、NaHSO3、Na2S2O3、Na2SO3、Na2SO4、CS2One of thiol, thioether, sulfone, sulfoxide, thioylide, thiophenol, thio-substituted aldehyde, thio-substituted ketone, thio-substituted amine, thio-substituted amide, thio-substituted carboxylic acid, derivative of thio-substituted carboxylic acid, thioalkanolamine, sulfur-containing heterocyclic compound, disulfide, polysulfide, isothiocyanate, organic sulfur-containing polymer, etc.;
the sulfur-containing organic compound as described above uses an organic solvent as a dispersant; the sulfur powder and the sulfur-containing inorganic compound use an aqueous solution of a surfactant as a dispersant; the ratio of the dispersing agent (volume, ml) to the activated carbon/graphene composite material (mass, g) is controlled between 1 ml/g and 100ml/g (1-100 ml/g).
The organic solvent includes, but is not limited to, one of liquid alcohols, liquid amines, liquid alcamines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane, and acetonitrile;
the surfactant as described above includes, but is not limited to, one of quaternary ammonium compounds, sulfated oils, higher fatty alcohol sulfates, soaps, fatty sulfonates, alkylaryl sulfonates, alkylnaphthalene sulfonates, lecithin, amino acid zwitterionic surfactants, betaine zwitterionic surfactants, fatty acid glycerides, polyhydric alcohols, polyoxyethylene nonionic surfactants, polyoxyethylene-polyoxypropylene copolymers; the concentration of the surfactant aqueous solution is between 0.0001 mol/L and 0.5 mol/L (0.0001-0.5 mol/L);
the mixing method of the sulfur source and the activated carbon/graphene composite material in the liquid-phase impregnation method can adopt one of impregnation, ultrasound, stirring, ball milling and high-speed shearing;
the reaction temperature in the liquid phase impregnation method is between 20 ℃ and 100 ℃ (20-100 ℃); the reaction time is between 0.5 hour and 144 hours (0.5-144 hours);
the heating melting method comprises the following specific steps: (1) mixing a sulfur source with the activated carbon/graphene composite material, and carrying out heat treatment to obtain a crude sulfur-activated carbon/graphene composite material; (2) purifying the crude sulfur-activated carbon/graphene composite material, carrying out solid-liquid separation, and drying to obtain the sulfur-activated carbon/graphene composite material;
the sulfur content of the sulfur-activated carbon/graphene composite material prepared by the heating melting method is adjustable from 10% to 90% (10-90%);
the sulfur source in the heating and melting method as described above includes, but is not limited to, one of sulfur powder, thiourea, solid thiol, solid thioether, solid sulfone, solid sulfoxide, solid thioylide, solid thiophenol, solid thio-substituted aldehyde, solid thio-substituted ketone, solid thio-substituted amide, solid thio-substituted carboxylic acid, derivative of solid thio-substituted carboxylic acid, solid thio-containing heterocyclic compound, solid organic disulfide, solid organic polysulfide, solid isothiocyanate, solid organic thio-containing polymer, etc.;
the mixing mode of the sulfur source and the activated carbon/graphene composite material in the heating melting method is one of mechanical mixing and ultrasonic mixing; the mechanical mixing comprises ball milling or stirring;
in the heating melting method, the heating temperature of the sulfur filling of the activated carbon/graphene is 100-1000 ℃ (100-1000 ℃), the heating time is 0.5-96 hours (0.5-96 hours), and the protective gas is one of nitrogen, argon and helium, so that the crude sulfur-activated carbon/graphene composite material is obtained;
the purification of the crude sulfur-activated carbon/graphene composite material comprises one of heat treatment and washing methods;
the heat treatment temperature for purifying the crude sulfur-activated carbon/graphene composite material is 200-500 ℃ (200-500 ℃), and the heating time is 0.5-96 hours (0.5-96 hours); the protective gas is one of nitrogen, argon and helium;
the solvent used for washing the crude sulfur-activated carbon/graphene composite material as described above includes, but is not limited to, one of water, liquid alcohols, liquid amines, liquid alcamines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane, acetonitrile, and the like;
the purification of the crude sulfur-activated carbon/graphene composite material comprises one of mechanical/magnetic stirring and ultrasound.
The high-energy ball milling method comprises the following specific steps: (1) mixing and grinding a sulfur source and the activated carbon/graphene composite material to obtain a crude sulfur-activated carbon/graphene composite material; (2) purifying the crude sulfur-activated carbon/graphene composite material, carrying out solid-liquid separation, and drying to obtain the sulfur-activated carbon/graphene composite material;
the sulfur content of the sulfur-activated carbon/graphene composite material prepared by the high-energy ball milling method is between 10% and 90% (10-90%) by mass;
the sulfur source in the high energy ball milling method includes but is not limited to one of sulfur powder, thiourea, thiol, thioether, sulfone, sulfoxide, thioylide, thiophenol, sulfur-substituted aldehyde, sulfur-substituted ketone, sulfur-substituted amide, sulfur-substituted carboxylic acid, derivative of sulfur-substituted carboxylic acid, sulfur-containing heterocyclic compound, disulfide, polysulfide, isothiocyanate, organic sulfur-containing polymer, etc.;
dispersing agents can be added or not added in the ball milling process; after entering a dispersing agent, carrying out solid-liquid separation to obtain a sulfur-activated carbon/graphene composite material;
the dispersing agent in ball milling can be one of liquid sulfur source, water and organic solvent; the ratio of dispersant (volume, ml) to solid mixture (mass, g) is between 1 ml/g and 100ml/g (1-100 ml/g);
the organic solvent comprises but is not limited to one of liquid alcohols, liquid amines, liquid alcohol amines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane and acetonitrile;
the solvent used for washing the crude sulfur-activated carbon/graphene composite material prepared by the high-speed ball milling method as described above includes, but is not limited to, one of water, liquid alcohols, liquid amines, liquid alcamines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane, and acetonitrile;
the washing of the crude sulfur-activated carbon/graphene composite material uses one of mechanical/magnetic stirring and ultrasound.
The precipitation method comprises the following specific steps: mixing the sulfur source solution with the activated carbon/graphene composite material, adding a precipitator, carrying out solid-liquid separation, and drying to obtain the sulfur-activated carbon/graphene composite material;
the sulfur content of the sulfur-activated carbon/graphene composite material prepared by the precipitation method is adjustable from 10% to 90% (10-90%); sources of sulfur include, but are not limited to NaSx、(NH4)2S、(NH4)2S2O8、NaHSO3、Na2S2O3、Na2SO3、H2S、SO2、SO3、Na2SO4One of (1);
mixing the sulfur source with the activated carbon/graphene composite material, and adding a dispersing agent;
the dispersant for mixing the sulfur source with the activated carbon/graphene composite material is water or alcamines; the ratio of dispersant (volume, mL) to solid mixture (mass, g) is between 1 mL/g and 100mL/g (1-100 mL/g);
the mixing mode of the sulfur source and the activated carbon/graphene composite material comprises but is not limited to one of magnetic or mechanical stirring mixing and ultrasonic mixing;
the precipitant includes but is not limited to hydrochloric acid, sulfuric acid, nitric acid, SO2、SO3、H2One of S; wherein the mass percentage of the effective components in the inorganic acid (concentrated or diluted) is between 1 percent and 98 percent (1-98 percent); said H2S、SO2、SO3The volume percentage of the effective component in the composition is between 1 percent and 100 percent (1-100 percent); the other components are one of nitrogen, argon and helium;
the solvent used for washing the crude sulfur-activated carbon/graphene composite material as described above is water;
the washing mode of the crude sulfur-activated carbon/graphene composite material comprises but is not limited to one of stirring and ultrasonic treatment;
the solvent thermal method comprises the following specific steps: (1) mixing a sulfur source and a solvent with the activated carbon/graphene composite material, carrying out thermal reaction on the solvent, and carrying out solid-liquid separation to obtain a crude sulfur-activated carbon/graphene composite material; (2) purifying the composite material, carrying out solid-liquid separation, and drying to obtain a sulfur-activated carbon/graphene composite material;
the sulfur content of the sulfur-activated carbon/graphene composite material prepared by the solvothermal method is between 10% and 90% (10-90%);
the sulfur source in the solvothermal method comprises but is not limited to sulfur powder and NaSx、(NH4)2S、(NH4)2S2O8、H2S、NaHSO3、Na2S2O3、Na2SO3、Na2SO4、CS2One of thiol, thioether, sulfone, sulfoxide, thioylide, thiophenol, thio-substituted aldehyde, thio-substituted ketone, thio-substituted amide, thio-substituted carboxylic acid, derivative of thio-substituted carboxylic acid, thio-containing heterocyclic compound, disulfide, polysulfide, isothiocyanate, organic sulfur-containing polymer, etc.;
the solvent used in the above solvothermal method includes, but is not limited to, one of water, liquid alcohols, liquid amines, liquid alcamines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane, acetonitrile, and the like;
the reaction temperature of the solvothermal method is between 80 and 400 ℃ (80-400 ℃); the reaction time is between 1 hour and 96 hours (1-96 hours);
the solvent used for washing the crude sulfur-activated carbon/graphene composite material as described above includes, but is not limited to, one of water, liquid alcohols, liquid alcamines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane, acetonitrile, and the like;
one of magnetic force/mechanical stirring and ultrasonic is adopted in the washing process of the crude sulfur-activated carbon/graphene composite material;
the preparation method comprises the following specific operation modes of dipping, ultrasound, stirring, high-speed shearing, ball milling, solid-liquid separation and drying:
the dipping time is 2 hours to 144 hours (2 hours to 144 hours); the dipping temperature is 20 ℃ to 60 ℃ (20 ℃ to 60 ℃);
the frequency of the ultrasonic wave is 20 kHz to 30 kHz (20-30 kHz), the power density is 500W to 1000W (500-;
the stirring adopts magnetic force or/and mechanical stirring, the time is 3 hours to 60 hours (3 hours to 60 hours), and the stirring temperature is 20 ℃ to 60 ℃ (20 ℃ to 60 ℃);
the working temperature of the high-speed shearing machine is 20-60 ℃ (20-60 ℃) and is adjustable; the rotating speed is 50 to 3000 revolutions per minute (50 to 3000 rpm) and can be adjusted; the shearing time is adjustable from 0.5 h to 72 h (0.5-72 h);
the ball milling balls in the ball milling can be one of stainless steel balls, agate balls, zirconia balls, alumina balls, silicon carbide balls and the like; the diameter of the ball is 1 mm to 15 mm (1-15 mm); the ball milling tank can be made of stainless steel, agate or zirconia; the ball-material ratio (mass ratio) is 15-150: 1; the ball milling speed is as follows: 50 rpm to 580 rpm (50-580 rpm); the gas is more than one of air, nitrogen, argon or helium; the ball milling time is 0.5 to 72 hours (0.5 to 72 hours);
the above solid-liquid separation of the sulfur-containing composite after the sulfur-complexing includes, but is not limited to, the use of porous polymer (e.g., polypropylene, polyethylene, polystyrene, polyester, and cellulose) bags or membranes having an average pore size between 0.2 microns and 20 microns (0.2-20 μm). The porous polymer bag is beneficial to liquid-solid separation, the solid is left in the bag, and the liquid is thrown, extruded, pressed or flowed out;
the sulfur-activated carbon/graphene composite material solid obtained by the solid-liquid separation can be subjected to freeze drying at the temperature of minus 50 ℃ (minus 50 ℃), the drying time is 10 hours to 96 hours (10 hours to 96 hours), and sulfur-activated carbon/graphene composite material powder can be obtained; drying by blowing or vacuum at 70-120 deg.C (70-120 deg.C) for 2-96 hr (2-96 hr); sulfur-activated carbon/graphene composite material powder can be obtained;
the technical scheme of the invention mainly comprises three types of liquid, wherein one type of liquid is an activating agent used for activating biomass, the second type of liquid is used for purifying a crude activated carbon/graphene composite material, and the third type of liquid is used as a sulfur source or for dissolving a sulfur-containing compound. When the liquid for purifying the crude activated carbon/graphene composite material is inorganic aqueous liquid, the three types of liquid are controlled within the mutual solubility range, so that the recycling is facilitated; when the organic solution is used for purifying the liquid of the crude activated carbon/graphene composite material, the three types of liquid are controlled within the mutual solubility range, and the recycling is facilitated.
Compared with the prior art, the invention has the following advantages:
1. the raw material of the activated carbon has wide source, low price, easy obtaining and regeneration;
2. the preparation method of the active carbon/graphene composite material is simple and easy to implement, and is easy to realize industrial production;
3. the activated carbon/graphene composite material is applied to the lithium-sulfur battery, so that on one hand, the weight of the battery can be greatly reduced, the internal resistance of the battery is reduced, the conductivity of an electrode material is improved, and the specific capacity and the comprehensive performance of the battery are improved; on the other hand, the shuttle flying effect is reduced, the influence of volume expansion of sulfur on the performance of the battery is reduced to a certain extent, and the utilization rate of active substances is improved;
4. most of the dispersant, the solvent and the activator in the process can be recycled, so that the cost is low;
5. the preparation process of the sulfur-activated carbon/graphene composite material is simple in steps, high in efficiency, low in energy consumption and capable of realizing large-scale production.
6. The sulfur-activated carbon/graphene composite material prepared by the invention is composed of sulfur, activated carbon and graphene, the activated carbon and the graphene can be used as the positive electrode material of the lithium-sulfur battery after being compounded with the sulfur, the synergistic effect of the activated carbon and the graphene is obvious, and under the same test conditions, the comprehensive performance of the lithium-sulfur battery assembled by taking the composite material as the positive electrode is obviously superior to that of the lithium-sulfur battery assembled by taking the same type of positive electrode material as the positive electrode.
7. The limited domain surface performance of the two-dimensional atomic crystal lamella of the electrochemically prepared graphene can provide a strong interface effect to control the size of the hole in the active carbon/graphene composite material, and the graphene has the advantages of good quality, few defects, high conductivity, high specific surface area, good flexibility and the like;
8. the graphene sheet is larger than 200 micrometers multiplied by 200 micrometers, is doped with heteroatoms and contains a large number of micropores and mesoporous nanopores, so that the electronic conductivity and the ion migration rate of the lithium-sulfur battery can be improved, polysulfide can be adsorbed by chemical absorption, physical absorption and the like, the shuttle effect can be effectively inhibited, the flexible characteristic of the graphene can inhibit the volume expansion formed in the recharging and discharging process of the lithium-sulfur battery together with porous carbon, the structure of the positive electrode material is more stable, and the cycle performance and the rate capability of the battery are improved;
9. the sulfur-activated carbon/graphene composite material has good conductivity, can realize high-rate charge and discharge of a lithium-sulfur battery, can fully charge the battery within 15 minutes, and can meet the requirement of portable digital electrical appliances on quick charge and discharge of the battery;
10. the graphene has good heat-conducting property, so that the temperature for preparing the activated carbon/graphene composite material by activating the biomass/graphene mixture is obviously reduced by adding the graphene, and the energy is saved;
description of the drawings:
fig. 1 is an SEM image of the nitrogen-doped graphene-based hierarchical porous carbon composite prepared in example 2. It can be seen from the figure that a large number of micropores and mesopores are grown on the graphene sheet.
Fig. 2 is an SEM image of the nitrogen-doped graphene-based hierarchical porous carbon-supported sulfur composite prepared in example 2.
FIG. 3 is a schematic view of nitrogen-doped graphene-based hierarchical porous carbon pre-sulfur-loading TEM before cycle
FIG. 4 is a TEM schematic diagram of nitrogen-doped graphene-based hierarchical porous carbon sulfur-loading cycle after 100 cycles
FIG. 5 is a schematic XRD of elemental sulfur and nitrogen doped graphene-based hierarchical pore carbon
Fig. 6 is a thermal schematic diagram of nitrogen-doped graphene-based hierarchical porous carbon.
Fig. 7 is a cycle efficiency curve of the nitrogen-doped graphene-based hierarchical porous carbon-supported sulfur composite prepared in example 1 at a current density of 1.7-2.8V and 0.1C. The first discharge was 1101 mAh/g. After 100 times of circulation, the discharge capacity is 715mAh/g, and the circulation efficiency reaches 99.5 percent.
Fig. 8 is a cycle efficiency curve of the nitrogen-doped graphene-based hierarchical porous carbon-supported sulfur composite prepared in example 2 at a current density of 1.7-2.8V and 0.1C. The first discharge was 1687 mAh/g. After 100 times of circulation, the discharge capacity is 785 mAh/g, and the circulation efficiency reaches 99.7 percent.
Fig. 9 is a cycle efficiency curve of the nitrogen-doped graphene-based hierarchical porous carbon-supported sulfur composite prepared in example 3 at a current density of 1.7-2.8V and 0.1C. The first discharge was 1231 mAh/g. After 100 times of circulation, the discharge capacity is 661mAh/g and the circulation efficiency reaches 99.9%.
Fig. 10 is a cycle efficiency curve of the nitrogen-doped graphene-based hierarchical porous carbon-supported sulfur composite prepared in example 4 at a current density of 1.7-2.8V and 0.1C. The first discharge was 1087 mAh/g. After 100 times of circulation, the discharge capacity is 785 mAh/g, and the circulation efficiency reaches 99.8 percent.
Fig. 11 is a cycle efficiency curve of the nitrogen-doped graphene-based hierarchical porous carbon-supported sulfur composite prepared in example 5 at a current density of 1.7-2.8V and 0.1C. The first discharge was 1289 mAh/g. After 100 times of circulation, the discharge capacity is 420mAh/g, and the circulation efficiency reaches 100%.
Fig. 12 is a cycle efficiency curve of the nitrogen-doped graphene-based hierarchical porous carbon sulfur-loaded composite material prepared in example 2 at a current density of 1.7-2.8V and 1C. After 500 times of circulation, the specific capacity is 500 mAh/g. The circulation efficiency reaches 99.8 percent.
Fig. 13 is a cycle efficiency curve of the nitrogen-doped graphene-based hierarchical porous carbon-supported sulfur composite prepared in example 2 at a current density of 1.7-2.8V and 1.5C. The specific capacity after 1000 times of circulation is 279 mAh/g. The circulation efficiency reaches 99.7 percent.
FIG. 14 is a cyclic voltammogram of the nitrogen-doped graphene-based hierarchical porous carbon-supported sulfur composite material prepared in example 2 at 1.7-3.0V and a sweep rate of 0.01 mV/s.
FIG. 15 is a Raman diagram of the nitrogen-doped graphene-based hierarchical porous carbon sulfur-loaded composite material and graphene-based hierarchical porous carbon prepared in example 2
FIG. 16 is a schematic view of the specific surface area before sulfur charging.
FIG. 17 is a schematic view showing the specific surface area after sulfur charging.
FIG. 18 is a schematic view of pore distribution before and after sulfur charging.
Detailed Description
Example 1: (1) naturally drying the rice hulls for 14 days, then sealing 50.0 g of agate ball milling balls with the diameter of 1-1.3 cm and 100 g of the rice hulls into an agate ball milling tank under the protection of argon, and then placing the ball milling tank on a planetary ball mill and carrying out ball milling for 2 hours at the rotating speed of 580 revolutions per minute. And taking the agate balls out by using tweezers, sieving the ball-milled samples by using a three-dimensional vibrating screen, and washing the 20-mesh samples by using 5% sulfuric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours; (2) 20 g of biomass and 100 g of graphene are stirred and mixed in 50 ml of 10 mass percent KOH aqueous solution. The magnetic stirring time was 5 hours at 20 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 96 hours at 350 ℃ in a nitrogen atmosphere, then washing the solid material to be neutral by using deionized water, performing solid-liquid separation by using a polypropylene bag (with the aperture of 0.2 micron), and freeze-drying the obtained solid for 10 hours to obtain activated carbon/graphene composite material powder; (4) 20 g of sulfur powder and 10 g of activated carbon/graphene composite material powder are dispersed in 10 ml of 0.0001 mol/L P123 aqueous solution and mixed by an ultrasonic method. The frequency of the ultrasound was 20 kHz, the power density was 500 w, the time was 30 hours and the temperature was 20 ℃. And reacting the obtained mixture at 20 ℃ for 144 hours, then carrying out solid-liquid separation by adopting a polypropylene bag (with the aperture of 0.2 micrometer), and freeze-drying the solid for 96 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 2: (1) the jujube pits are naturally dried for 3 days, then 1500.0 g of zirconia ball grinding balls with the diameter of 3-8 mm and 200 g of jujube pits are sealed in a zirconia ball milling pot under the protection of nitrogen, and then the ball milling pot is placed on a planetary ball mill and is ball milled for 30 hours at the rotating speed of 300 r/min. Taking out the zirconia balls by using tweezers, sieving the ball-milled samples by using an ultrasonic vibration sieve, and taking out the samples with 50 meshesThe sample of (2) was washed 3 times with 5% aqueous hydrochloric acid and deionized water, respectively. Performing solid-liquid separation by using a polypropylene membrane (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 24 hours; (2) 100 g of biomass and 10 g of nitrogen-doped graphene are added into 100ml of K with the mass percentage of 20%2CO3Stirring and mixing the aqueous solution. The time of mechanical stirring was 20 hours and the temperature was 40 ℃. A polyethylene bag (with the aperture of 1 micron) is adopted to realize solid-liquid separation, the solid is left in the bag, and the liquid is thrown out, extruded, pressed out or flowed out; (3) the solid material was activated for 84 hours at 450 ℃ under argon atmosphere and then successively with 1% H2SO4Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 1 micron), and freeze-drying the obtained solid for 30 hours to obtain activated carbon/graphene composite material powder; (4) 100 g of thiourea and 50 g of activated carbon/graphene composite powder were dispersed in 50 ml of 0.01 mol/l aqueous solution of sodium dodecylbenzenesulfonate and mixed by an ultrasonic method. The frequency of the ultrasound was 30 kHz, the power density was 800 w, the time was 10 hours and the temperature was 40 ℃. And reacting the obtained mixture at 60 ℃ for 60 hours, then carrying out solid-liquid separation by adopting a polypropylene membrane (with the aperture of 1 micron), and freeze-drying the solid for 50 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 3: (1) the bamboo powder is naturally dried for 30 days, then 500.0 g of alumina ball milling balls with the diameter of 8-15 mm and 300 g of bamboo powder are sealed into an agate ball milling tank under the protection of air, and then the ball milling tank is placed on a planetary ball mill and is ball milled for 60 hours at the rotating speed of 100 r/min. And (3) taking out the alumina ball by using a pair of tweezers, sieving the ball-milled sample by using an ultrasonic vibration sieve, and washing the 80-mesh sample by using 30% hydrochloric acid water solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (aperture is 2 microns), and the obtained solid is dried by air blast for 1 hour at 120 ℃; (2) 2 g of biomass and 100 g of phosphorus-doped graphene are ultrasonically mixed in 300 ml of NaOH aqueous solution with the mass percent of 50%. The ultrasonic frequency is 20 KHz, the power density is 500 w, the time is 30 hours, and the temperature is 20 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), and the solid is remained in the bagThe liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 72 hours at 500 ℃ in a helium atmosphere, and then sequentially using 80% H3PO4Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by using a polyethylene bag (with the aperture of 2 microns), and freeze-drying the obtained solid for 50 hours to obtain activated carbon/graphene composite material powder; (4) 80 g (NH)4)2S2O8And 100 g of activated carbon/graphene composite material powder are dispersed in 100ml of 0.5 mol/L hexadecyl trimethyl ammonium bromide aqueous solution and mixed by an ultrasonic method. The frequency of the ultrasound was 25 kHz, the power density was 1000 w, the time was 30 minutes and the temperature was 60 ℃. And reacting the obtained mixture at 100 ℃ for 30 hours, then carrying out solid-liquid separation by using a polyethylene bag (with the aperture of 2 microns), and freeze-drying the solid for 10 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 4: (1) naturally drying poplar sawdust for 12 hours, and then crushing 200 g of poplar sawdust by adopting ultrasonic waves. The ultrasonic frequency is 20 kHz, the power density is 500 w, the time is 28 h, and the temperature is 25 ℃. And sieving the ultrasonically crushed sample by using a high-frequency vibrating screen, and washing the 100-mesh sample by using 30% sulfuric acid aqueous solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (the aperture is 0.2 micron), and the obtained solid is dried by air blast for 30 hours at the temperature of 80 ℃; (2) 200 g of biomass, 10 g of boron-doped graphene and 10 g of solid Na2CO3And (4) ultrasonic mixing. The ultrasonic frequency is 25 KHz, the power density is 800 w, the time is 10 hours, and the temperature is 40 ℃. The solid-liquid separation is realized by adopting a polystyrene membrane (the aperture is 2 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 1% NH at 600 ℃3/N2Activating for 60 hours in a gas atmosphere, washing with 50% HCl aqueous solution and deionized water in sequence until the solution is neutral, performing solid-liquid separation by using a polyethylene film (with the aperture of 5 microns), and freeze-drying the obtained solid for 96 hours to obtain activated carbon/graphene composite material powder; (4) 150 g of CS2And 20 g of activated carbon/graphene composite material powder are mixed by a mechanical stirring method. The mechanical stirring time is 60 hoursAt a temperature of 20 degrees celsius. And (3) reacting the obtained mixture at 80 ℃ for 100 hours, then carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and carrying out vacuum drying on the solid at 70 ℃ for 96 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 5: (1) vacuum drying the alcohol residue at 70 deg.C for 96 hr, and pulverizing 200 g of alcohol residue with ultrasonic wave. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. And sieving the ultrasonically crushed sample by using an airflow sieve, and washing the 40-mesh sample by using 80% phosphoric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 50 hours; (2) 30 g of biomass and 1 g of sulfur-doped graphene are added into 300 ml of H with the mass percent of 50%3PO4Ultrasonic mixing in the water solution. The ultrasonic frequency is 30 KHz, the power density is 1000 w, the time is 1 hour, and the temperature is 60 ℃. The solid-liquid separation is realized by adopting a polyethylene film (with the aperture of 1 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the obtained solid material is activated for 48 hours in an atmosphere of 5 percent NH3/Ar at 700 ℃, and then 60 percent HNO is used in sequence3Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by using a polystyrene bag (with the aperture of 10 microns), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours to obtain activated carbon/graphene composite material powder; (4) 150 g of ethanethiol and 30 g of activated carbon/graphene composite powder were dispersed in isopropanol and mixed with magnetic stirring. The magnetic stirring time was 80 hours and the temperature was 40 ℃. And reacting the obtained mixture at 50 ℃ for 75 hours, then carrying out solid-liquid separation by using a polystyrene bag (with the aperture of 10 microns), and carrying out forced air drying on the solid at 100 ℃ for 60 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 6: (1) vacuum drying sweet potato residue at 120 deg.C for 2 hr, and pulverizing 300 g sweet potato residue with ultrasonic wave. The ultrasonic frequency is 30 kHz, the power density is 1000 w, the time is 2 h, and the temperature is 60 ℃. Sieving the ultrasonically crushed sample with a drum sieve, and washing the 40-mesh sample with 10% perchloric acid aqueous solution and deionized water for 3 times. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 2 g of biomass and 100 g of nitrogen and phosphorus co-doped graphene are added into 1000 ml of ZnCl with the mass percent of 10%2Soaking and mixing in the water solution. The immersion time was 30 hours and the temperature was 40 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 10% NH at 800 DEG C3Activating in He gas atmosphere for 32 hours, and sequentially using 70% HClO4Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polystyrene membrane (with the aperture of 15 microns), and performing vacuum drying on the obtained solid at 75 ℃ for 75 hours to obtain activated carbon/graphene composite material powder; (4) 150 g of ethyl sulfide and 60 g of activated carbon/graphene composite material powder are dispersed in ethanolamine and mixed by mechanical stirring. The time of mechanical stirring was 30 hours and the temperature was 60 ℃. And reacting the obtained mixture at 75 ℃ for 2 hours, then carrying out solid-liquid separation by adopting a polystyrene membrane (with the aperture of 20 microns), and carrying out forced air drying on the solid at 120 ℃ for 2 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 7: (1) and (3) drying the fruit and vegetable processing residues by blowing at 100 ℃ for 36 hours, and then crushing 240 g of the fruit and vegetable processing residues by adopting ultrasonic waves. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. Sieving the ultrasonically pulverized sample with a straight-line filter sieve, and respectively using 10% HClO to obtain 80-mesh samples3The S aqueous solution and deionized water were washed 3 times. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 300 g of biomass and 10 g of nitrogen and boron co-doped graphene are added into 500 ml of ZnCl with the mass percent of 100%2Soaking and mixing in the water solution. The immersion time was 90 hours and the temperature was 30 ℃. A polyethylene bag (with the aperture of 1 micron) is adopted to realize solid-liquid separation, the solid is left in the bag, and the liquid is thrown out, extruded, pressed out or flowed out; (3) the solid material obtained is 50% NH at 900 DEG C3/N2Activating for 16 hours under the atmosphere, then washing to be neutral by using 1 percent NaOH aqueous solution and deionized water in sequence,performing solid-liquid separation by using a polypropylene bag (with the aperture of 20 microns), and performing vacuum drying on the obtained solid at 80 ℃ for 60 hours to obtain activated carbon/graphene composite material powder; (4) 200 g of sulfolane and 80 g of activated carbon/graphene composite material powder are dispersed in ethylenediamine, and mixed by magnetic stirring. The magnetic stirring time was 5 hours and the temperature was 50 ℃. Reacting the obtained mixture for 1 hour at 60 ℃, then carrying out solid-liquid separation by adopting a polystyrene membrane (with the aperture of 0.2 micron), and carrying out forced air drying on the solid for 12 hours at 110 ℃ to obtain the sulfur-activated carbon/graphene composite material powder.
Example 8: (1) the wheat straws are naturally dried for 14 days, then 50.0 g of agate ball milling balls with the diameter of 1-1.3 cm and 100 g of wheat straws are sealed in an agate ball milling tank under the protection of argon, and then the ball milling tank is placed on a planetary ball mill and is ball milled for 2 hours at the rotating speed of 580 revolutions per minute. And taking the agate balls out by using tweezers, sieving the ball-milled samples by using a three-dimensional vibrating screen, and washing the 20-mesh samples by using 5% sulfuric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours; (2) 500 g of biomass and 30 g of nitrogen and sulfur co-doped graphene are added into 400 ml of H with the mass percentage of 10%3PO4Soaking and mixing in the water solution. The immersion time was 50 hours and the temperature was 60 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 2 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 90% NH at 1050 DEG C3/N2Activating for 0.5 hour in the atmosphere, then washing with 5% KOH aqueous solution and deionized water in sequence to be neutral, performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 0.2 micron), and performing vacuum drying on the obtained solid for 45 hours at 85 ℃ to obtain activated carbon/graphene composite material powder; (4) 250 g of benzothiophene and 40 g of activated carbon/graphene composite powder were dispersed in benzene and mixed with high shear. The temperature of the high-speed shearing is 20 ℃, the rotating speed is 3000 r/min, and the time is 72 hours. Reacting the obtained mixture at 60 ℃ for 100 hours, then carrying out solid-liquid separation by adopting a polystyrene bag (with the aperture of 1 micron), and carrying out vacuum drying on the solid at 80 ℃ for 24 hoursAnd then, obtaining the sulfur-activated carbon/graphene composite material powder.
Example 9: (1) the walnut shells were naturally dried for 3 days, then 1500.0 g of zirconia ball milling balls with a diameter of 3-8 mm and 200 g of walnut shells were sealed in a zirconia ball milling pot under nitrogen protection, and then the ball milling pot was placed on a planetary ball mill and ball milled at a rotation speed of 300 revolutions per minute for 30 hours. And (3) taking out the zirconia balls by using tweezers, sieving the ball-milled samples by using an ultrasonic vibration sieve, and washing the 50-mesh samples by using 5% hydrochloric acid water solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polypropylene membrane (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 24 hours; (2) 2 g of biomass and 100 g of phosphorus and sulfur co-doped graphene are added into 550 ml of ZnCl with the mass percent of 5%2Soaking in ethanol solution, and mixing. The immersion time was 10 hours and the temperature was 20 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 1 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the obtained solid material is N at 550 DEG C2Activating for 90 hours in atmosphere, and then sequentially using 10% Na2CO3Washing the aqueous solution and deionized water to be neutral, carrying out solid-liquid separation by adopting a polyethylene bag (with the aperture of 2 microns), and carrying out forced air drying on the obtained solid at 90 ℃ for 30 hours to obtain activated carbon/graphene composite material powder; (4) 5 g of dimethyl sulfoxide and 15 g of activated carbon/graphene composite material powder are mixed by high-speed shearing. The temperature of the high-speed shearing is 40 ℃, the time is 40 hours, and the rotating speed is 1000 r/min. Reacting the obtained mixture for 80 hours at 30 ℃, performing solid-liquid separation by using a polyethylene bag (with the aperture of 2 microns), and performing vacuum drying on the solid for 36 hours at 75 ℃ to obtain sulfur-activated carbon/graphene composite material powder.
Example 10: (1) the cassava skin is naturally dried for 30 days, then 500.0 g of alumina ball milling balls with the diameter of 8-15 mm and 300 g of cassava skin are sealed into an agate ball milling tank under the protection of air, and then the ball milling tank is placed on a planetary ball mill and is ball milled for 60 hours at the rotating speed of 100 r/min. Taking out the alumina ball by using tweezers, sieving the ball-milled sample by using an ultrasonic vibration sieve, and washing the 80-mesh sample by using 30% hydrochloric acid aqueous solution and deionized water respectivelyAnd washing for 3 times. Solid-liquid separation is carried out by adopting a polystyrene membrane (aperture is 2 microns), and the obtained solid is dried by air blast for 1 hour at 120 ℃; (2) 300 g of biomass and 10 g of nitrogen, phosphorus and sulfur co-doped graphene are added into 1000 ml of ZnCl with the mass percentage of 30%2Soaking in ethanol solution, and mixing. The immersion time was 140 hours and the temperature was 40 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 15 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the resulting solid material was activated at 650 ℃ for 75 hours in Ar atmosphere and then successively treated with 10% H2SO4Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and performing forced air drying on the obtained solid at 100 ℃ for 15 hours to obtain activated carbon/graphene composite material powder; (4) 50 g of allyl sulfur ylide and 25 g of activated carbon/graphene composite material are dispersed in n-butanone and mixed by high-speed shearing. The temperature of high-speed shearing is 60 ℃, the time is 1 hour, and the rotating speed is 2000 r/min. And reacting the obtained mixture at 40 ℃ for 5 hours, performing solid-liquid separation by using a polyethylene film (with the aperture of 5 microns), and performing vacuum drying on the solid at 80 ℃ for 5 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 11: (1) the cotton hulls were naturally dried for 12 hours and then 200 g of cotton hulls were crushed using ultrasonic waves. The frequency of the ultrasonic wave is 20 KHz, the power density is 500 w, the time is 28 h, and the temperature is 25 ℃. And sieving the ultrasonically crushed sample by using a high-frequency vibrating screen, and washing the 100-mesh sample by using 30% sulfuric acid aqueous solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (the aperture is 0.2 micron), and the obtained solid is dried by air blast for 30 hours at the temperature of 80 ℃; (2) 20 g of biomass and 100 g of phosphorus and boron co-doped graphene are added into 400 ml of H with the mass percent of 80%3PO4And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 30 hours, the temperature is 40 ℃, and the rotating speed is 100 r/min. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 20 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 50 hours in a helium atmosphere at 750 ℃, and then sequentially using 50% K2CO3Aqueous solutionWashing with deionized water to be neutral, performing solid-liquid separation by using a polystyrene bag (with the aperture of 10 microns), and performing forced air drying on the obtained solid at 110 ℃ for 8 hours to obtain activated carbon/graphene composite material powder; (4) 150 g of thiophenol and 35 g of activated carbon/graphene composite material were dispersed in 1, 4-dioxane and mixed by high-speed shearing. The temperature of the high-speed shearing is 20 ℃, the time is 48 hours, and the rotating speed is 100 r/min. Reacting the obtained mixture at 70 ℃ for 1 hour, performing solid-liquid separation by using a polypropylene bag (with the aperture of 10 microns), and performing vacuum drying on the solid at 70 ℃ for 2 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 12: (1) the oil meal is dried in vacuum at 70 ℃ for 96 hours, and then 200 g of the oil meal is crushed by ultrasonic waves. The ultrasonic frequency is 25 KHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. And sieving the ultrasonically crushed sample by using an airflow sieve, and washing the 40-mesh sample by using 80% phosphoric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 50 hours; (2) 350 g of biomass and 10 g of nitrogen, sulfur and boron co-doped graphene are added into 200 ml of ZnCl with the mass percent of 400%2And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 1 hour, the temperature is 60 ℃, and the rotating speed is 3000 r/min. The solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 5 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the obtained solid material is NH at 850 DEG C3Activating for 40 hours in atmosphere, and then sequentially using 10% CH3Washing the COOH aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polystyrene membrane (with the aperture of 10 microns), and performing forced air drying on the obtained solid at 120 ℃ for 2 hours to obtain activated carbon/graphene composite material powder; (4) 300 g of thioaldehyde and 55 g of activated carbon/graphene composite material are mixed by high-speed shearing. The temperature of the high-speed shearing is 30 ℃, the time is 24 hours, and the rotating speed is 500 r/min. Reacting the obtained mixture for 50 hours at 90 ℃, performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 20 microns), and performing vacuum drying on the solid for 12 hours at 85 ℃ to obtain sulfur-activated carbon/graphene composite material powder.
Example 13: (1) drying cattail wool in vacuum at 120 ℃ for 2 hours, and then crushing 300 g cattail wool by ultrasonic waves. The ultrasonic frequency is 30 KHz, the power density is 1000 w, the time is 2 h, and the temperature is 60 ℃. The sample after ultrasonic crushing is sieved by a drum sieve, and a 40-mesh sample is respectively washed 3 times by 10% perchloric acid aqueous solution and deionized water. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 150 g of biomass and 10 g of phosphorus-sulfur-boron co-doped graphene are added into 800 ml of ZnCl with the mass percent of 80%2And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 56 hours, the temperature is 20 ℃, and the rotating speed is 1500 rpm. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 10 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in a nitrogen atmosphere at 950 ℃ for 20 hours, then sequentially washing the solid material to be neutral by adopting a 5% oxalic acid water solution and deionized water, carrying out solid-liquid separation by adopting a polypropylene bag (with the aperture of 0.2 micron), and drying the obtained solid at 80 ℃ for 96 hours in vacuum to obtain activated carbon/graphene composite material powder; (4) 50.0 g of agate ball milling balls with the diameter of 1-1.3 cm, 100 g of thioacetamide and 65 g of activated carbon/graphene composite material are sealed into an agate ball milling pot under the protection of argon, and then the ball milling pot is placed on a planetary ball mill and ball milled for 2 hours at the rotating speed of 580 revolutions per minute. And (3) taking the agate balls out by using tweezers, reacting the obtained mixture for 50 hours at 90 ℃, performing solid-liquid separation by using a polypropylene membrane (with the aperture of 20 microns), and drying the solid for 12 hours at 85 ℃ in vacuum to obtain the sulfur-activated carbon/graphene composite material powder.
Example 14: (1) the cedar chips were dried by blowing at 100 ℃ for 36 hours, and then 240 g of the cedar chips were pulverized by ultrasonic waves. The ultrasonic frequency is 25 KHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. Sieving the ultrasonically pulverized sample with a straight-line filter sieve, and respectively using 10% HClO to obtain 80-mesh samples3The S aqueous solution and deionized water were washed 3 times. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 20 g of biomass and 100 g of graphene are mixed in a mass of 50 ml10% KOH aqueous solution is stirred and mixed. The magnetic stirring time was 5 hours at 20 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in an argon atmosphere at 1000 ℃ for 10 hours, then sequentially washing the solid material to be neutral by adopting 30% formic acid water solution and deionized water, carrying out solid-liquid separation by adopting a polypropylene membrane (with the aperture of 1 micron), and carrying out forced air drying on the obtained solid at 95 ℃ for 50 hours to obtain activated carbon/graphene composite material powder; (4) 1500.0 g of zirconia ball milling balls with a diameter of 3-8 mm, 100 g of 2-mercaptopyrimidine and 75 g of activated carbon/graphene composite material were dispersed in tetrahydrofuran, sealed into a zirconia ball milling jar under nitrogen protection, and then the jar was placed on a planetary ball mill and ball milled at a rotational speed of 300 revolutions per minute for 30 hours. And (3) taking out the zirconia balls by using tweezers, reacting the obtained mixture for 1 hour at 70 ℃, performing solid-liquid separation by using a polypropylene bag (with the aperture of 10 microns), and performing vacuum drying on the solid for 2 hours at 70 ℃ to obtain the sulfur-activated carbon/graphene composite material powder.
Example 15: (1) the corncobs were naturally dried for 14 days, then 50.0 g of agate balls with a diameter of 1-1.3 cm were milled, 100 g of the corncobs were sealed in an agate milling pot under argon protection, and then the milling pot was placed on a planetary ball mill and ball-milled at 580 revolutions per minute for 2 hours. And taking the agate balls out by using tweezers, sieving the ball-milled samples by using a three-dimensional vibrating screen, and washing the 20-mesh samples by using 5% sulfuric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours; (2) 100 g of biomass and 10 g of nitrogen-doped graphene are added into 100ml of K with the mass percentage of 20%2CO3Stirring and mixing the aqueous solution. The time of mechanical stirring was 20 hours and the temperature was 40 ℃. A polyethylene bag (with the aperture of 1 micron) is adopted to realize solid-liquid separation, the solid is left in the bag, and the liquid is thrown out, extruded, pressed out or flowed out; (3) activating the obtained solid material in a helium atmosphere at 500 ℃ for 2 hours, then sequentially washing the solid material to be neutral by using 60% trifluoroacetic acid aqueous solution and deionized water, and adopting polyethyleneCarrying out solid-liquid separation on the graphene bag (with the aperture of 2 microns), and carrying out forced air drying on the obtained solid at 100 ℃ for 20 hours to obtain activated carbon/graphene composite material powder; (4) 500.0 g of alumina ball milling balls with the diameter of 8-15 mm, 100 g of 2-furanthiocarboxylic acid and 85 g of activated carbon/graphene composite material are dispersed in diethyl isovalerate, sealed in an agate ball milling pot under the protection of air, and then the ball milling pot is placed on a planetary ball mill and ball milled for 60 hours at the rotating speed of 100 revolutions per minute. And (3) taking out the alumina ball by using a pair of tweezers, reacting the obtained mixture for 5 hours at 40 ℃, performing solid-liquid separation by using a polyethylene film (with the aperture of 5 microns), and drying the solid for 5 hours at 80 ℃ in vacuum to obtain the sulfur-activated carbon/graphene composite material powder.
Example 16: (1) the small eucalyptus waste is naturally dried for 3 days, then 1500.0 g of zirconia balls with the diameter of 3-8 mm are ground, 200 g of the small eucalyptus waste is sealed into a zirconia ball milling pot under the protection of nitrogen, and then the ball milling pot is placed on a planetary ball mill and is ball milled for 30 hours at the rotating speed of 300 r/min. And (3) taking out the zirconia balls by using tweezers, sieving the ball-milled samples by using an ultrasonic vibration sieve, and washing the 50-mesh samples by using 5% hydrochloric acid water solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polypropylene membrane (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 24 hours; (2) 2 g of biomass and 100 g of phosphorus-doped graphene are ultrasonically mixed in 300 ml of NaOH aqueous solution with the mass percent of 50%. The ultrasonic frequency is 20 KHz, the power density is 500 w, the time is 30 hours, and the temperature is 20 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in a nitrogen atmosphere at 600 ℃ for 5 hours, then sequentially washing the solid material with 1% pyridine water solution and deionized water to be neutral, carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and carrying out forced air drying on the obtained solid at 120 ℃ for 4 hours to obtain activated carbon/graphene composite material powder; (4) 500.0 g of silicon carbide ball milling balls with the diameter of 8-15 mm, 100 g of 2-furancarbothioic acid and 85 g of activated carbon/graphene composite material are dispersed in diethyl isovalerate, sealed in a silicon carbide tank under the protection of air, and then the ball milling tank is placed on a planetary ball mill and ball milled for 60 hours at the rotating speed of 100 revolutions per minute. And (3) taking out the silicon carbide spheres by using tweezers, reacting the obtained mixture for 80 hours at 30 ℃, performing solid-liquid separation by using a polyethylene bag (with the aperture of 2 microns), and performing vacuum drying on the solid for 36 hours at 75 ℃ to obtain sulfur-activated carbon/graphene composite material powder.
Example 17: (1) the tea/coffee grounds were naturally dried for 30 days, then 500.0 g of alumina balls with a diameter of 8-15 mm were milled, 300 g of tea/coffee grounds were sealed in an agate jar under air protection, and then the jar was placed on a planetary ball mill and ball milled at 100 revolutions per minute for 60 hours. And (3) taking out the alumina ball by using a pair of tweezers, sieving the ball-milled sample by using an ultrasonic vibration sieve, and washing the 80-mesh sample by using 30% hydrochloric acid water solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (aperture is 2 microns), and the obtained solid is dried by air blast for 1 hour at 120 ℃; (2) 200 g of biomass, 10 g of boron-doped graphene and 10 g of solid Na2CO3And (4) ultrasonic mixing. The ultrasonic frequency is 25 KHz, the power density is 800 w, the time is 10 hours, and the temperature is 40 ℃. The solid-liquid separation is realized by adopting a polystyrene membrane (the aperture is 2 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in a nitrogen atmosphere at 800 ℃ for 1 hour, then sequentially washing the solid material with 5% methylamine water solution and deionized water to be neutral, performing solid-liquid separation by using a polystyrene bag (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at 110 ℃ for 12 hours to obtain activated carbon/graphene composite material powder; (4) 100 g of thiobenzoic acid and 30 g of activated carbon/graphene composite material were dispersed in acetic acid and mixed by ultrasonic waves. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. Reacting the obtained mixture for 80 hours at 30 ℃, performing solid-liquid separation by using a polyethylene bag (with the aperture of 2 microns), and performing vacuum drying on the solid for 36 hours at 75 ℃ to obtain sulfur-activated carbon/graphene composite material powder.
Example 18: (1) naturally drying the vinegar residue for 12 hours, and then crushing 200 g of the vinegar residue by adopting ultrasonic waves. The frequency of the ultrasonic wave is 20 kHz, and the power density is 500 wTime 28 h, temperature 25 ℃. And sieving the ultrasonically crushed sample by using a high-frequency vibrating screen, and washing the 100-mesh sample by using 30% sulfuric acid aqueous solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (the aperture is 0.2 micron), and the obtained solid is dried by air blast for 30 hours at the temperature of 80 ℃; (2) 30 g of biomass and 1 g of sulfur-doped graphene are added into 300 ml of H with the mass percent of 50%3PO4Ultrasonic mixing in the water solution. The ultrasonic frequency is 30 KHz, the power density is 1000 w, the time is 1 hour, and the temperature is 60 ℃. The solid-liquid separation is realized by adopting a polyethylene film (with the aperture of 1 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 60 hours at 400 ℃ in an ammonia atmosphere, then sequentially washing the solid material to be neutral by using 10% sodium methoxide aqueous solution and deionized water, performing solid-liquid separation by using a polystyrene membrane (with the aperture of 1 micron), and performing vacuum drying on the obtained solid for 85 hours at 70 ℃ to obtain activated carbon/graphene composite material powder; (4) 100 g of thioethanolamine and 40 g of activated carbon/graphene composite material are dispersed in benzaldehyde, and ultrasonic mixing is adopted. The ultrasonic frequency is 30 kHz, the power density is 1000 w, the time is 2 h, and the temperature is 60 ℃. And reacting the obtained mixture at 60 ℃ for 100 hours, then carrying out solid-liquid separation by using a polystyrene bag (with the aperture of 1 micron), and carrying out vacuum drying on the solid at 80 ℃ for 24 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 19: (1) teak sawdust was vacuum-dried at 70 ℃ for 96 hours, and then 200 g of teak sawdust was pulverized by ultrasonic waves. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. And sieving the ultrasonically crushed sample by using an airflow sieve, and washing the 40-mesh sample by using 80% phosphoric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 50 hours; (2) 2 g of biomass and 100 g of nitrogen and phosphorus co-doped graphene are added into 1000 ml of ZnCl with the mass percent of 10%2Soaking and mixing in the water solution. The immersion time was 30 hours and the temperature was 40 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out;(3) activating the obtained solid material for 70 hours at 500 ℃ in a nitrogen atmosphere, then sequentially washing the solid material to be neutral by using 30% Schiff base aqueous solution and deionized water, performing solid-liquid separation by using a polyethylene film (with the aperture of 3 microns), and performing forced air drying on the obtained solid for 5 hours at 115 ℃ to obtain activated carbon/graphene composite material powder; (4) 100 g of TiS2And 60 g of activated carbon/graphene composite material powder are dispersed in 0.2 mol/L of sorbitol aqueous solution and mixed by ultrasonic wave. The ultrasonic frequency is 20 kHz, the power density is 500 w, the time is 28 h, and the temperature is 25 ℃. Reacting the obtained mixture for 1 hour at 60 ℃, then carrying out solid-liquid separation by adopting a polystyrene membrane (with the aperture of 0.2 micron), and carrying out forced air drying on the solid for 12 hours at 110 ℃ to obtain the sulfur-activated carbon/graphene composite material powder.
Example 20: (1) drying the date pits in vacuum at 120 ℃ for 2 hours, and then crushing 300 g of the date pits by ultrasonic waves. The ultrasonic frequency is 30 kHz, the power density is 1000 w, the time is 2 h, and the temperature is 60 ℃. The sample after ultrasonic crushing is sieved by a drum sieve, and a 40-mesh sample is respectively washed 3 times by 10% perchloric acid aqueous solution and deionized water. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 300 g of biomass and 10 g of nitrogen and boron co-doped graphene are added into 500 ml of ZnCl with the mass percent of 100%2Soaking and mixing in the water solution. The immersion time was 90 hours and the temperature was 30 ℃. A polyethylene bag (with the aperture of 1 micron) is adopted to realize solid-liquid separation, the solid is left in the bag, and the liquid is thrown out, extruded, pressed out or flowed out; (3) activating the obtained solid material in argon atmosphere at 750 ℃ for 1 hour, then sequentially washing the solid material with 50% butylamine aqueous solution and deionized water to be neutral, carrying out solid-liquid separation by adopting a polypropylene bag (with the aperture of 20 microns), and carrying out forced air drying on the obtained solid at 120 ℃ for 3 hours to obtain activated carbon/graphene composite material powder; (4) 50 g of Na2SxAnd 30 g of activated carbon/graphene composite material powder are dispersed in 0.4 mol/L of lecithin aqueous solution and mixed by ultrasonic wave. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 30 h, and the temperature is 60 ℃. The resulting mixture was reacted at 75 ℃ for 2 hours, thenAnd then carrying out solid-liquid separation by adopting a polystyrene membrane (with the aperture of 20 microns), and carrying out forced air drying on the solid at 120 ℃ for 2 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 21: (1) the pine needles are dried by blowing at 100 ℃ for 36 hours, and then 240 g of the pine needles are crushed by ultrasonic waves. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. Sieving the ultrasonically pulverized sample with a straight-line filter sieve, and respectively using 10% HClO to obtain 80-mesh samples3The S aqueous solution and deionized water were washed 3 times. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 500 g of biomass and 30 g of nitrogen and sulfur co-doped graphene are added into 400 ml of H with the mass percentage of 10%3PO4Soaking and mixing in the water solution. The immersion time was 50 hours and the temperature was 60 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 2 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 96 hours at 350 ℃ in a nitrogen atmosphere, then washing the solid material to be neutral by using deionized water, performing solid-liquid separation by using a polypropylene bag (with the aperture of 0.2 micron), and freeze-drying the obtained solid for 10 hours to obtain activated carbon/graphene composite material powder; (4) 1 g of cystine and 50 g of activated carbon/graphene composite material are dispersed in N, N-dimethylformamide and mixed by mechanical stirring. The time of mechanical stirring was 60 hours at a temperature of 20 ℃. And (3) reacting the obtained mixture at 80 ℃ for 100 hours, then carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and carrying out vacuum drying on the solid at 70 ℃ for 96 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 22: (1) the sunflower stalks are naturally dried for 14 days, then 50.0 g of agate ball milling balls with the diameter of 1-1.3 cm and 100 g of sunflower stalks are sealed into an agate ball milling pot under the protection of argon, and then the ball milling pot is placed on a planetary ball mill and is ball milled for 2 hours at the rotating speed of 580 revolutions per minute. And taking the agate balls out by using tweezers, sieving the ball-milled samples by using a three-dimensional vibrating screen, and washing the 20-mesh samples by using 5% sulfuric acid aqueous solution and deionized water for 3 times respectively. Adopts polyethylene film (aperture 0.2 micron) solid-liquidSeparating, and air-blast drying the obtained solid at 70 ℃ for 96 hours; (2) 2 g of biomass and 100 g of phosphorus and sulfur co-doped graphene are added into 550 ml of ZnCl with the mass percent of 5%2Soaking in ethanol solution, and mixing. The immersion time was 10 hours and the temperature was 20 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 1 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material was activated for 84 hours at 450 ℃ under argon atmosphere and then successively with 1% H2SO4Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 1 micron), and freeze-drying the obtained solid for 30 hours to obtain activated carbon/graphene composite material powder; (4) 1 g of polythiophene and 25 g of activated carbon/graphene composite material were dispersed in N-methylpyrrolidone and mixed by mechanical stirring. The time of mechanical stirring was 30 hours and the temperature was 60 ℃. And reacting the obtained mixture at 75 ℃ for 2 hours, then carrying out solid-liquid separation by adopting a polystyrene membrane (with the aperture of 20 microns), and carrying out forced air drying on the solid at 120 ℃ for 2 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 23: (1) the vine sawdust is naturally dried for 3 days, then 1500.0 g of zirconia ball grinding balls with the diameter of 3-8 mm and 200 g of vine sawdust are sealed into a zirconia ball grinding tank under the protection of nitrogen, and then the ball grinding tank is placed on a planetary ball mill and is ball-milled for 30 hours at the rotating speed of 300 revolutions per minute. And (3) taking out the zirconia balls by using tweezers, sieving the ball-milled samples by using an ultrasonic vibration sieve, and washing the 50-mesh samples by using 5% hydrochloric acid water solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polypropylene membrane (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 24 hours; (2) 300 g of biomass and 10 g of nitrogen, phosphorus and sulfur co-doped graphene are added into 1000 ml of ZnCl with the mass percentage of 30%2Soaking in ethanol solution, and mixing. The immersion time was 140 hours and the temperature was 40 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 15 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 72 hours at 500 ℃ in a helium atmosphere, and then sequentially using 80% H3PO4Aqueous solution and deionizationWashing with water to neutrality, performing solid-liquid separation by using a polyethylene bag (with the aperture of 2 microns), and freeze-drying the obtained solid for 50 hours to obtain activated carbon/graphene composite material powder; (4) 1 g of guanidinium glucosinolate and 35 g of activated carbon/graphene composite material were dispersed in p-xylene and mixed by magnetic stirring. The magnetic stirring time was 5 hours and the temperature was 50 ℃. Reacting the obtained mixture for 1 hour at 60 ℃, then carrying out solid-liquid separation by adopting a polystyrene membrane (with the aperture of 0.2 micron), and carrying out forced air drying on the solid for 12 hours at 110 ℃ to obtain the sulfur-activated carbon/graphene composite material powder.
Example 24: (1) the algae are naturally dried for 30 days, then 500.0 g of alumina balls with the diameter of 8-15 mm are ground, 300 g of the algae are sealed into an agate ball milling pot under the protection of air, and then the ball milling pot is placed on a planetary ball mill and is ball milled for 60 hours at the rotating speed of 100 revolutions per minute. And (3) taking out the alumina ball by using a pair of tweezers, sieving the ball-milled sample by using an ultrasonic vibration sieve, and washing the 80-mesh sample by using 30% hydrochloric acid water solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (aperture is 2 microns), and the obtained solid is dried by air blast for 1 hour at 120 ℃; (2) 20 g of biomass and 100 g of phosphorus and boron co-doped graphene are added into 400 ml of H with the mass percent of 80%3PO4And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 30 hours, the temperature is 40 ℃, and the rotating speed is 100 r/min. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 20 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 1% NH at 600 ℃3/N2Activating for 60 hours in a gas atmosphere, washing with 50% HCl aqueous solution and deionized water in sequence until the solution is neutral, performing solid-liquid separation by using a polyethylene film (with the aperture of 5 microns), and freeze-drying the obtained solid for 96 hours to obtain activated carbon/graphene composite material powder; (4) mixing 20 g of sulfur powder and 10 g of activated carbon/graphene composite material powder by an ultrasonic method. The frequency of the ultrasound was 20 kHz, the power density was 500 w, the time was 30 hours and the temperature was 20 ℃. The resulting mixture was reacted at 100 c for 96 hours and then at 200 c for a subsequent 96 hours to remove excess sulfur,and obtaining sulfur-activated carbon/graphene composite material powder.
Example 25: (1) will be provided withReedNaturally drying for 12 hours, and then mixing 200 gReedAnd (4) crushing by adopting ultrasonic waves. The ultrasonic frequency is 20 kHz, the power density is 500 w, the time is 28 h, and the temperature is 25 ℃. And sieving the ultrasonically crushed sample by using a high-frequency vibrating screen, and washing the 100-mesh sample by using 30% sulfuric acid aqueous solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (the aperture is 0.2 micron), and the obtained solid is dried by air blast for 30 hours at the temperature of 80 ℃; (2) 350 g of biomass and 10 g of nitrogen, sulfur and boron co-doped graphene are added into 200 ml of ZnCl with the mass percent of 400%2And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 1 hour, the temperature is 60 ℃, and the rotating speed is 3000 r/min. The solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 5 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 5% NH at 700 deg.C3Activating for 48 hours in an Ar gas atmosphere, and then sequentially using 60 percent HNO3Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by using a polystyrene bag (with the aperture of 10 microns), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours to obtain activated carbon/graphene composite material powder; (4) 100 g of thiourea and 50 g of activated carbon/graphene composite powder were mixed by an ultrasonic method. The frequency of the ultrasound was 30 kHz, the power density was 800 w, the time was 10 hours and the temperature was 40 ℃. The resulting mixture was reacted at 155 ℃ for 84 hours followed by 250 ℃ for 80 hours to remove excess sulfur and obtain sulfur-activated carbon/graphene composite powder.
Example 26: (1) vacuum drying the alcohol residue at 70 deg.C for 96 hr, and pulverizing 200 g of alcohol residue with ultrasonic wave. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. And sieving the ultrasonically crushed sample by using an airflow sieve, and washing the 40-mesh sample by using 80% phosphoric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 50 hours; (2) 150 g of biomass and 10 g of phosphorus, sulfur and boron co-doped graphene are mixed in 800 ml of ZnC with the mass percent of 80%l2And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 56 hours, the temperature is 20 ℃, and the rotating speed is 1500 rpm. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 10 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 10% NH at 800 DEG C3Activating in He gas atmosphere for 32 hours, and sequentially using 70% HClO4Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polystyrene membrane (with the aperture of 15 microns), and performing vacuum drying on the obtained solid at 75 ℃ for 75 hours to obtain activated carbon/graphene composite material powder; (4) mixing 80 g of glutathione and 100 g of activated carbon/graphene composite material powder by an ultrasonic method. The frequency of the ultrasound was 25 kHz, the power density was 1000 w, the time was 30 minutes and the temperature was 60 ℃. And reacting the obtained mixture at 200 ℃ for 80 hours, then reacting at 300 ℃ for 60 hours, and removing redundant sulfur to obtain sulfur-activated carbon/graphene composite material powder.
Example 27: (1) and (3) drying the furfural residues for 2 hours in vacuum at 120 ℃, and then crushing 300 g of furfural residues by adopting ultrasonic waves. The ultrasonic frequency is 30 kHz, the power density is 1000 w, the time is 2 h, and the temperature is 60 ℃. The sample after ultrasonic crushing is sieved by a drum sieve, and a 40-mesh sample is respectively washed 3 times by 10% perchloric acid aqueous solution and deionized water. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 20 g of biomass and 100 g of graphene are stirred and mixed in 50 ml of 10 mass percent KOH aqueous solution. The magnetic stirring time was 5 hours at 20 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 50% NH at 900 DEG C3/N2Activating for 16 hours under a gas atmosphere, then washing with 1% NaOH aqueous solution and deionized water in sequence until the solution is neutral, performing solid-liquid separation by using a polypropylene bag (with the aperture of 20 microns), and drying the obtained solid for 60 hours at 80 ℃ in vacuum to obtain activated carbon/graphene composite material powder; (4) 150 g of lansoprazole sulfide and 20 g of activated carbon/graphene composite material powder are adoptedMixing by mechanical stirring. The time of mechanical stirring was 60 hours at a temperature of 20 ℃. And reacting the obtained mixture at 300 ℃ for 70 hours, then reacting at 350 ℃ for 50 hours, and removing redundant sulfur to obtain sulfur-activated carbon/graphene composite material powder.
Example 28: (1) the olive residue filter cake was dried by air blowing at 100 ℃ for 36 hours and then 240 g of the olive residue filter cake was crushed by ultrasound. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. Sieving the ultrasonically pulverized sample with a straight-line filter sieve, and respectively using 10% HClO to obtain 80-mesh samples3The S aqueous solution and deionized water were washed 3 times. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 100 g of biomass and 10 g of nitrogen-doped graphene are added into 100ml of K with the mass percentage of 20%2CO3Stirring and mixing the aqueous solution. The time of mechanical stirring was 20 hours and the temperature was 40 ℃. A polyethylene bag (with the aperture of 1 micron) is adopted to realize solid-liquid separation, the solid is left in the bag, and the liquid is thrown out, extruded, pressed out or flowed out; (3) the solid material obtained is 90% NH at 1050 DEG C3/N2Activating for 0.5 hour in gas atmosphere, washing with 5% KOH aqueous solution and deionized water in sequence to be neutral, performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 0.2 micron), and performing vacuum drying on the obtained solid for 45 hours at 85 ℃ to obtain activated carbon/graphene composite material powder; (4) 150 g of dixylylsulfone and 30 g of activated carbon/graphene composite material powder are mixed by magnetic stirring. The magnetic stirring time was 80 hours and the temperature was 40 ℃. The obtained mixture is reacted for 60 hours at 400 ℃, and then reacted for 40 hours at 400 ℃, and the excessive sulfur is removed, so that the sulfur-activated carbon/graphene composite material powder is obtained.
Example 29: (1) the papermulberry bark is naturally dried for 14 days, then 50.0 g of agate ball milling balls with the diameter of 1-1.3 cm and 100 g of papermulberry bark are sealed in an agate ball milling tank under the protection of argon, and then the ball milling tank is arranged on a planetary ball mill and is ball milled for 2 hours at the rotating speed of 580 r/min. Taking the agate balls out by using tweezers, sieving the ball-milled samples by using a three-dimensional vibrating screen,a20-mesh sample was washed 3 times with 5% aqueous sulfuric acid and deionized water, respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours; (2) 2 g of biomass and 100 g of phosphorus-doped graphene are ultrasonically mixed in 300 ml of NaOH aqueous solution with the mass percent of 50%. The ultrasonic frequency is 20 KHz, the power density is 500 w, the time is 30 hours, and the temperature is 20 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the obtained solid material is N at 550 DEG C2Activating for 90 hours in atmosphere, and then sequentially using 10% Na2CO3Washing the aqueous solution and deionized water to be neutral, carrying out solid-liquid separation by adopting a polyethylene bag (with the aperture of 2 microns), and carrying out forced air drying on the obtained solid at 90 ℃ for 30 hours to obtain activated carbon/graphene composite material powder; (4) 150 g of di-n-dodecyl sulfoxide and 60 g of activated carbon/graphene composite material powder are mixed by mechanical stirring. The time of mechanical stirring was 30 hours and the temperature was 60 ℃. The obtained mixture is reacted for 50 hours at 500 ℃, and then reacted for 20 hours at 450 ℃ to obtain the sulfur-activated carbon/graphene composite material powder.
Example 30: (1) the plum kernel was naturally dried for 3 days, and then 1500.0 g of zirconia balls having a diameter of 3-8 mm, 200 g of the plum kernel were sealed in a zirconia ball-milling jar under nitrogen protection, and then the jar was placed on a planetary ball mill and ball-milled at a rotation speed of 300 rpm for 30 hours. And (3) taking out the zirconia balls by using tweezers, sieving the ball-milled samples by using an ultrasonic vibration sieve, and washing the 50-mesh samples by using 5% hydrochloric acid water solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polypropylene membrane (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 24 hours; (2) 200 g of biomass, 10 g of boron-doped graphene and 10 g of solid Na2CO3And (4) ultrasonic mixing. The ultrasonic frequency is 25 KHz, the power density is 800 w, the time is 10 hours, and the temperature is 40 ℃. The solid-liquid separation is realized by adopting a polystyrene membrane (the aperture is 2 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the obtained solid material is activated in an Ar atmosphere at the temperature of 650 DEG CTake 75 hours, then use 10% H2SO4Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and performing forced air drying on the obtained solid at 100 ℃ for 15 hours to obtain activated carbon/graphene composite material powder; (4) 200 g of chiral camphor sulfur ylide and 80 g of activated carbon/graphene composite material powder are mixed by magnetic stirring. The magnetic stirring time was 5 hours and the temperature was 50 ℃. The obtained mixture is reacted for 40 hours at 600 ℃, and then reacted for 0.5 hour at 500 ℃ to obtain the sulfur-activated carbon/graphene composite material powder.
Example 31: (1) the bamboo powder is naturally dried for 30 days, then 500.0 g of alumina ball milling balls with the diameter of 8-15 mm and 300 g of bamboo powder are sealed into an agate ball milling tank under the protection of air, and then the ball milling tank is placed on a planetary ball mill and is ball milled for 60 hours at the rotating speed of 100 r/min. And (3) taking out the alumina ball by using a pair of tweezers, sieving the ball-milled sample by using an ultrasonic vibration sieve, and washing the 80-mesh sample by using 30% hydrochloric acid water solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (aperture is 2 microns), and the obtained solid is dried by air blast for 1 hour at 120 ℃; (2) 30 g of biomass and 1 g of sulfur-doped graphene are added into 300 ml of H with the mass percent of 50%3PO4Ultrasonic mixing in the water solution. The ultrasonic frequency is 30 KHz, the power density is 1000 w, the time is 1 hour, and the temperature is 60 ℃. The solid-liquid separation is realized by adopting a polyethylene film (with the aperture of 1 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 50 hours in a helium atmosphere at 750 ℃, and then sequentially using 50% K2CO3Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by using a polystyrene bag (with the aperture of 10 microns), and performing forced air drying on the obtained solid at 110 ℃ for 8 hours to obtain activated carbon/graphene composite material powder; (4) 250 g of p-phenylene disulfide powder and 40 g of activated carbon/graphene composite powder were mixed using high shear. The temperature of the high-speed shearing is 20 ℃, the rotating speed is 3000 r/min, and the time is 72 hours. The resulting mixture was reacted at 700 ℃ for 30 hours and then washed with m-xylene under magnetic stirringAnd stirring and washing. The magnetic stirring time was 5 hours and the temperature was 50 ℃. And (3) carrying out solid-liquid separation by using a polystyrene bag (with the aperture of 1 micron), and carrying out forced air drying on the solid at the temperature of 80 ℃ for 24 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 32: (1) naturally drying poplar sawdust for 12 hours, and then crushing 200 g of poplar sawdust by adopting ultrasonic waves. The ultrasonic frequency is 20 kHz, the power density is 500 w, the time is 28 h, and the temperature is 25 ℃. And sieving the ultrasonically crushed sample by using a high-frequency vibrating screen, and washing the 100-mesh sample by using 30% sulfuric acid aqueous solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (the aperture is 0.2 micron), and the obtained solid is dried by air blast for 30 hours at the temperature of 80 ℃; (2) 2 g of biomass and 100 g of nitrogen and phosphorus co-doped graphene are added into 1000 ml of ZnCl with the mass percent of 10%2Soaking and mixing in the water solution. The immersion time was 30 hours and the temperature was 40 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the obtained solid material is NH at 850 DEG C3Activating for 40 hours in atmosphere, and then sequentially using 10% CH3Washing the COOH aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polystyrene membrane (with the aperture of 10 microns), and performing forced air drying on the obtained solid at 120 ℃ for 2 hours to obtain activated carbon/graphene composite material powder; (4) 5 g of benzophenone and 15 g of activated carbon/graphene composite material powder are mixed by high-speed shearing. The temperature of the high-speed shearing is 40 ℃, the time is 40 hours, and the rotating speed is 1000 r/min. The resulting mixture was reacted at 800 ℃ for 20 hours and then washed with toluene under mechanical stirring. The time of mechanical stirring was 30 hours and the temperature was 60 ℃. And (3) carrying out solid-liquid separation by using a polyethylene bag (with the aperture of 2 microns), and carrying out vacuum drying on the solid at the temperature of 75 ℃ for 96 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 33: (1) oat hulls are vacuum dried at 70 ℃ for 96 hours and then 200 g of oat hulls are crushed using ultrasound. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. Sieving the ultrasonically pulverized sample with airflow sieve, and collecting 40 mesh sampleWashed 3 times with 80% aqueous phosphoric acid and deionized water, respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 50 hours; (2) 300 g of biomass and 10 g of nitrogen and boron co-doped graphene are added into 500 ml of ZnCl with the mass percent of 100%2Soaking and mixing in the water solution. The immersion time was 90 hours and the temperature was 30 ℃. A polyethylene bag (with the aperture of 1 micron) is adopted to realize solid-liquid separation, the solid is left in the bag, and the liquid is thrown out, extruded, pressed out or flowed out; (3) activating the obtained solid material in a nitrogen atmosphere at 950 ℃ for 20 hours, then sequentially washing the solid material to be neutral by adopting a 5% oxalic acid water solution and deionized water, carrying out solid-liquid separation by adopting a polypropylene bag (with the aperture of 0.2 micron), and drying the obtained solid at 80 ℃ for 96 hours in vacuum to obtain activated carbon/graphene composite material powder; (4) 50 g of 2, 2-dithiodibenzoic acid and 25 g of activated carbon/graphene composite material are mixed by high-speed shearing. The temperature of high-speed shearing is 60 ℃, the time is 1 hour, and the rotating speed is 2000 r/min. The resulting mixture was reacted at 900 ℃ for 10 hours, and then washed with ethyl acetate under mechanical stirring. The time of mechanical stirring was 60 hours at a temperature of 20 ℃. And (3) carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and carrying out forced air drying on the solid at 120 ℃ for 2 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 34: (1) bagasse was vacuum-dried at 120 ℃ for 2 hours, and then 300 g of bagasse was pulverized by ultrasonic waves. The ultrasonic frequency is 30 kHz, the power density is 1000 w, the time is 2 h, and the temperature is 60 ℃. The sample after ultrasonic crushing is sieved by a drum sieve, and a 40-mesh sample is respectively washed 3 times by 10% perchloric acid aqueous solution and deionized water. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 500 g of biomass and 30 g of nitrogen and sulfur co-doped graphene are added into 400 ml of H with the mass percentage of 10%3PO4Soaking and mixing in the water solution. The immersion time was 50 hours and the temperature was 60 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 2 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the obtained solid material is in argon atmosphere at 1000 DEG CActivating for 10 hours, washing the activated carbon/graphene composite material to be neutral by sequentially adopting 30% formic acid water solution and deionized water, performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 1 micron), and performing forced air drying on the obtained solid at 95 ℃ for 50 hours to obtain activated carbon/graphene composite material powder; (4) and 34, mixing 150 g of chaloogenophyrium and 35 g of the activated carbon/graphene composite material by high-speed shearing. The temperature of the high-speed shearing is 20 ℃, the time is 48 hours, and the rotating speed is 100 r/min. The resulting mixture was reacted at 1000 ℃ for 0.5 hour and then mixed with chloroform under ultrasound. The frequency of the ultrasound was 25 kHz, the power density was 1000 w, the time was 30 minutes and the temperature was 60 ℃. And (3) performing solid-liquid separation by using a polypropylene bag (with the aperture of 10 microns), and performing vacuum drying on the solid at 70 ℃ for 2 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 35: (1) air-drying distiller's grains at 100 deg.C for 36 hr, and pulverizing 240 g of distiller's grains with ultrasonic wave. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. Sieving the ultrasonically pulverized sample with a straight-line filter sieve, and respectively using 10% HClO to obtain 80-mesh samples3The S aqueous solution and deionized water were washed 3 times. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 2 g of biomass and 100 g of phosphorus and sulfur co-doped graphene are added into 550 ml of ZnCl with the mass percent of 5%2Soaking in ethanol solution, and mixing. The immersion time was 10 hours and the temperature was 20 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 1 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in a helium atmosphere at 500 ℃ for 2 hours, then sequentially washing the solid material with 60% trifluoroacetic acid aqueous solution and deionized water to be neutral, carrying out solid-liquid separation by adopting a polyethylene bag (with the aperture of 2 microns), and carrying out forced air drying on the obtained solid at 100 ℃ for 20 hours to obtain activated carbon/graphene composite material powder; (4) 300 g of 8-mercaptoquinoline and 55 g of activated carbon/graphene composite material were mixed with high shear. The temperature of the high-speed shearing is 30 ℃, the time is 24 hours, and the rotating speed is 500 r/min. The resulting mixture was reacted at 250 ℃ for 50 hours, then a ring was usedHexanone was washed in ultrasound. The frequency of the ultrasound was 30 kHz, the power density was 800 w, the time was 10 hours and the temperature was 40 ℃. And (3) carrying out solid-liquid separation by adopting a polypropylene membrane (with the aperture of 20 microns), and carrying out forced air drying on the solid at 85 ℃ for 12 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 36: (1) the paper making leftover materials are naturally dried for 14 days, then 50.0 g of agate ball milling balls with the diameter of 1-1.3 cm and 100 g of paper making leftover materials are sealed into an agate ball milling tank under the protection of argon, and then the ball milling tank is placed on a planetary ball mill and is ball milled for 2 hours at the rotating speed of 580 r/min. And taking the agate balls out by using tweezers, sieving the ball-milled samples by using a three-dimensional vibrating screen, and washing the 20-mesh samples by using 5% sulfuric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours; (2) 300 g of biomass and 10 g of nitrogen, phosphorus and sulfur co-doped graphene are added into 1000 ml of ZnCl with the mass percentage of 30%2Soaking in ethanol solution, and mixing. The immersion time was 140 hours and the temperature was 40 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 15 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in a nitrogen atmosphere at 600 ℃ for 5 hours, then sequentially washing the solid material with 1% pyridine water solution and deionized water to be neutral, carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and carrying out forced air drying on the obtained solid at 120 ℃ for 4 hours to obtain activated carbon/graphene composite material powder; (4) 50.0 g of agate ball milling balls with the diameter of 1-1.3 cm, 100 g of 4-bromo-2-trifluoromethoxyphenyl thiocyanate and 65 g of the activated carbon/graphene composite material are sealed into an agate ball milling pot under the protection of argon, and then the ball milling pot is placed on a planetary ball mill and ball milled for 2 hours at the rotating speed of 580 revolutions per minute. The agate spheres were removed with tweezers and the resulting mixture was reacted at 350 ℃ for 12 hours and then washed under ultrasound in carbon tetrachloride. The frequency of the ultrasound was 20 kHz, the power density was 500 w, the time was 30 hours and the temperature was 20 ℃. Performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 20 microns), and freeze-drying the solid for 10 hours to obtain the sulfur-activated carbon/graphene composite material powderAnd (3) grinding.
Example 37: (1) the shaddock peel was naturally dried for 3 days, then 1500.0 g of zirconia balls with a diameter of 3-8 mm were milled, 200 g of shaddock peel was sealed under nitrogen protection into a zirconia ball milling jar, and then the jar was placed on a planetary ball mill and ball milled at 300 rpm for 30 hours. And (3) taking out the zirconia balls by using tweezers, sieving the ball-milled samples by using an ultrasonic vibration sieve, and washing the 50-mesh samples by using 5% hydrochloric acid water solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polypropylene membrane (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 24 hours; (2) 20 g of biomass and 100 g of phosphorus and boron co-doped graphene are added into 400 ml of H with the mass percent of 80%3PO4And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 30 hours, the temperature is 40 ℃, and the rotating speed is 100 r/min. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 20 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in a nitrogen atmosphere at 800 ℃ for 1 hour, then sequentially washing the solid material with 5% methylamine water solution and deionized water to be neutral, performing solid-liquid separation by using a polystyrene bag (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at 110 ℃ for 12 hours to obtain activated carbon/graphene composite material powder; (4) 1500.0 g of zirconia ball milling balls with a diameter of 3-8 mm, 100 g of p-toluylene urea and 75 g of activated carbon/graphene composite material were sealed in a zirconia ball milling pot under nitrogen protection, and then the ball milling pot was placed on a planetary ball mill and ball milled for 30 hours at a rotation speed of 300 revolutions per minute. The zirconia balls were removed with tweezers, and the resulting mixture was reacted at 450 ℃ for 24 hours, and then washed in n-butanol with magnetic stirring. The magnetic stirring time was 5 hours and the temperature was 50 ℃. And (3) performing solid-liquid separation by using a polypropylene bag (with the aperture of 10 microns), and freeze-drying the solid for 50 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 38: (1) naturally drying the biomass cracking residual carbon for 30 days, then grinding 500.0 g of alumina balls with the diameter of 8-15 mm and 300 g of biomass cracking residual carbon into agate ball-milling tanks in a sealed mode under the protection of air, and then placing the ball-milling tanks into a planetary typeBall milling was carried out on a ball mill at 100 rpm for 60 hours. And (3) taking out the alumina ball by using a pair of tweezers, sieving the ball-milled sample by using an ultrasonic vibration sieve, and washing the 80-mesh sample by using 30% hydrochloric acid water solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (aperture is 2 microns), and the obtained solid is dried by air blast for 1 hour at 120 ℃; (2) 350 g of biomass and 10 g of nitrogen, sulfur and boron co-doped graphene are added into 200 ml of ZnCl with the mass percent of 400%2And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 1 hour, the temperature is 60 ℃, and the rotating speed is 3000 r/min. The solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 5 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 60 hours at 400 ℃ in an ammonia atmosphere, then sequentially washing the solid material to be neutral by using 10% sodium methoxide aqueous solution and deionized water, performing solid-liquid separation by using a polystyrene membrane (with the aperture of 1 micron), and performing vacuum drying on the obtained solid for 85 hours at 70 ℃ to obtain activated carbon/graphene composite material powder; (4) 500.0 g of alumina ball milling balls with the diameter of 8-15 mm, 100 g of polydimercaptothiadiazole and 85 g of activated carbon/graphene composite material are sealed into an agate ball milling pot under the protection of air, and then the ball milling pot is placed on a planetary ball mill and is ball milled for 60 hours at the rotating speed of 100 revolutions per minute. The alumina spheres were removed with tweezers and the resulting mixture reacted at 550 ℃ for 5 hours and then washed with carbon disulfide under mechanical agitation. The time of mechanical stirring was 30 hours and the temperature was 60 ℃. And (3) carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and freeze-drying the solid for 96 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 39: (1) the oat hulls were naturally dried for 12 hours and then 200 g of the oat hulls were pulverized using ultrasonic waves. The ultrasonic frequency is 20 kHz, the power density is 500 w, the time is 28 h, and the temperature is 25 ℃. And sieving the ultrasonically crushed sample by using a high-frequency vibrating screen, and washing the 100-mesh sample by using 30% sulfuric acid aqueous solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (the aperture is 0.2 micron), and the obtained solid is dried by air blast for 30 hours at the temperature of 80 ℃; (2) 150 g of biomass and 10 g of phosphorus, sulfur and boron co-doped graphene are mixed in 800 mlZnCl with the weight percentage of 80 percent2And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 56 hours, the temperature is 20 ℃, and the rotating speed is 1500 rpm. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 10 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 70 hours at 500 ℃ in a nitrogen atmosphere, then sequentially washing the solid material to be neutral by using 30% Schiff base aqueous solution and deionized water, performing solid-liquid separation by using a polyethylene film (with the aperture of 3 microns), and performing forced air drying on the obtained solid for 5 hours at 115 ℃ to obtain activated carbon/graphene composite material powder; (4) 50.0 g of agate ball milling balls with the diameter of 1-1.3 cm, 100 g of thioacetamide and 65 g of activated carbon/graphene composite material are dispersed in carbon disulfide, sealed in an agate ball milling pot under the protection of argon, and then the ball milling pot is placed on a planetary ball mill and ball milled for 2 hours at the rotating speed of 580 revolutions per minute. The agate ball was removed with forceps and the pellet was washed with n-butanol in ultrasound. The frequency of the ultrasound was 20 kHz, the power density was 500 w, the time was 30 hours and the temperature was 20 ℃. And (3) performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 20 microns), and performing vacuum drying on the solid at 70 ℃ for 96 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 40: (1) vacuum drying the waste pepper straws at 70 ℃ for 96 hours, and then crushing 200 g of the waste pepper straws by using ultrasonic waves. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. And sieving the ultrasonically crushed sample by using an airflow sieve, and washing the 40-mesh sample by using 80% phosphoric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 50 hours; (2) 20 g of biomass and 100 g of graphene are stirred and mixed in 50 ml of 10 mass percent KOH aqueous solution. The magnetic stirring time was 5 hours at 20 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in argon atmosphere at 750 ℃ for 1 hour, then sequentially washing the solid material with 50% butylamine aqueous solution and deionized water to be neutral, carrying out solid-liquid separation by adopting a polypropylene bag (with the aperture of 20 microns), and carrying out forced air drying on the obtained solid at 120 ℃ for 3 hours to obtain activated carbon/graphene composite material powder; (4) 1500.0 g of zirconia ball milling balls with a diameter of 3-8 mm, 100 g of 2-mercaptopyrimidine and 75 g of activated carbon/graphene composite material were dispersed in tetrahydrofuran, sealed into a zirconia ball milling jar under nitrogen protection, and then the jar was placed on a planetary ball mill and ball milled at a rotational speed of 300 revolutions per minute for 30 hours. The zirconia balls were removed with tweezers and the resulting mixture was washed with n-pentanoic acid under ultrasound. The frequency of the ultrasound was 30 kHz, the power density was 800 w, the time was 10 hours and the temperature was 40 ℃. And (3) performing solid-liquid separation by using a polypropylene bag (with the aperture of 10 microns), and performing vacuum drying on the solid at 100 ℃ for 40 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 41: (1) vacuum drying oil tea shell at 120 deg.C for 2 hr, and pulverizing 300 g of oil tea shell with ultrasonic wave. The ultrasonic frequency is 30 kHz, the power density is 1000 w, the time is 2 h, and the temperature is 60 ℃. The sample after ultrasonic crushing is sieved by a drum sieve, and a 40-mesh sample is respectively washed 3 times by 10% perchloric acid aqueous solution and deionized water. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 100 g of biomass and 10 g of nitrogen-doped graphene are added into 100ml of K with the mass percentage of 20%2CO3Stirring and mixing the aqueous solution. The time of mechanical stirring was 20 hours and the temperature was 40 ℃. A polyethylene bag (with the aperture of 1 micron) is adopted to realize solid-liquid separation, the solid is left in the bag, and the liquid is thrown out, extruded, pressed out or flowed out; (3) activating the obtained solid material for 96 hours at 350 ℃ in a nitrogen atmosphere, then washing the solid material to be neutral by using deionized water, performing solid-liquid separation by using a polypropylene bag (with the aperture of 0.2 micron), and freeze-drying the obtained solid for 10 hours to obtain activated carbon/graphene composite material powder; (4) dispersing 500.0 g of alumina ball grinding balls with the diameter of 8-15 mm, 100 g of 2-furanthiocarboxylic acid and 85 g of activated carbon/graphene composite material in diethyl isovalerate, sealing the mixture in an agate ball grinding tank under the protection of air, then placing the ball grinding tank on a planetary ball mill, and carrying out ball grinding for 60 hours at the rotating speed of 100 revolutions per minute. The alumina spheres were removed with forceps and the resulting mixture was washed with o-xylene under ultrasound. The frequency of the ultrasound was 25 kHz, the power density was 1000 w, the time was 30 minutes and the temperature was 60 ℃. And (3) carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and carrying out forced air drying on the solid at 120 ℃ for 2 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 42: (1) the orange peel was air-dried at 100 ℃ for 36 hours, and then 240 g of the orange peel was pulverized by ultrasonic waves. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. Sieving the ultrasonically pulverized sample with a straight-line filter sieve, and respectively using 10% HClO to obtain 80-mesh samples3The S aqueous solution and deionized water were washed 3 times. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 2 g of biomass and 100 g of phosphorus-doped graphene are ultrasonically mixed in 300 ml of NaOH aqueous solution with the mass percent of 50%. The ultrasonic frequency is 20 KHz, the power density is 500 w, the time is 30 hours, and the temperature is 20 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material was activated for 84 hours at 450 ℃ under argon atmosphere and then successively with 1% H2SO4Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 1 micron), and freeze-drying the obtained solid for 30 hours to obtain activated carbon/graphene composite material powder; (4) 500.0 g of silicon carbide ball milling balls with the diameter of 8-15 mm, 100 g of 2-furancarbothioic acid and 85 g of activated carbon/graphene composite material are dispersed in thiophene, sealed in a silicon carbide tank under the protection of air, and then the ball milling tank is placed on a planetary ball mill and ball milled for 60 hours at the rotating speed of 100 revolutions per minute. The silicon carbide spheres were removed with tweezers and the resulting mixture was washed with acetonitrile under mechanical agitation. The time of mechanical stirring was 60 hours at a temperature of 20 ℃. And (3) carrying out solid-liquid separation by using a polyethylene bag (with the aperture of 2 microns), and freeze-drying the solid for 96 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 43: (1) naturally drying water caltrop skinAfter 14 days, 50.0 g of agate balls with the diameter of 1-1.3 cm and 100 g of water chestnut skin are sealed into an agate ball milling pot under the protection of argon, and then the ball milling pot is placed on a planetary ball mill and ball milled for 2 hours at the rotating speed of 580 revolutions per minute. And taking the agate balls out by using tweezers, sieving the ball-milled samples by using a three-dimensional vibrating screen, and washing the 20-mesh samples by using 5% sulfuric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours; (2) 200 g of biomass, 10 g of boron-doped graphene and 10 g of solid Na2CO3And (4) ultrasonic mixing. The ultrasonic frequency is 25 KHz, the power density is 800 w, the time is 10 hours, and the temperature is 40 ℃. The solid-liquid separation is realized by adopting a polystyrene membrane (the aperture is 2 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 72 hours at 500 ℃ in a helium atmosphere, and then sequentially using 80% H3PO4Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by using a polyethylene bag (with the aperture of 2 microns), and freeze-drying the obtained solid for 50 hours to obtain activated carbon/graphene composite material powder; (4) 50.0 g of agate ball milling balls with the diameter of 1-1.3 cm, 100 g of 2-furanthiocarboxylic acid and 65 g of activated carbon/graphene composite material are dispersed in carbon disulfide, sealed in an agate ball milling pot under the protection of argon, and then the ball milling pot is placed on a planetary ball mill and ball milled for 2 hours at the rotating speed of 580 revolutions per minute. The agate ball was removed with tweezers and the pellet was washed with n-butanol under magnetic stirring. The magnetic stirring time was 80 hours and the temperature was 40 ℃. And (3) performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 0.2 micron), and freeze-drying the solid for 60 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 44: (1) the coffee pods were naturally dried for 3 days, then 1500.0 g of zirconia balls with a diameter of 3-8 mm were ground, 200 g of coffee pods were sealed under nitrogen protection into a zirconia ball milling jar, and then the jar was placed on a planetary ball mill and ball milled at 300 revolutions per minute for 30 hours. Taking out the zirconia balls by using tweezers, sieving the ball-milled samples by using an ultrasonic vibration sieve, and taking 50-mesh samples for respective use5% hydrochloric acid aqueous solution and deionized water were washed 3 times. Performing solid-liquid separation by using a polypropylene membrane (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 24 hours; (2) 30 g of biomass and 1 g of sulfur-doped graphene are added into 300 ml of H with the mass percent of 50%3PO4Ultrasonic mixing in the water solution. The ultrasonic frequency is 30 KHz, the power density is 1000 w, the time is 1 hour, and the temperature is 60 ℃. The solid-liquid separation is realized by adopting a polyethylene film (with the aperture of 1 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 1% NH at 600 ℃3/N2Activating for 60 hours in a gas atmosphere, washing with 50% HCl aqueous solution and deionized water in sequence until the solution is neutral, performing solid-liquid separation by using a polyethylene film (with the aperture of 5 microns), and freeze-drying the obtained solid for 96 hours to obtain activated carbon/graphene composite material powder; (4) 1500.0 g of zirconia ball milling balls with a diameter of 3-8 mm, 100 g of 2-mercaptopyrimidine and 75 g of activated carbon/graphene composite material were dispersed in tetrahydrofuran, sealed into a zirconia ball milling jar under nitrogen protection, and then the jar was placed on a planetary ball mill and ball milled at a rotational speed of 300 revolutions per minute for 30 hours. The zirconia balls were removed with tweezers and the resulting mixture was washed with n-pentanoic acid under mechanical agitation. The time of mechanical stirring was 30 hours and the temperature was 60 ℃. And (3) carrying out solid-liquid separation by using a polyethylene bag (with the aperture of 1 micron), and freeze-drying the solid for 30 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 45: (1) the bamboo shoot shells are naturally dried for 30 days, then 500.0 g of alumina balls with the diameter of 8-15 mm are ground, 300 g of the bamboo shoot shells are sealed in an agate ball milling pot under the protection of air, and then the ball milling pot is placed on a planetary ball mill and is ball milled for 60 hours at the rotating speed of 100 r/min. And (3) taking out the alumina ball by using a pair of tweezers, sieving the ball-milled sample by using an ultrasonic vibration sieve, and washing the 80-mesh sample by using 30% hydrochloric acid water solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (aperture is 2 microns), and the obtained solid is dried by air blast for 1 hour at 120 ℃; (2) 2 g of biomass and 100 g of nitrogen and phosphorus co-doped graphene are added into 1000 ml of ZnCl with the mass percent of 10%2Soaking and mixing in the water solution. Time of impregnation30 hours at 40 degrees celsius. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 5% NH at 700 deg.C3Activating for 48 hours in an Ar gas atmosphere, and then sequentially using 60 percent HNO3Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by using a polystyrene bag (with the aperture of 10 microns), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours to obtain activated carbon/graphene composite material powder; (4) 500.0 g of alumina ball milling balls with the diameter of 8-15 mm, 100 g of 2-furanthiocarboxylic acid and 85 g of activated carbon/graphene composite material are dispersed in diethyl isovalerate, sealed in an agate ball milling pot under the protection of air, and then the ball milling pot is placed on a planetary ball mill and ball milled for 60 hours at the rotating speed of 100 revolutions per minute. The alumina spheres were removed with tweezers and the resulting mixture was washed with o-xylene under magnetic stirring. The magnetic stirring time was 5 hours and the temperature was 50 ℃. And (3) carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and freeze-drying the solid for 10 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 46: (1) naturally drying the sorghum husk for 12 hours, and then crushing 200 g of the sorghum husk by using ultrasonic waves. The ultrasonic frequency is 20 kHz, the power density is 500 w, the time is 28 h, and the temperature is 25 ℃. And sieving the ultrasonically crushed sample by using a high-frequency vibrating screen, and washing the 100-mesh sample by using 30% sulfuric acid aqueous solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (the aperture is 0.2 micron), and the obtained solid is dried by air blast for 30 hours at the temperature of 80 ℃; (2) 300 g of biomass and 10 g of nitrogen and boron co-doped graphene are added into 500 ml of ZnCl with the mass percent of 100%2Soaking and mixing in the water solution. The immersion time was 90 hours and the temperature was 30 ℃. A polyethylene bag (with the aperture of 1 micron) is adopted to realize solid-liquid separation, the solid is left in the bag, and the liquid is thrown out, extruded, pressed out or flowed out; (3) the solid material obtained is 10% NH at 800 DEG C3Activating in He gas atmosphere for 32 hours, and sequentially using 70% HClO4Washing the water solution and deionized water to neutrality, performing solid-liquid separation by using a polystyrene membrane (with the aperture of 15 microns), and performing solid-liquid separation on the obtained solid at 75 DEG CVacuum drying for 75 hours to obtain activated carbon/graphene composite material powder; (4) adding 10 g of Na2SO3And 10 g of activated carbon/graphene composite powder are dispersed in 10 ml of water and mixed by an ultrasonic method. The frequency of the ultrasound was 20 kHz, the power density was 500 w, the time was 30 hours and the temperature was 20 ℃. Then, 5 wt% aqueous hydrochloric acid was added to the resulting mixture until the precipitation of sulfur was complete. And (3) performing solid-liquid separation by adopting a polypropylene bag (with the aperture of 0.2 micron), washing the solid in deionized water to be neutral, performing solid-liquid separation by adopting the polypropylene bag (with the aperture of 1 micron), and freeze-drying for 96 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 47: (1) the plum kernel was vacuum-dried at 70 ℃ for 96 hours, and then 200 g of the plum kernel was pulverized by ultrasonic waves. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. And sieving the ultrasonically crushed sample by using an airflow sieve, and washing the 40-mesh sample by using 80% phosphoric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 50 hours; (2) 500 g of biomass and 30 g of nitrogen and sulfur co-doped graphene are added into 400 ml of H with the mass percentage of 10%3PO4Soaking and mixing in the water solution. The immersion time was 50 hours and the temperature was 60 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 2 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 50% NH at 900 DEG C3/N2Activating for 16 hours under a gas atmosphere, then washing with 1% NaOH aqueous solution and deionized water in sequence until the solution is neutral, performing solid-liquid separation by using a polypropylene bag (with the aperture of 20 microns), and drying the obtained solid for 60 hours at 80 ℃ in vacuum to obtain activated carbon/graphene composite material powder; (4) adding 10 g of Na2S2O3And 50 g of activated carbon/graphene composite material powder are dispersed in 50 ml of water and mixed by an ultrasonic method. The frequency of the ultrasound was 30 kHz, the power density was 800 w, the time was 10 hours and the temperature was 40 ℃. Then, a 30 wt% aqueous solution of sulfuric acid was added to the resulting mixture until the precipitation of sulfur was complete. Adopts a polyethylene bag (with the aperture of 2 microns) for solid-liquid separationAnd washing the solid in deionized water to be neutral, performing solid-liquid separation by using a polyethylene bag (with the aperture of 5 microns), and freeze-drying for 60 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 48: (1) vacuum drying beetroot at 120 deg.C for 2 hr, and pulverizing 300 g beetroot with ultrasonic wave. The ultrasonic frequency is 30 kHz, the power density is 1000 w, the time is 2 h, and the temperature is 60 ℃. The sample after ultrasonic crushing is sieved by a drum sieve, and a 40-mesh sample is respectively washed 3 times by 10% perchloric acid aqueous solution and deionized water. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 2 g of biomass and 100 g of phosphorus and sulfur co-doped graphene are added into 550 ml of ZnCl with the mass percent of 5%2Soaking in ethanol solution, and mixing. The immersion time was 10 hours and the temperature was 20 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 1 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the solid material obtained is 90% NH at 1050 DEG C3/N2Activating for 0.5 hour in gas atmosphere, washing with 5% KOH aqueous solution and deionized water in sequence to be neutral, performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 0.2 micron), and performing vacuum drying on the obtained solid for 45 hours at 85 ℃ to obtain activated carbon/graphene composite material powder; (4) 200 mL of H2S and 100 g of activated carbon/graphene composite material powder are dispersed in 100ml of diethanolamine solution and mixed by an ultrasonic method. The frequency of the ultrasound was 25 kHz, the power density was 1000 w, the time was 30 minutes and the temperature was 60 ℃. Then, 10% SO was introduced into the resultant mixture2/N2Mixing the gas until the sulfur precipitation is complete. And (3) carrying out solid-liquid separation by adopting a polyethylene bag (with the aperture of 10 microns), washing the solid in deionized water to be neutral, carrying out solid-liquid separation by adopting the polyethylene bag (with the aperture of 20 microns), and freeze-drying for 12 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 49: (1) the plum kernel was dried by blowing at 100 ℃ for 36 hours, and then 240 g of the plum kernel was pulverized by ultrasonic waves. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. Directly discharging the ultrasonically crushed sampleSieving with a filter sieve, and respectively using 10% HClO to obtain 80 mesh samples3The S aqueous solution and deionized water were washed 3 times. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 300 g of biomass and 10 g of nitrogen, phosphorus and sulfur co-doped graphene are added into 1000 ml of ZnCl with the mass percentage of 30%2Soaking in ethanol solution, and mixing. The immersion time was 140 hours and the temperature was 40 ℃. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 15 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the obtained solid material is N at 550 DEG C2Activating for 90 hours in atmosphere, and then sequentially using 10% Na2CO3Washing the aqueous solution and deionized water to be neutral, carrying out solid-liquid separation by adopting a polyethylene bag (with the aperture of 2 microns), and carrying out forced air drying on the obtained solid at 90 ℃ for 30 hours to obtain activated carbon/graphene composite material powder; (4) 150 mL of SO2And 20 g of activated carbon/graphene composite powder were dispersed in 100mL of water and mixed by a mechanical stirring method. The time of mechanical stirring was 60 hours at a temperature of 20 ℃. Then introducing H into the mixture2S gas until sulfur precipitation is complete. And (3) performing solid-liquid separation by using a polystyrene bag (with the aperture of 10 microns), washing the solid in deionized water to be neutral, performing solid-liquid separation by using a polystyrene membrane (with the aperture of 20 microns), and performing vacuum drying on the solid at 70 ℃ for 96 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 50: (1) the tobacco rods were naturally dried for 14 days, then 50.0 g of agate balls with a diameter of 1-1.3 cm, 100 g of the tobacco rods were sealed under argon protection in an agate jar, which was then placed on a planetary ball mill and ball milled at 580 revolutions per minute for 2 hours. And taking the agate balls out by using tweezers, sieving the ball-milled samples by using a three-dimensional vibrating screen, and washing the 20-mesh samples by using 5% sulfuric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours; (2) 20 g of biomass and 100 g of phosphorus and boron co-doped graphene are added into 400 ml of H with the mass percent of 80%3PO4And (4) high-speed shearing and mixing in the aqueous solution. At high shearThe time is 30 hours, the temperature is 40 ℃, and the rotating speed is 100 r/min. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 20 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the resulting solid material was activated at 650 ℃ for 75 hours in Ar atmosphere and then successively treated with 10% H2SO4Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and performing forced air drying on the obtained solid at 100 ℃ for 15 hours to obtain activated carbon/graphene composite material powder; (4) 15 g (NH4)2S2O8And 30 g of activated carbon/graphene composite material powder are dispersed in 80mL of deionized water, and are mixed by magnetic stirring. The magnetic stirring time was 80 hours and the temperature was 40 ℃. Then, 60 wt% aqueous nitric acid was added to the resulting mixture until the sulfur precipitation was complete. And (3) carrying out solid-liquid separation by using a polyethylene bag (with the aperture of 0.2 micron), washing the solid in deionized water to be neutral, carrying out solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and carrying out forced air drying on the solid at 100 ℃ for 60 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 51: (1) the hazelnut shells were naturally dried for 3 days, then 1500.0 g of zirconia balls with a diameter of 3-8 mm, 200 g of hazelnut shells were sealed under nitrogen protection into a zirconia ball mill pot, which was then placed on a planetary ball mill and ball milled at 300 revolutions per minute for 30 hours. And (3) taking out the zirconia balls by using tweezers, sieving the ball-milled samples by using an ultrasonic vibration sieve, and washing the 50-mesh samples by using 5% hydrochloric acid water solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polypropylene membrane (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 24 hours; (2) 350 g of biomass and 10 g of nitrogen, sulfur and boron co-doped graphene are added into 200 ml of ZnCl with the mass percent of 400%2And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 1 hour, the temperature is 60 ℃, and the rotating speed is 3000 r/min. The solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 5 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material for 50 hours in a helium atmosphere at 750 ℃, and then sequentially using 50% K2CO3Washing the aqueous solution and deionized water to be neutral, performing solid-liquid separation by using a polystyrene bag (with the aperture of 10 microns), and performing forced air drying on the obtained solid at 110 ℃ for 8 hours to obtain activated carbon/graphene composite material powder; (4) 30 g (NH)4)2S and 60 g of activated carbon/graphene composite material powder are dispersed in 30 mL of deionized water and are mixed by mechanical stirring. The time of mechanical stirring was 30 hours and the temperature was 60 ℃. Then, 10 wt% aqueous hydrochloric acid was added to the resulting mixture until the precipitation of sulfur was complete. And (3) performing solid-liquid separation by using a polystyrene bag (with the aperture of 0.2 micrometer), washing the solid in deionized water to be neutral, performing solid-liquid separation by using a polystyrene membrane (with the aperture of 1 micrometer), and performing forced air drying on the solid at 120 ℃ for 2 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 52: (1) the kenaf stalk cores are naturally dried for 30 days, then 500.0 g of alumina ball milling balls with the diameter of 8-15 mm and 300 g of kenaf stalk cores are sealed in an agate ball milling tank under the protection of air, and then the ball milling tank is placed on a planetary ball mill and is ball milled for 60 hours at the rotating speed of 100 revolutions per minute. And (3) taking out the alumina ball by using a pair of tweezers, sieving the ball-milled sample by using an ultrasonic vibration sieve, and washing the 80-mesh sample by using 30% hydrochloric acid water solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (aperture is 2 microns), and the obtained solid is dried by air blast for 1 hour at 120 ℃; (2) 150 g of biomass and 10 g of phosphorus-sulfur-boron co-doped graphene are added into 800 ml of ZnCl with the mass percent of 80%2And (4) high-speed shearing and mixing in the aqueous solution. The high-speed shearing time is 56 hours, the temperature is 20 ℃, and the rotating speed is 1500 rpm. The solid-liquid separation is realized by adopting a polypropylene bag (the aperture is 10 microns), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) the obtained solid material is NH at 850 DEG C3Activating for 40 hours in atmosphere, and then sequentially using 10% CH3Washing the COOH aqueous solution and deionized water to be neutral, performing solid-liquid separation by adopting a polystyrene membrane (with the aperture of 10 microns), and performing forced air drying on the obtained solid at 120 ℃ for 2 hours to obtain activated carbon/graphene composite material powder; (4) dispersing 20 g of sulfur powder and 10 g of activated carbon/graphene composite material powder in 10 ml of n-butyl alcoholMixing by an ultrasonic method. The frequency of the ultrasound was 20 kHz, the power density was 500 w, the time was 30 hours and the temperature was 20 ℃. The resulting mixture was reacted at 100 ℃ for 96 hours, then solid-liquid separated using a polypropylene bag (pore size 0.2 microns), and the resulting was washed with n-butanol in ultrasound. The frequency of the ultrasound was 20 kHz, the power density was 500 w, the time was 30 hours and the temperature was 20 ℃. And (3) performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 20 microns), and performing vacuum drying on the solid at 70 ℃ for 96 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 53: (1) cassava stalks are naturally dried for 12 hours, and then 200 g of the cassava stalks are crushed by ultrasonic waves. The ultrasonic frequency is 20 kHz, the power density is 500 w, the time is 28 h, and the temperature is 25 ℃. And sieving the ultrasonically crushed sample by using a high-frequency vibrating screen, and washing the 100-mesh sample by using 30% sulfuric acid aqueous solution and deionized water for 3 times respectively. Solid-liquid separation is carried out by adopting a polystyrene membrane (the aperture is 0.2 micron), and the obtained solid is dried by air blast for 30 hours at the temperature of 80 ℃; (2) 20 g of biomass and 100 g of graphene are stirred and mixed in 50 ml of 10 mass percent KOH aqueous solution. The magnetic stirring time was 5 hours at 20 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in a nitrogen atmosphere at 950 ℃ for 20 hours, then sequentially washing the solid material to be neutral by adopting a 5% oxalic acid water solution and deionized water, carrying out solid-liquid separation by adopting a polypropylene bag (with the aperture of 0.2 micron), and drying the obtained solid at 80 ℃ for 96 hours in vacuum to obtain activated carbon/graphene composite material powder; (4) 100 g of thiourea and 50 g of activated carbon/graphene composite material powder are dispersed in 50 ml of triethylamine and mixed by an ultrasonic method. The frequency of the ultrasound was 30 kHz, the power density was 800 w, the time was 10 hours and the temperature was 40 ℃. The obtained mixture reacts for 60 hours at 200 ℃, then a polypropylene membrane (with the aperture of 1 micron) is adopted for solid-liquid separation, and the obtained mixture is washed by n-valeric acid under ultrasound. The frequency of the ultrasound was 30 kHz, the power density was 800 w, the time was 10 hours and the temperature was 40 ℃. And (3) performing solid-liquid separation by using a polypropylene bag (with the aperture of 10 microns), and performing vacuum drying on the solid at 100 ℃ for 40 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 54: (1) drying the lotus stalks in vacuum at 70 ℃ for 96 hours, and then crushing 200 g of the lotus stalks by ultrasonic waves. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. And sieving the ultrasonically crushed sample by using an airflow sieve, and washing the 40-mesh sample by using 80% phosphoric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 50 hours; (2) 100 g of biomass and 10 g of nitrogen-doped graphene are added into 100ml of K with the mass percentage of 20%2CO3Stirring and mixing the aqueous solution. The time of mechanical stirring was 20 hours and the temperature was 40 ℃. A polyethylene bag (with the aperture of 1 micron) is adopted to realize solid-liquid separation, the solid is left in the bag, and the liquid is thrown out, extruded, pressed out or flowed out; (3) activating the obtained solid material in an argon atmosphere at 1000 ℃ for 10 hours, then sequentially washing the solid material to be neutral by adopting 30% formic acid water solution and deionized water, carrying out solid-liquid separation by adopting a polypropylene membrane (with the aperture of 1 micron), and carrying out forced air drying on the obtained solid at 95 ℃ for 50 hours to obtain activated carbon/graphene composite material powder; (4) 80 g (NH)4)2S2O8And 100 g of activated carbon/graphene composite material powder are dispersed in 100ml of water and mixed by an ultrasonic method. The frequency of the ultrasound was 25 kHz, the power density was 1000 w, the time was 30 minutes and the temperature was 60 ℃. The mixture was reacted at 300 ℃ for 30 hours, then subjected to solid-liquid separation using a polyethylene bag (pore size 2 μm), and washed with o-xylene under ultrasound. The frequency of the ultrasound was 25 kHz, the power density was 1000 w, the time was 30 minutes and the temperature was 60 ℃. And (3) carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and carrying out forced air drying on the solid at 120 ℃ for 2 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 55: (1) vacuum drying the durian peel at 120 ℃ for 2 hours, and then crushing 300 g of the durian peel by adopting ultrasonic waves. The ultrasonic frequency is 30 kHz, the power density is 1000 w, the time is 2 h, and the temperature is 60 DEG C. The sample after ultrasonic crushing is sieved by a drum sieve, and a 40-mesh sample is respectively washed 3 times by 10% perchloric acid aqueous solution and deionized water. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 2 g of biomass and 100 g of phosphorus-doped graphene are ultrasonically mixed in 300 ml of NaOH aqueous solution with the mass percent of 50%. The ultrasonic frequency is 20 KHz, the power density is 500 w, the time is 30 hours, and the temperature is 20 ℃. Solid-liquid separation is realized by adopting a polypropylene bag (with the aperture of 0.2 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in a helium atmosphere at 500 ℃ for 2 hours, then sequentially washing the solid material with 60% trifluoroacetic acid aqueous solution and deionized water to be neutral, carrying out solid-liquid separation by adopting a polyethylene bag (with the aperture of 2 microns), and carrying out forced air drying on the obtained solid at 100 ℃ for 20 hours to obtain activated carbon/graphene composite material powder; (4) 150 g of CS2And 20 g of activated carbon/graphene composite material powder are mixed by a mechanical stirring method. The time of mechanical stirring was 60 hours at a temperature of 20 ℃. The resulting mixture was reacted at 400 ℃ for 20 hours, then subjected to solid-liquid separation using a polyethylene membrane (pore size 5 μm), and the resulting mixture was washed with acetonitrile under mechanical stirring. The time of mechanical stirring was 60 hours at a temperature of 20 ℃. And (3) carrying out solid-liquid separation by using a polyethylene bag (with the aperture of 2 microns), and freeze-drying the solid for 96 hours to obtain sulfur-activated carbon/graphene composite material powder.
Example 56: (1) the pods were dried by air blowing at 100 ℃ for 36 hours and then 240 g of the pods were crushed by ultrasonic waves. The ultrasonic frequency is 25 kHz, the power density is 800 w, the time is 15 h, and the temperature is 40 ℃. Sieving the ultrasonically pulverized sample with a straight-line filter sieve, and respectively using 10% HClO to obtain 80-mesh samples3The S aqueous solution and deionized water were washed 3 times. Performing solid-liquid separation by using a polyethylene film (with the aperture of 1 micron), and performing forced air drying on the obtained solid at the temperature of 100 ℃ for 40 hours; (2) 200 g of biomass, 10 g of boron-doped graphene and 10 g of solid Na2CO3And (4) ultrasonic mixing. The ultrasonic frequency is 25 KHz, the power density is 800 w, the time is 10 hours, and the temperature is 40 ℃. The solid-liquid is realized by adopting a polystyrene film (with the aperture of 2 microns)Separating, leaving the solid in the bag, and throwing out, extruding, pressing out or flowing out the liquid; (3) activating the obtained solid material in a nitrogen atmosphere at 600 ℃ for 5 hours, then sequentially washing the solid material with 1% pyridine water solution and deionized water to be neutral, carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and carrying out forced air drying on the obtained solid at 120 ℃ for 4 hours to obtain activated carbon/graphene composite material powder; (4) 150 g of ethanethiol and 30 g of activated carbon/graphene composite powder were dispersed in isopropanol and mixed with magnetic stirring. The magnetic stirring time was 80 hours and the temperature was 40 ℃. The resulting mixture was reacted at 150 ℃ for 75 hours, then solid-liquid separated using a polystyrene bag (pore size 10 microns), and the resulting solution was washed with n-butanol under magnetic stirring. The magnetic stirring time was 80 hours and the temperature was 40 ℃. And (3) performing solid-liquid separation by adopting a polypropylene membrane (with the aperture of 0.2 micron), and freeze-drying the solid for 60 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 57: (1) the rape straws are naturally dried for 14 days, then 50.0 g of agate balls with the diameter of 1-1.3 cm are ground, 100 g of rape straws are sealed in an agate ball milling tank under the protection of argon, and then the ball milling tank is placed on a planetary ball mill and is ball milled for 2 hours at the rotating speed of 580 revolutions per minute. And taking the agate balls out by using tweezers, sieving the ball-milled samples by using a three-dimensional vibrating screen, and washing the 20-mesh samples by using 5% sulfuric acid aqueous solution and deionized water for 3 times respectively. Performing solid-liquid separation by using a polyethylene film (with the aperture of 0.2 micron), and performing forced air drying on the obtained solid at 70 ℃ for 96 hours; (2) 30 g of biomass and 1 g of sulfur-doped graphene are added into 300 ml of H with the mass percent of 50%3PO4Ultrasonic mixing in the water solution. The ultrasonic frequency is 30 KHz, the power density is 1000 w, the time is 1 hour, and the temperature is 60 ℃. The solid-liquid separation is realized by adopting a polyethylene film (with the aperture of 1 micron), the solid is left in the bag, and the liquid is thrown, extruded, pressed out or flowed out; (3) activating the obtained solid material in nitrogen atmosphere at 800 deg.C for 1 hr, washing with 5% methylamine water solution and deionized water to neutrality, performing solid-liquid separation with polystyrene bag (pore diameter 0.2 μm), and air drying the obtained solid at 110 deg.C for 12 hr to obtain activated carbon/ionGraphene composite powder; (4) 150 g of ethyl sulfide and 60 g of activated carbon/graphene composite material powder are dispersed in ethanolamine and mixed by mechanical stirring. The time of mechanical stirring was 30 hours and the temperature was 60 ℃. The resulting mixture was reacted at 275 ℃ for 45 hours, then subjected to solid-liquid separation using a polystyrene membrane (pore size 20 μm), and the resulting mixture was washed with o-xylene under magnetic stirring. The magnetic stirring time was 5 hours and the temperature was 50 ℃. And (3) carrying out solid-liquid separation by adopting a polyethylene film (with the aperture of 5 microns), and freeze-drying the solid for 10 hours to obtain the sulfur-activated carbon/graphene composite material powder.
Example 58: lithium sulfur battery assembly and performance testing
The sulfur-activated carbon/graphene composite materials prepared in examples 2 and 4, super conductive carbon (super P) and binder PVDF are ground in an agate mortar for 10 minutes according to the mass ratio of 8:1:1, then a certain amount of azomethylpyrrolidone is added, and the grinding is continued for 20 minutes to 1 hour until uniform slurry is obtained. The slurry was coated on 20 micron aluminum foil with a film scraper and vacuum dried at 60 degrees celsius for 24 hours. Then, the dried aluminum foil is punched into an electrode sheet with a diameter of 12 mm by a punching machine. The tablet press is used to press the electrode plate at 8 MP for 2 minutes to enhance the contact of the solid particles with the aluminum foil. And a 2430 type button battery is assembled by taking a metal lithium sheet as a negative electrode, taking a cellgard 2400 porous membrane as a diaphragm and taking stainless steel as a gasket. And placing the buckle battery in a battery testing mold, and testing the cycle performance (the current density is 0.1C and 1C) and the rate performance (the current density is 0.1C, 0.2C,0.5C,1C,2C,10C and 0.1C) of the battery by adopting a blue battery testing system. The impedance of the cell was tested using CHI660 e.
As can be seen from FIG. 8, the material obtained in example 2 has a specific discharge capacity of 1687mAh/g at a current density of 0.1C and a specific discharge capacity of 785 mAh/g after 100 cycles, and has a cycle efficiency of 99.7%. From FIG. 12, it can be seen that the specific capacity of the material is 500mAh/g after the material is cycled for 500 times under the current density of 1.7-2.8V and 1C. The circulation efficiency reaches 99.8 percent. From FIG. 13, it can be seen that the specific capacity of the material is 279mAh/g after the material is cycled for 1000 times under the current density of 1.7-2.8V and 1.5C. The circulation efficiency reaches 99.7 percent. The materials have good cycle performance and can rapidly complete charge and discharge under larger current.
From fig. 10, it can be seen that the first discharge specific capacity of the material obtained in example 4 reaches 1087mAh/g at 1.7-2.8V and 0.1C current density, the first discharge specific capacity is maintained at 785 mAh/g after 100 cycles, and the cycle efficiency reaches 99.8%, indicating that the material has better electrochemical performance.
Example 59: lithium sulfur battery assembly and performance testing
The sulfur-activated carbon/graphene composite material prepared in example 1, super conductive carbon (super P) and a binder PTFE are ground in an agate mortar for 30 minutes according to a mass ratio of 90:5:5, then a certain amount of ethanol is added, and grinding is continued for 20 minutes to 1 hour until uniform slurry is obtained. The slurry was coated on 20 micron aluminum foil with a film scraper and vacuum dried at 60 degrees celsius for 24 hours. Then, the dried aluminum foil is punched into an electrode sheet with a diameter of 12 mm by a punching machine. The tablet press is used to press the electrode plate at 8 MP for 10 minutes to enhance the contact of the solid particles with the aluminum foil. And a 2430 type button battery is assembled by taking a metal lithium sheet as a negative electrode, taking a cellgard 2400 porous membrane as a diaphragm and taking stainless steel as a gasket. And placing the buckle battery in a battery testing mold, and testing the cycle performance (the current density is 0.1C and 1C) and the rate performance (the current density is 0.1C, 0.2C,0.5C,1C,2C,10C and 0.1C) of the battery by adopting a blue battery testing system. The impedance of the cell was tested using CHI660 e.
As can be seen from FIG. 7, the material obtained in example 1 has a first discharge specific capacity of 1101mAh/g under a current density of 1.7-2.8V and 0.1C, and the first discharge specific capacity is maintained at 715mAh/g and the cycle efficiency reaches 99.5% after 100 cycles, which indicates that the material has a better electrochemical performance.
Example 60:
grinding the sulfur-activated carbon/graphene composite material prepared in example 5, super conductive carbon (super P) and sodium diatomate serving as a binder in a mass ratio of 8:1:1 in an agate mortar for 10 minutes, adding a certain amount of deionized water, and continuing grinding for 20 minutes to 1 hour until uniform slurry is obtained. The slurry was coated on 20 micron aluminum foil with a film scraper and vacuum dried at 60 degrees celsius for 24 hours. Then, the dried aluminum foil is punched into an electrode sheet with a diameter of 12 mm by a punching machine. The tablet press is used to press the electrode sheet at 10 MP for 1 minute to enhance the contact of the solid particles with the aluminum foil. And a 2430 type button battery is assembled by taking a metal lithium sheet as a negative electrode, taking a cellgard 2400 porous membrane as a diaphragm and taking stainless steel as a gasket. And placing the buckle battery in a battery testing mold, and testing the cycle performance (the current density is 0.1C, 1C and 10C) and the rate performance (the current density is 0.1C, 0.2C,0.5C,1C,2C,10C and 0.1C) of the battery by adopting a blue battery testing system. The impedance of the cell was tested using CHI660 e.
As can be seen from FIG. 11, the first discharge specific capacity of the material obtained in example 5 reaches 1289mAh/g under the current density of 1.7-2.8V and 0.1C, the first discharge specific capacity is maintained at 420mAh/g after 100 times of cyclic discharge, and the cyclic efficiency reaches 100%, which indicates that the material has better electrochemical performance.
Example 61:
the sulfur-activated carbon/graphene composite material prepared in example 3, super conductive carbon (super P) and a binder PVDF are ground in an agate mortar for 10 minutes according to the mass ratio of 8:1:1, then a certain amount of azomethylpyrrolidone is added, and the grinding is continued for 20 minutes to 1 hour until uniform slurry is obtained. The slurry was coated on a 20 micron aluminum foil with a film scraper and vacuum dried at 60 degrees celsius for 12 hours. Then, the dried aluminum foil is punched into an electrode plate with a diameter of 9 mm by a punching machine. The tablet press is used to press the electrode sheet at 12 MP for 30 seconds to enhance the contact of the solid particles with the aluminum foil. And a 2430 type button battery is assembled by taking a metal lithium sheet as a negative electrode, taking a cellgard 2400 porous membrane as a diaphragm and taking stainless steel as a gasket. And placing the buckle battery in a battery testing mold, and testing the cycle performance (the current density is 0.1C, 1C and 5C) and the rate performance (the current density is 0.1C, 0.2C,0.5C,1C,2C,10C and 0.1C) of the battery by adopting a blue battery testing system. The impedance of the cell was tested using CHI660 e.
As can be seen from FIG. 9, the first discharge specific capacity of the material obtained in example 3 at 1.7-2.8V and 0.1C current density reaches 1231mAh/g, the first discharge specific capacity is maintained at 661mAh/g after 100 cycles, and the cycle efficiency reaches 99.9%, which indicates that the material has better electrochemical performance.

Claims (34)

1. A preparation method of a sulfur-activated carbon/graphene composite material is characterized by comprising the following steps:
(1) pretreating a biomass raw material;
the pretreatment of the biomass raw material comprises one or more than two steps of predrying, crushing, screening, washing, solid-liquid separation and drying;
the biomass raw material comprises one or more than two of agriculture and forestry resources and wastes, light industrial resources and wastes;
(2) mixing the pretreated biomass raw material with graphene and an activating agent to form a solid mixed material;
the graphene is one of pure graphene or heteroatom-doped graphene; the heteroatom-doped graphene comprises one of nitrogen-doped graphene, phosphorus-doped graphene, sulfur-doped graphene, boron-doped graphene, nitrogen-phosphorus-codoped graphene, nitrogen-sulfur-codoped graphene, nitrogen-boron-codoped graphene, phosphorus-sulfur-codoped graphene, phosphorus-boron-codoped graphene, sulfur-boron-codoped graphene, nitrogen-phosphorus-sulfur-codoped graphene, nitrogen-phosphorus-boron-codoped graphene, nitrogen-sulfur-boron-codoped graphene, phosphorus-sulfur-boron-codoped graphene, and nitrogen-phosphorus-sulfur-boron-codoped graphene;
the activating agent comprises KOH, NaOH and ZnCl2、K2CO3、Na2CO3、H3PO4、H2SO4One of (1);
the mixing mode adopts one of dipping, stirring, ultrasonic, high-speed shearing and ball milling;
(3) activating, washing, carrying out solid-liquid separation and drying on the solid mixed material to obtain an activated carbon/graphene composite material;
the activation temperature of the solid material is 350-600 ℃; the activation time is 60-96 h;
washing the activated material by using one of water, water-soluble inorganic acid, water-soluble organic acid, water-soluble inorganic base and water-soluble organic base;
the solid-liquid separation is carried out by using a porous polymer bag or a membrane;
the drying mode is one of freeze drying, blast air or vacuum drying;
(4) compounding the activated carbon/graphene composite material with sulfur to obtain a sulfur-activated carbon/graphene composite material;
the compounding process comprises purification, solid-liquid separation and drying, and any one of the following modes is used for compounding the sulfur and the activated carbon/graphene composite material:
1) the liquid phase impregnation method comprises the following steps:
dispersing a sulfur source in a solvent; the mixing method of the sulfur source and the solvent adopts one of dipping, ultrasonic treatment, stirring, ball milling and high-speed shearing;
secondly, mixing a sulfur source with the activated carbon/graphene composite material, and carrying out solid-liquid separation and drying to obtain the sulfur-activated carbon/graphene composite material; the sulfur-activated carbon/graphene composite material prepared by the liquid-phase impregnation method contains 10-90% of sulfur by mass; the sulfur source in the liquid phase impregnation method comprises thiourea and NaSx、(NH4)2S、(NH4)2S2O8、H2S、NaHSO3、Na2S2O3、Na2SO3、Na2SO4、CS2One of thiol, thioether, sulfone, sulfoxide, thioylide, thiophenol, thio-substituted aldehyde, thio-substituted ketone, thio-substituted amine, thio-substituted alcohol amine, thio-substituted amide, thio-substituted carboxylic acid, derivative of thio-substituted carboxylic acid, sulfur-containing heterocyclic compound, disulfide, polysulfide, isothiocyanate and organic sulfur-containing polymer;
the sulfur-containing organic compound uses an organic solvent as a dispersant, and the sulfur-containing inorganic compound uses an aqueous solution of a surfactant as a dispersant; the proportion of the dispersing agent to the active carbon/graphene composite material is controlled to be 1-100 ml/g;
the organic solvent comprises one of liquid alcohols, liquid amines, liquid alcohol amines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane and acetonitrile;
the surfactant comprises one of quaternary ammonium compound, sulfated oil, higher fatty alcohol sulfate, soaps, aliphatic sulfonate, alkylaryl sulfonate, alkyl naphthalene sulfonate, lecithin, amino acid zwitterionic surfactant, betaine zwitterionic surfactant, fatty glyceride, polyhydric alcohol, polyoxyethylene nonionic surfactant and polyoxyethylene-polyoxypropylene copolymer; the concentration of the surfactant aqueous solution is between 0.0001 mol/L and 0.5 mol/L;
2) the heating and melting method comprises the following steps:
mixing a sulfur source with the activated carbon/graphene composite material for heat treatment to obtain a crude sulfur-activated carbon/graphene composite material; the mixing mode of the sulfur source and the activated carbon/graphene composite material in the heating melting method is one of mechanical mixing and ultrasonic mixing; the mechanical mixing comprises ball milling or stirring;
purifying the crude sulfur-activated carbon/graphene composite material, performing solid-liquid separation, and drying to obtain the sulfur-activated carbon/graphene composite material;
3) the high-energy ball milling method comprises the following steps:
mixing and grinding a sulfur source and an activated carbon/graphene composite material to obtain a crude sulfur-activated carbon/graphene composite material;
purifying the crude sulfur-activated carbon/graphene composite material, performing solid-liquid separation, and drying to obtain the sulfur-activated carbon/graphene composite material;
4) the precipitation method comprises the following steps:
mixing the sulfur source solution with the activated carbon/graphene composite material, adding a precipitator, and carrying out solid-liquid separation, purification and drying;
the mixing mode of the sulfur source and the activated carbon/graphene composite material comprises one of magnetic or mechanical stirring mixing and ultrasonic mixing;
5) the solvothermal process comprises the steps of:
mixing a sulfur source and a solvent with the activated carbon/graphene composite material, carrying out solvothermal reaction, and carrying out solid-liquid separation to obtain a crude sulfur-activated carbon/graphene composite material;
purifying the composite material, performing solid-liquid separation, and drying to obtain a sulfur-activated carbon/graphene composite material;
the frequency of the ultrasonic wave is 20 KHz to 30 KHz, the power density is 500W to 1000W, the time is 10 minutes to 30 hours, and the temperature is 20 ℃ to 60 ℃;
the stirring adopts magnetic force or/and mechanical stirring, the time is 3 hours to 60 hours, and the stirring temperature is 20 ℃ to 60 ℃;
the working temperature of the high-speed shearing is 20-60 ℃; the rotating speed is 50 to 3000 r/min; the shearing time is 0.5 to 72 hours; the dispersant added in the shearing is water;
the dipping time is 2 hours to 144 hours; the impregnation temperature is from 20 ℃ to 60 ℃.
2. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the agriculture and forestry resources and wastes comprise rice hulls, shaddock peels, durian peels, lotus leaves, wheat straws, corn straws, corncobs, jute stalks, hemp stalks, lotus flower stalks, catkin, spartina alterniflora, plant ash, orange peels, bean stalks, melon seed peels, wood sawdust, cotton stalks, cattail wool, droughts, lotus flower stalks, poplar wood chips, waste chaff, pods, cotton stalks, straw, cedar wood chips, rape stalks, pine wood chips, red wood chips, juniper chips, birch wood chips, cedar wood chips, coconut trees, cassava stalks, small eucalyptus wastes, cashew shells, tree wastes, mulberry branches, bamboo woods and processing residues, switchgrass, kenaf stalk cores, poplar and wastes thereof, willow and wastes thereof, elm and wastes thereof, peach trees and wastes thereof, apricot trees and wastes thereof, pear trees and wastes thereof, walnut trees and wastes thereof, albizia julibrissin trees and wastes thereof, hemp stalks and wastes thereof, cotton stalks, waste thereof, waste of pine, pine and wastes thereof, pine, coconut wood and its waste, bamboo shoot shell, palm wood, date wood and its waste, grapevine, Chinese wolfberry stem, sorghum stalk, cypress, ryegrass, violet, eggplant, papaya, reed, aquatic weeds, sorghum shell, aegilops tauschii, pine wood, tobacco stem, walnut shell, apricot kernel, coconut shell, pistachio shell, palm shell, hawthorn kernel, oak shell, peanut shell, water chestnut shell, olive kernel, date kernel, mixed southern hardwood after hydrolysis of plum kernel, chestnut wood and its waste, carbonized apricot kernel, hazelnut shell, chestnut shell, wheat shell, oak sawdust, plant rhizome, wood chip, date kernel, walnut shell, waste tea leaf, beetroot, cotton shell, banana skin, cherry kernel, orange skin, coffee bean pod, cassava skin, vine bud, oil palm shell, larch charcoal, red eucalyptus wood and its waste, sawdust, peanut straw, rubber shell, corn cob, chestnut shell, chrysanthemum gum, etc, One or more of waste pepper straw, oil tea hull, rapeseed, erythrina indica sawdust, bean straw, date palm kernel, rice bran, beet leaf, oat straw, sunflower straw, pine needle, olive branch tamarind, fir tree and waste thereof, teak sawdust, oil palm tree, cotton linter, mulberry bark, paper mulberry bark, grape seed, oat hull, vine sawdust, oak sawdust, algae, sesame straw, potatoes, hemp, chick pea hull, tobacco stem, vine sawdust, plum kernel, palm hull, foot wood, switchgrass;
the light industrial byproduct comprises one or more of alcohol lees, oil meal, white spirit lees, beer lees, vinegar lees, traditional Chinese medicine residues, sweet potato residues, tea/coffee residues, furfural residues, coconut shell residues, sisal residues, antibiotic bacteria residues, papermaking black liquor, bagasse, fermentation bacteria residues, papermaking leftover materials, black liquor soluble residues, fruit and vegetable processing residues, olive residue filter cakes, oil palm shell filter cakes, end product biomass charcoal of refined biomass oil, and biomass cracking residual charcoal.
3. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the pre-drying of the biomass raw material comprises one of natural drying, forced air drying and vacuum drying;
the natural drying time is 1 hour to 30 days.
4. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the crushing of the biomass raw material comprises a mechanical crushing or ultrasonic crushing method; the particle size of the crushed biomass raw material is 20 meshes to 100 meshes; the crushed biomass raw material is screened by adopting one of a three-dimensional vibrating screen, a swinging screen, a mine screen, a linear vibrating screen, an ultrasonic vibrating screen, an airflow screen, a drum screen, a direct discharge filter screen, a checking screen and a high-frequency vibrating screen.
5. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 4, wherein: the mechanical crushing comprises one of ball milling or crushing by a crusher; the ball grinding ball is one of a stainless steel ball, an agate ball, a zirconia ball, an alumina ball or a silicon carbide ball; the diameter of the ball is 1 mm to 15 mm; the ball milling tank is made of stainless steel, agate or zirconia; the ball-material ratio is 15-150: 1; the ball milling speed is as follows: 50 rpm to 580 rpm; the gas is more than one of air, nitrogen, argon or helium; the ball milling time is 0.5 to 72 hours.
6. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the washing of the biomass raw material comprises the steps of using concentrated or diluted inorganic acid and water; the concentrated or dilute mineral acid comprises H2SO4、H3PO4、HNO3、HClO4、HClO3One of S; the mass percentage of the effective components in the inorganic acid is between 1 percent and 98 percent.
7. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: mixing the biomass raw material and the graphene, wherein a dispersing agent is required to be added; the dispersant comprises one of water, an organic solvent, concentrated or diluted inorganic acid, a soluble inorganic alkali aqueous solution, and an organic solution or an aqueous solution of a soluble inorganic salt; the ratio of the dispersing agent to the solid material is controlled between 1 ml/g and 100 ml/g.
8. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 7, wherein: the organic solvent comprises one of liquid alcohol, acetone, diethyl ether and other liquid oxygen-containing organic solvents.
9. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 7, wherein: the concentrated or diluted inorganic acid is H3PO4(ii) a The mass percentage of the effective components in the inorganic acid is between 1 and 85 percent.
10. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 7, wherein: the soluble inorganic base comprises NaOH, KOH and Na2CO3、K2CO3One of (1); the mass percentage of the inorganic base in the soluble inorganic base aqueous solution is 0.5-100%.
11. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 7, wherein: the soluble inorganic salt is ZnCl2(ii) a The mass percentage of the inorganic salt in the soluble inorganic salt water solution is 0.01-43.2%; the mass percentage of the inorganic salt in the soluble inorganic salt organic solution is between 0.01 and 40 percent.
12. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the mass ratio of the biomass raw material to the graphene is 0:10-10: 0; the mass ratio of the total mass of the biomass raw material and the graphene solid material to the activating agent is 1 (0.1-10).
13. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the mass percentage of the active components in the activator is 1-98%.
14. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: gas is required to be introduced in the activation process in the step (3), and the introduced gas is one of nitrogen, argon, helium and ammonia; the ammonia gas is pure ammonia gas or a mixed gas of the ammonia gas and inert gas; the volume fraction of ammonia in the ammonia gas mixture is 1-99%; the inert gas comprises one of nitrogen, argon and helium.
15. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: in the washing process in the step (3), the water-soluble inorganic acid contains H2SO4、H3PO4、HCl、HNO3、HClO4、HClO3One of S; the mass percentage of the effective components in the water-soluble inorganic acid is 1-98%;
the water-soluble inorganic base comprises NaOH, KOH and Na2CO3、NH3·H2O、K2CO3One of (1); the mass percentage of the inorganic base in the water-soluble inorganic base aqueous solution is 0.5-50%;
the water-soluble organic acid comprises one of water-soluble carboxylic acid and derivatives thereof, water-soluble sulfonic acid and derivatives thereof, water-soluble sulfinic acid and derivatives thereof, and water-soluble thiocarboxylic acid and derivatives thereof; the mass percentage of the effective components in the water-soluble organic acid is 1-60%;
the water-soluble organic alkali comprises one of water-soluble amine compounds, water-soluble alkali metal salts of alcohols, water-soluble alkaloids and pyridine; the mass percentage of the effective components in the water-soluble organic alkali is 1.5-65%.
16. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the reaction temperature of a liquid phase impregnation method in compounding the activated carbon/graphene composite material and sulfur is 20-100 ℃; the reaction time is 0.5 to 144 hours.
17. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the sulfur-activated carbon/graphene composite material prepared by the heating and melting method has the sulfur content of 10-90% by mass; the sulfur source in the heat melting process comprises one of thiourea, solid thiol, solid thioether, solid sulfone, solid sulfoxide, solid thioylide, solid thiophenol, solid thio-substituted aldehyde, solid thio-substituted ketone, solid thio-substituted amine, solid thio-substituted amide, solid thio-substituted carboxylic acid, derivative of solid thio-substituted carboxylic acid, solid thio-containing heterocyclic compound, solid organic disulfide, solid organic polysulfide, solid isothiocyanate, and solid organic sulfur-containing polymer.
18. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: in the heating melting method, the heating temperature of the sulfur filling of the activated carbon/graphene is 100-1000 ℃, the heating time is 0.5-96 hours, and the protective gas is one of nitrogen, argon and helium, so that the crude sulfur-activated carbon/graphene composite material is obtained.
19. The method of preparing a sulfur-activated carbon/graphene composite material of claim 18, wherein: in the heating melting method, the purification method of the crude sulfur-activated carbon/graphene composite material is one of heat treatment or washing;
the heat treatment temperature is 200 ℃ to 500 ℃, and the heating time is 0.5 hour to 96 hours; the protective gas is one of nitrogen, argon and helium;
the solvent used for washing comprises one of water, liquid alcohols, liquid amines, liquid alcohol amines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane and acetonitrile; one of mechanical stirring and ultrasonic is used in the washing process.
20. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the sulfur-activated carbon/graphene composite material prepared by the high-energy ball milling method has the sulfur content of 10-90% by mass; the sulfur source in the high-energy ball milling method comprises one of thiourea, thiol, thioether, sulfone, sulfoxide, sulfur ylide, thiophenol, sulfur-substituted aldehyde, sulfur-substituted ketone, sulfur-substituted amine, sulfur-substituted amide, sulfur-substituted carboxylic acid, derivative of sulfur-substituted carboxylic acid, sulfur-containing heterocyclic compound, disulfide, polysulfide, isothiocyanate and organic sulfur-containing polymer.
21. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: in the high-energy ball milling method, the dispersant used in ball milling is one of liquid sulfur source, water and organic solvent; the ratio of the dispersing agent to the solid mixture is 1-100 ml/g;
the organic solvent comprises one of water, liquid alcohols, liquid amines, liquid alcohol amines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane and acetonitrile.
22. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the crude sulfur-activated carbon/graphene composite material prepared by the high-speed ball milling method is purified by adopting a washing mode, and a solvent used in washing comprises one of liquid alcohols, liquid amines, liquid alcohol amines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane and acetonitrile;
the washing process uses one of mechanical/magnetic stirring and ultrasound.
23. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the sulfur-activated carbon/graphene composite material prepared by the precipitation method has the sulfur content of 10-90% by mass; the sulfur source in the precipitation process comprises NaSx、(NH4)2S、(NH4)2S2O8、NaHSO3、Na2S2O3、Na2SO3、H2S、Na2SO4、SO2、SO3One kind of (1).
24. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: in the precipitation method, a sulfur source is mixed with the activated carbon/graphene composite material, and a dispersing agent is added;
the dispersant for mixing the sulfur source with the activated carbon/graphene composite material is water or alcamines; the ratio of dispersant to solid mixture is between 1 ml/g and 100 ml/g.
25. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the precipitant comprises hydrochloric acid, sulfuric acid, nitric acid and H2S、SO2、SO3One of (1); the mass percentage of the effective components in the inorganic acid is between 1% and 98%;
said H2S、SO2、SO3The volume percentage of the effective component in the composition is between 1% and 100%; the other component is one of nitrogen, argon and helium.
26. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: in the precipitation method, the crude sulfur-activated carbon/graphene composite material is purified in a washing mode, and the used solvent is water;
the washing mode of the crude sulfur-activated carbon/graphene composite material comprises one of stirring and ultrasonic treatment.
27. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the mass percentage of sulfur in the sulfur-activated carbon/graphene composite material prepared by the solvothermal method is between 10% and 90%; the sulfur source in the solvothermal process comprises NaSx、(NH4)2S、(NH4)2S2O8、H2S、NaHSO3、Na2S2O3、Na2SO3、Na2SO4、CS2One of thiol, thioether, sulfone, sulfoxide, thioylide, thiophenol, thio substituted aldehyde, thio substituted ketone, thio substituted amide, thio substituted carboxylic acid, derivative of thio substituted carboxylic acid, thio containing heterocyclic compound, disulfide, polysulfide, isothiocyanate, organic sulfur containing polymer.
28. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the solvent used in the solvothermal method comprises one of water, liquid alcohols, liquid amines, liquid alcohol amines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, chloroform, dichloromethane and acetonitrile.
29. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: the reaction temperature of the solvothermal reaction is between 80 and 400 ℃; the reaction time is between 1 hour and 96 hours.
30. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: in the solvothermal method, the crude sulfur-activated carbon/graphene composite material is purified by adopting a washing mode, and a solvent used for washing comprises one of water, liquid alcohols, liquid amines, liquid alcamines, liquid ketones, liquid ethers, liquid esters, liquid carboxylic acids, liquid aldehydes, liquid heterocyclic compounds, liquid sulfones, liquid sulfoxides, liquid amides, benzene, toluene, carbon tetrachloride, carbon disulfide, o-xylene, p-xylene, m-xylene, N-methylpyrrolidone, chloroform, dichloromethane and acetonitrile;
and one of magnetic force/mechanical stirring and ultrasonic wave is adopted in the washing process of the crude sulfur-activated carbon/graphene composite material.
31. The method of preparing a sulfur-activated carbon/graphene composite material of claim 30, wherein: the frequency of the ultrasonic wave is 20 KHz to 30 KHz, the power density is 500W to 1000W, the time is 10 minutes to 30 hours, and the temperature is 20 ℃ to 60 ℃.
32. The method of preparing a sulfur-activated carbon/graphene composite material of claim 30, wherein: the stirring adopts magnetic force or/and mechanical stirring, the time is 3 hours to 60 hours, and the stirring temperature is 20 ℃ to 60 ℃.
33. The method of preparing a sulfur-activated carbon/graphene composite material according to claim 1, wherein: in the steps (3) and (4), the solid-liquid separation process after adding the dispersing agent or the solid-liquid separation of the washed composite material refers to the use of a porous polymer bag or a porous polymer membrane; the porous polymer is one of polypropylene, polyethylene, polystyrene, polyester or cellulose; the porous polymer bag is beneficial to liquid-solid separation, the solid is left in the bag, and the liquid is thrown, extruded, pressed or flowed out; the average pore size of the porous polymer is 0.2 to 20 microns.
34. The method for preparing a sulfur-activated carbon/graphene composite material according to claim 1 or 3, wherein: in the steps (3) and (4), freeze drying, air blast or vacuum drying is adopted for the composite material solid to obtain composite material powder;
the freeze drying is carried out at-50 ℃ for 10 to 96 hours;
and in the blowing or vacuum drying process, the temperature is 70-120 ℃, and the drying time is 2-96 hours.
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