CN114220953B - C@S/SnS x Biochar composite material and bionic construction method thereof - Google Patents

C@S/SnS x Biochar composite material and bionic construction method thereof Download PDF

Info

Publication number
CN114220953B
CN114220953B CN202111435207.8A CN202111435207A CN114220953B CN 114220953 B CN114220953 B CN 114220953B CN 202111435207 A CN202111435207 A CN 202111435207A CN 114220953 B CN114220953 B CN 114220953B
Authority
CN
China
Prior art keywords
sns
biochar
composite material
biochar composite
drying
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111435207.8A
Other languages
Chinese (zh)
Other versions
CN114220953A (en
Inventor
王彩薇
杜江昊
贺桂铭泉
龚聪聪
杨郭超
黄志航
田新宇
肖渠成
杨夏钰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Aeronautical University
Original Assignee
Xian Aeronautical University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Aeronautical University filed Critical Xian Aeronautical University
Priority to CN202111435207.8A priority Critical patent/CN114220953B/en
Publication of CN114220953A publication Critical patent/CN114220953A/en
Application granted granted Critical
Publication of CN114220953B publication Critical patent/CN114220953B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M4/38—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a C@S/SnS x The biological carbon composite material and the bionic construction method thereof, the needle-like tubular biomass is subjected to hydrothermal treatment and heat treatment to obtain biological carbon; the biological carbon and the tin source are subjected to hydrothermal treatment, and the obtained product and the sulfur source are subjected to heat treatment to obtain SnS x Biochar composite; snS (SnS) x Soaking biochar composite material in polysaccharide compound solution, drying, and heat treating the obtained product to obtain carbon coated SnS x Biochar composite; carbon-coated SnS x Adding the biochar composite material into sodium polysulfide solution, then dropwise adding dilute sulfuric acid, and standing to obtain C@S/SnS x Biochar composite. The invention discloses a C@S/SnS x The biochar composite material and the bionic construction method thereof realize the rapid adsorption and conversion capability of polysulfide, improve the capacity of a lithium-sulfur battery, ensure the stability of a composite structure in the circulation process, and reduce the capacity loss caused by structural damage.

Description

C@S/SnS x Biochar composite material and bionic construction method thereof
Technical Field
The invention belongs to the technical field of lithium-sulfur battery electrode preparation methods, and particularly relates to a C@S/SnS x Biochar composite material and its bionic construction method.
Background
The lithium ion battery has been widely applied to the production and life of people due to the characteristics of high energy density, good safety performance and environmental friendliness, and becomes one of the most interesting electrochemical energy storage devices in the future. In particular, with the recent great increase in market demand for electric vehicles and mobile electronic devices, there is a higher demand for rapid and high-capacity storage of lithium batteries. Graphite is used as the negative electrode of the lithium ion battery, and the theoretical specific capacity is only 372 mAh.g -1 This severely limits further capacity improvement. The theoretical specific capacity of sulfur is 4.4 times that of carbon (1673 mAh.g -1 ) And sulfur is abundant in the crust and environment-friendly, so that the research and development of the lithium-sulfur battery can effectively solve the problem of low capacity of the traditional lithium battery, and the lithium-sulfur battery becomes outstanding as a new generation of electrochemical energy storage device. However, polysulfide shuttling effects can occur during the lithium-sulfur battery reaction, resulting in capacity losses. In addition, sulfur and reaction product Li 2 The electrical insulation of S prevents the continued progress of the electrochemical reaction.
Based on the above, the composite structure design for stabilizing the sulfur load can effectively solve the problems of electrical insulation of sulfur, polysulfide solubility and the like, and promote the electrochemical stability of the lithium-sulfur battery. The carbon material is considered as a good conductive carrier, has rich raw materials and easy preparation, and can improve the conductivity of the composite material; metal sulfide SnS x The method has higher ionic conductivity and low lithiation voltage, is favorable for rapidly capturing and converting polysulfide and inhibits the dissolution of the polysulfide in electrolyte.
However, extensive research has shown that, in order to achieve rapid and high capacity storage of lithium-sulfur batteries, snS x SnS in carbon composite structure x The problems of weak binding energy with carbon and unstable structure caused by volume change of sulfur still need to be solved. On the one hand, snS with strong polarity x The surface is mainly Sn-S ionic bond, which is bonded with carbonThe non-polar C-C/C=C bond on the surface of the material has weak bonding capability, so that SnS is greatly reduced x The loading capacity on the carbon surface reduces the bonding strength of the two, is unfavorable for the loading of polysulfide with strong polarity on the surface of the composite structure, increases the dissolution probability of the polysulfide in the electrolyte, and limits the improvement of the cycle stability [ Li, X, G.Guo, N.Qin, et al, snS ] 2 /TiO 2 nanohybrids chemically bonded on nitrogen-doped graphene for lithium-sulfur batteries:Synergy of vacancy defects and heterostructures,Nanoscale 10(2018)15505-15512.]. On the other hand, the conversion of sulfur and lithium sulfide during the reaction brings about a large volume change, which makes it necessary for the composite structure to have a strong structural stability [ Yang, w., yang, a.song., et al, 3D interconnected porous carbon nanosheets/carbon nanotubes as apolysulfide reservoir for high performance lithium-sulfur batteries, nanoscales 10 (2018) 816-824.]. While SnS x Binding to carbon does not alleviate SnS x The volume expansion during lithiation and polysulfide conversion causes destruction of the composite structure and loss of capacity during cycling.
In view of the foregoing, it is highly desirable to provide a composite structural design that stabilizes the sulfur load to address the capacity enhancing stability problem of lithium-sulfur batteries.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a C@S/SnS x The biochar composite material and the bionic construction method thereof can realize the rapid adsorption and conversion capability of polysulfide, improve the capacity of a lithium-sulfur battery, ensure the stability of a composite structure in the circulating process, reduce the capacity loss caused by structural damage, and solve the problems of unstable sulfur-loaded composite structure and unstable electrochemical performance in the prior art.
The technical scheme adopted by the invention is that a C@S/SnS x The bionic construction method of the biochar composite material comprises the following steps:
s1: adding 50mL of acid mixed solution into 1.0 g-4.0 g needle-like tubular biomass, uniformly stirring, transferring to a hydrothermal reaction kettle, reacting for 2-24 h at 140-180 ℃, and carrying out suction filtration and drying on the obtained product to obtain low-carbonization biochar;
s2: transferring the low-carbonization biochar obtained in the step S1 into a tube furnace, heating to 800-1000 ℃ under a mixed atmosphere, preserving heat for 1-6 h, and cleaning and drying the obtained product to obtain the biochar;
s3: the biochar obtained in S2 is mixed with an organotin source in a ratio of 1: (0.2-0.6), adding 50mL of acetone, uniformly mixing, transferring to a hydrothermal reaction kettle, reacting for 2-24 h at 160-200 ℃, filtering and drying the obtained product to obtain SnO 2 Biochar composite;
s4: snO obtained by S3 2 Biochar composite and sulfur source at 1: (0.38-0.64) mass ratio is placed in a tube furnace, and the sulfur source is placed in SnO 2 Heating to 500-700 ℃ under vacuum condition between the biochar composite material and the furnace door of the tubular furnace, and preserving heat for 1-3 h to obtain SnS x The range of x is 1-2;
s5: snS obtained by S4 x Placing the biochar composite material into 100mL of polysaccharide compound aqueous solution, soaking for 0.5-12 h, and drying the obtained product to obtain polysaccharide coated SnS x Biochar composite;
s6: coating the polysaccharide obtained in S5 with SnS x Transferring the biochar composite material into a tube furnace, heating to 400-600 ℃ under a mixed atmosphere, and preserving heat for 1-3 h to obtain the carbon-coated SnS x Biochar composite;
s7: coating the carbon obtained in S6 with SnS x Gradually adding the biochar composite material into 50mL of sodium polysulfide solution containing 0.1 g-10.0 g of sodium polysulfide, stirring for 10min-20min, then dripping 1 mL-10 mL of dilute sulfuric acid, standing for 12 h-24 h, washing the obtained product with water, and drying to obtain C@S/SnS x Biochar composite.
Further, in S1, the needle-like tubular biomass includes: any one of Albizia tree fluff, fructus Persicae fluff, radix et caulis Opuntiae Dillenii thorn, folium Cedar, folium et cacumen Sabinae chinensis, folium et cacumen Arhat, and folium Cypress.
Further, in S1, the acid mixed solution is formed by mixing citric acid, malic acid and grape acid according to the molar ratio of (0.2-0.4): (0.1-0.7): (0.1-0.9); the concentration of the acidic mixed solution is 1 mol/L-10 mol/L.
Further, in S2, the mixed atmosphere is composed of argon and nitrogen; the nitrogen accounts for 10-40% of the mixed atmosphere by volume.
Further, in S3, the organic selenium source includes: any one to any three of tributyltin, triphenyltin, triethyltin acetate, triphenyltin acetate and dioctyltin.
Further, in S4, the sulfur source includes any one to any three of ethanethiol, thiophenol, ethanesulfide, phenylsulfide, and dimethylsulfoxide.
Further, in S5, the aqueous solution of the polysaccharide compound includes: any one to any three of inulin, gum, psyllium seed gum, pectin, heparin, chondroitin sulfate and hyaluronic acid; the concentration of the polysaccharide compound aqueous solution is 20mol/L-60mol/L.
In S6, the mixed atmosphere is composed of argon and hydrogen, wherein the hydrogen accounts for 5-20% of the mixed atmosphere by volume.
Further, in S7, the concentration of the dilute sulfuric acid is: 1mol/L to 10mol/L.
Another object of the present invention is to provide a method of C@S/SnS x Biochar composite materials, e.g. C@S/SnS as described above x And preparing the biochar composite material by a bionic construction method.
The beneficial effects of the invention are as follows:
(1) The embodiment of the invention successfully constructs the connection between bionics-chemical structure design-interface reaction mechanism-electrochemical performance, and applies the biological basic structure to the preparation process of the composite electrode material, thus deeply exploring the graphitization degree and SnS of conductive carbon x The influence of technological factors such as loading capacity, sugar compound solution impregnation concentration, heat treatment temperature, thiosulfate concentration and the like on the surface property of the composite structure, and the structure and the technology are subjected to feedback regulation and control through electrochemical performance test results and theoretical calculation results, and meanwhile, lithium-sulfur electricity is disclosedPool interface reaction mechanism: in the electrochemical reaction process, the inner layer and the outer layer carbon enhance the electron transmission rate of polysulfide conversion, and the middle layer SnS x Enhancing the capture capacity for polysulfide and the rapid conversion capacity for polysulfide). The association of structure and properties is useful for the deep elucidation of the interfacial reaction mechanism: at C@S/SnS x Under the action of the biochar composite material, the reversible capturing capability and the rapid conversion capability of polysulfide in the electrochemical reaction process are enhanced, and the electrode performance is optimized. The combination of bionics and electrochemistry is beneficial to the intersection and fusion of subjects, and has important research significance and reference value for the design and application of a composite structure.
(2) The embodiment of the invention adopts various needle-like tubular biomasses as carbon sources, and the needle-like tubular biomasses (such as albizia tree fluff, peach fluff, cactus thorns, cedar leaves, juniper leaves, cedar leaves, arhat pine leaves, and qualicarpae leaves) have slender tubular structures. The biomass raw material is natural and pollution-free, the reserve is rich, and the utilization rate of biomass is improved. In addition, the needle-tube-shaped biomass has a smaller tube diameter and a longer tube length than the conventional biomass tubular structure. In the pyrolysis process, the needle tube-shaped structure is not easy to be damaged, and the SnS is ensured x Stability of the composite structure during loading and cycling.
(3) In the embodiment of the invention, an organotin source and an organosulfur source are respectively used as the synthesis SnS x The surface of the biochar prepared by the method contains more organic functional groups (such as organic carboxylic acid, organic alcohol, organic ketone and the like), and the organic functional groups, the organic tin source and the organic sulfur source are polymerized to form more stable macromolecular substances in the reaction process, so that the combination of the organic functional groups and the organic carbon source is tighter in the synthesis process, and SnS in the cycle process of the lithium-sulfur battery is avoided x The falling off of the carbon surface ensures the stability of the structure.
(4) The embodiment of the invention adopts polysaccharide compound aqueous solution as a coated carbon source, and the polysaccharide compound is purified on plants per se, so that the polysaccharide compound is natural and pollution-free. The rich oxygen-containing functional groups on the surface of the polysaccharide compound are favorable for SnS with strong polarity x Surface coating of SnS is enhanced x With polysaccharide compoundsThe binding energy between the biological carbons avoids the damage of the composite structure caused by the volume expansion of sulfur.
(5) According to the embodiment of the invention, the sulfur is loaded in a solution impregnation mode, and the synthesis and diffusion of sulfur in a liquid phase are easier to operate compared with a method of diffusing sulfur after melting, so that sulfur is permeated into the composite structure at low temperature, the loss of sulfur in the loading process is reduced, and the utilization rate of sulfur is improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram of an embodiment C@S/SnS of the invention x A bionic construction method process flow chart of the biological carbon composite material.
FIG. 2 shows a human vascular wall structure and C@S/SnS obtained by the examples of the present invention x Comparison graph of biochar composite structure.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
C@S/SnS x The bionic construction method of the biochar composite material, as shown in figure 1, comprises the following steps:
step 1: placing 1.0 g-4.0 g needle-like tube biomass into a beaker, adding 50mL of mixed solution of citric acid, malic acid and grape acid in a molar ratio of (0.2-0.4) to (0.1-0.7) to (0.1-0.9) into the beaker, uniformly stirring for 10min-20min, transferring the reaction system into a hydrothermal reaction kettle, transferring the hydrothermal reaction kettle into a homogeneous reactor, reacting for 2-24 h at 140-180 ℃ to obtain a reaction solution, filtering the reaction solution with a suction filter, and drying for 12h at 60 ℃ of an oven to obtain low-carbonization biochar.
Needle-like biomass including Albizia tree fluff, fructus Persicae fluff, radix et caulis Opuntiae Dillenii, folium Cedar, folium et cacumen Sabinae chinensis, folium et cacumen Crohn pine or folium Cypress.
In the step, needle-like tubular biomass is subjected to hydrothermal reaction in an acid system, the needle-like tubular biomass still has a tubular structure, the inside of a product is carbonized to a certain extent, a certain number of pores which are uniformly distributed are formed on the surface of the product, and a plurality of organic functional groups such as organic carboxylic acid, organic alcohol, organic ketone and the like are also uniformly formed on the surface of the product, so that the specific surface area of low-carbonized biochar and the polarity of the product are increased, and the uniform loading degree of a selenium source in the subsequent step is increased.
Step 2: the preparation method comprises the steps of carrying out heat treatment on low-carbonization biochar in a tube furnace, controlling the sample to be under the protection of an argon/nitrogen mixed atmosphere, wherein nitrogen accounts for 10% -40% of the mixed atmosphere in volume percent, heating up to 800-1000 ℃ from room temperature at a heating rate of 10-20 ℃/min, preserving heat for 1-6 h, rearranging and combining carbon atoms in the biochar at the temperature to obtain more graphite carbon, gradually reducing the defect content, washing the obtained product with 20mL of hydrochloric acid solution (with the concentration of 5 mol/L) and 50mL of water, carrying out suction filtration on the product for three times, and drying the product in an oven at 60 ℃ for 12h to obtain the biochar.
The nitrogen is introduced into the argon/nitrogen mixed atmosphere to introduce more defects N on the surface of the low-carbonization biochar in the pyrolysis process, so that the electronegativity of the surface of the biochar is enhanced, and the SnS in the subsequent step is facilitated x And the loading of S.
The biochar obtained by the step is still in a porous tubular structure, and the graphitization degree of the inside of the product is higher due to high-temperature treatment and the introduction of the defect N, so that the nitrogen-containing defects and the oxygen-containing defects on the surface of the product are uniformly distributed and have a large number; the surface polarity of the biochar is increased, so that the subsequent selenium source loading is facilitated, and the conductivity is increased.
Step 3: mixing and grinding biochar and an organotin source, wherein the mixing mass ratio of the biochar to the organotin source is 1: (0.2-0.6), adding 50mL of acetone, stirring for 10-20 min, placing in a hydrothermal reaction kettle, transferring into a homogeneous reactor, reacting for 2-24 h at 160-200 ℃ to obtain a reaction solution, filtering the reaction solution with a suction filter, and drying for 12h at 60 ℃ in an oven to obtain SnO 2 Biochar composite.
The organic selenium source includes: any one to any three of tributyltin, triphenyltin, triethyltin acetate, triphenyltin acetate and dioctyltin. When the organic selenium source is formed by mixing any two substances, the mass ratio of the two substances is 1:1; when the organic selenium source is formed by mixing any three substances, the mass ratio of the three substances is 1:1:1.
In the step, the specific surface area of the biochar is larger, the surface polarity is larger, the loading amount of the organotin in the biochar is large and is uniformly distributed in the hydrothermal process, and the combination degree of the organotin and the biochar is high.
Step 4: snO is prepared 2 Heat treating biochar composite material in tubular furnace, and placing sulfur source in SnO according to the gas flow sequence 2 SnO between the biochar composite material and the furnace door of the tube furnace 2 The mass ratio of the biochar composite material to the sulfur source is 1: (0.38-0.64), controlling the sample to be heated from room temperature to 500-700 ℃ at a heating rate of 10-20 ℃/min under vacuum condition, and preserving heat for 1-3 h, wherein sulfur in the sulfur source replaces SnO at the temperature 2 The oxygen in the mixture is obtained to obtain SnS with strong crystallinity x X is in the range of 1-2 to obtain tubular-like biological carbon sheet SnS x Wrapped SnS x Biochar composite.
The sulfur source includes: any one to any three of ethanethiol, thiophenol, ethanesulfide, phenylsulfide and dimethyl sulfoxide; when the sulfur source is formed by mixing any two substances, the mass ratio of the two substances is 1:1; when the sulfur source is formed by mixing any three substances, the mass ratio of the three substances is 1:1:1.
Due to the decomposition of sulfur source during the pyrolysis of this step, a large amount of sulfur source is producedTo avoid loss of sulfur vapor during pyrolysis and the sulfur source in SnO 2 Uneven distribution of biochar composite material, the reaction system of this step is carried out under vacuum condition.
Step 5: snS is to be processed x Placing the biochar composite material into 100mL of polysaccharide compound aqueous solution with the concentration of 20-60 mol/L, soaking for 0.5-12 h, and drying the obtained product in a freeze dryer at minus 40-60 ℃ for 12-24 h to obtain polysaccharide coated SnS x Biological carbon composite material and polysaccharide coated SnS x The innermost layer of the biochar composite material is tubular-like biochar, and the middle layer is SnS x The outermost layer is a polysaccharide compound.
The aqueous polysaccharide compound solution comprises: any one to any three of inulin, gum, psyllium seed gum, pectin, heparin, chondroitin sulfate and hyaluronic acid; when the polysaccharide compound is formed by mixing any two substances, the mass ratio of the two substances is 1:1; when the polysaccharide compound is formed by mixing any three substances, the mass ratio of the three substances is 1:1:1.
Step 6: coating polysaccharide with SnS x Transferring the biochar composite material into a tubular furnace for heat treatment, controlling the volume percentage of hydrogen in the mixed atmosphere to be 5-20% by controlling the sample under the argon/hydrogen mixed atmosphere, heating from room temperature to 400-600 ℃ at the heating rate of 10-20 ℃/min, preserving heat for 1-3 h, performing heat treatment on the polysaccharide compound, performing dehydration condensation reaction on oxygen-containing functional groups in the polysaccharide compound to generate macromolecular organic matters, reducing defects, improving graphitization degree and obtaining the carbon-coated SnS x Biochar composite.
The effect of hydrogen in the mixed atmosphere is to introduce a reducing atmosphere to prevent SnS x Oxidized during the reaction.
Step 7: coating carbon with SnS x Gradually adding the biochar composite material into 50mL of sodium polysulfide solution, continuously stirring for 10-20 min, slowly dripping 1-10 mL of dilute sulfuric acid with the concentration of 1-10 mol/L until a large amount of yellow precipitation appears, and standing for 12-24 h, wherein SnS is generated x And polysulfide both have strong polarity, yellow precipitateSulfur is adsorbed to carbon-coated SnS x Inside the biological carbon composite material, finally, the carbon after absorbing sulfur is coated with SnS x Washing the biochar composite material with water for three times, and drying at minus 40-60 ℃ for 12-24 h in freeze drying to obtain C@S/SnS x Biochar composite.
The preparation scheme of the sodium polysulfide solution is as follows: 0.1 g-10.0 g sodium polysulfide is dispersed in 50mL water and stirred for 10min-20min to prepare sodium polysulfide solution.
Carbon-coated SnS x Dripping the biochar composite material into sodium polysulfide solution, and then dripping dilute sulfuric acid to separate out a large amount of yellow sediment S, wherein S is coated with SnS by carbon x The biochar composite material is adsorbed to the inside.
The reaction process of adding dilute sulfuric acid into sodium polysulfide to generate yellow precipitate S is as follows: s is S 2 O 3 2- +2H + →S↓+H 2 SO 3 。
C@S/SnS obtained by the invention x The bionic structure can effectively stabilize the load of sulfur, solve the problems of electrical insulation of sulfur, polysulfide solubility and the like, promote the electrochemical stability of a lithium-sulfur battery, realize the rapid adsorption and conversion capability of polysulfide, promote the capacity of the lithium-sulfur battery, ensure the stability of the composite structure in the circulation process and reduce the capacity loss caused by structural damage.
Example 1
(1) Taking 1.0g of albizia julibrissin tree fluff, putting the albizia julibrissin tree fluff into a beaker, adding 50mL of a mixed solution (the concentration is 1 mol/L) of citric acid, malic acid and grape acid, uniformly stirring for 10min, putting the mixture into a hydrothermal reaction kettle, uniformly reacting for 2h (without stirring) at 180 ℃ to obtain a reaction solution, filtering the reaction solution by a suction filter, and drying the reaction solution at 60 ℃ for 12h in an oven to obtain the low-carbonization biochar.
(2) The low-carbonization biochar is subjected to heat treatment in a tube furnace, a sample is controlled to be heated from room temperature to 800 ℃ at a heating rate of 10 ℃/min under the protection of argon/nitrogen mixed gas (the nitrogen accounts for 10%), the product is subjected to heat treatment for 1h at 800 ℃, 20mL of hydrochloric acid (the concentration is 5 mol/L) and 50mL of water are used for cleaning and suction filtration for three times, and the biochar is obtained by drying for 12h in an oven at 60 ℃.
(3) Mixing tributyltin and biochar, grinding (mixing mass ratio is 0.3:1), adding 50mL of acetone, stirring for 10min, placing in a hydrothermal reaction kettle, uniformly reacting at 180 ℃ for 24h (stirring) to obtain a reaction solution, filtering the reaction solution with a suction filter, and drying at 60 ℃ for 12h in an oven to obtain SnO 2 Biochar composite.
(4) SnO is prepared 2 Heat treating biochar composite material in a tube furnace, and placing ethanethiol in SnO according to the gas flow sequence 2 Before biochar composite material, snO 2 The mass ratio of the biochar composite material to the ethanethiol is 1:0.38. controlling the sample to be heated from room temperature to 600 ℃ at a heating rate of 10 ℃/min under vacuum condition, and performing heat treatment for 1h at 600 ℃ to obtain SnS x Biochar composite.
(5) SnS is to be processed x Soaking biochar composite material in 100mL inulin solution (20 mol/L concentration) for 30min, taking out, and drying at-40deg.C in freeze dryer for 12 hr to obtain polysaccharide coated SnS x Biochar composite.
(6) Coating polysaccharide with SnS x The biological carbon composite material is heat treated in a tube furnace, the sample is controlled under the condition of argon/hydrogen, the hydrogen ratio is 5 percent, the temperature is increased from room temperature to 400 ℃ at the heating rate of 10 ℃/min, and the heat treatment is carried out for 1h at the temperature, so as to obtain the carbon-coated SnS x Biochar composite.
(7) Dispersing 0.1g sodium sulfide in 50mL water solution, stirring for 10min to prepare sodium polysulfide solution, and coating SnS with carbon x Gradually adding the biochar composite material into sodium polysulfide solution, continuously stirring for 10min, slowly dripping 1mol/L dilute sulfuric acid (volume is 10 mL) until a large amount of yellow precipitate appears, standing for 12h, dripping the dilute sulfuric acid with volume of 10mL, washing the mixed solution with water for three times, and drying at minus 40 ℃ for 12h in freeze drying to obtain C@S/SnS x Biochar composite.
As shown in FIG. 2, C@S/SnS prepared in this example x Biochar composite material relative toThe biological carbon layer of the human vascular wall structure corresponds to the fiber layer structure of the inner layer of the human vascular wall, and plays a role in supporting and transmitting; its SnS x And the S layer corresponds to the fiber and amorphous matrix layer in the middle layer of the vascular wall of the human body and plays a role in polysulfide adsorption; the porous carbon layer corresponds to the elastic fiber layer on the outer layer of the vascular wall of the human body, is generally loose, so that the composite structure is protected from being damaged easily in the circulating process, and the diffusion of lithium ions on the surface of the composite structure is facilitated.
Example 2
(1) Taking 4.0g of peach fluff in a beaker, adding 50mL of mixed solution (with the concentration of 10 mol/L) of citric acid, malic acid and grape acid, controlling the molar ratio of the citric acid, the malic acid and the grape acid to be 0.4:0.2:0.9, uniformly stirring for 20min, placing in a hydrothermal reaction kettle, uniformly reacting for 5h (without stirring) at 140 ℃ to obtain a reaction solution, filtering the reaction solution by a suction filter, and drying for 8h at 80 ℃ in an oven to obtain the low-carbonization biochar.
(2) The low-carbonization biochar is subjected to heat treatment in a tube furnace, the sample is controlled under the protection of argon/nitrogen mixed gas, the nitrogen accounts for 40 percent, the temperature is raised to 900 ℃ from room temperature at the heating rate of 10 ℃/min, the heat treatment is carried out for 6 hours at 900 ℃, the product is washed with 20mL of hydrochloric acid (the concentration is 5 mol/L) and 50mL of water, the product is subjected to suction filtration for three times, and the product is dried for 12 hours at 60 ℃ in an oven to obtain the biochar.
(3) Mixing and grinding triphenyltin and biochar (mass ratio of 0.6:1), adding 50mL of acetone, stirring for 20min, placing in a hydrothermal reaction kettle, uniformly reacting at 200 ℃ for 2h (stirring) to obtain a reaction solution, filtering the reaction solution with a suction filter, and drying at 60 ℃ for 12h in an oven to obtain SnO 2 Biochar composite.
(4) SnO is prepared 2 Heat treating biochar composite material in a tube furnace, and placing dimethyl sulfoxide in SnO according to the gas flow sequence 2 Before biochar composite material, snO 2 The mass ratio of the biochar composite material to the dimethyl sulfoxide is 1:0.64, controlling the sample to be heated from room temperature to 600 ℃ at a heating rate of 10 ℃/min under vacuum condition, and performing heat treatment at 600 ℃ for 2 hours to obtain SnS x Biochar composite.
(5) SnS is to be processed x Soaking biochar composite material in 100mL hyaluronic acid aqueous solution (60 mol/L concentration) for 120min, taking out, and drying at-60deg.C in freeze dryer for 24 hr to obtain polysaccharide coated SnS x Biochar composite.
(6) Coating polysaccharide with SnS x The biological carbon composite material is heat treated in a tube furnace, the sample is controlled under the condition of argon/hydrogen, the hydrogen ratio is 20 percent, the temperature is increased from room temperature to 600 ℃ at the heating rate of 10 ℃/min, and the heat treatment is carried out for 3 hours at the temperature, so as to obtain the carbon-coated SnS x Biochar composite.
(7) 10.0g of sodium sulfide is dispersed in 50mL of water solution and stirred for 20min to prepare sodium polysulfide solution, and carbon is coated with SnS x Gradually adding the biochar composite material into sodium polysulfide solution, continuously stirring for 20min, slowly dripping 5mol/L dilute sulfuric acid (volume of 2 mL) until a large amount of yellow precipitate appears, standing for 24h, washing the mixed solution with water for three times, and drying at-60deg.C for 24h in freeze drying to obtain C@S/SnS x Biochar composite.
Example 3
(1) Taking 3.0g of cactus, putting the thorns into a beaker, adding 50mL of mixed solution (the concentration is 6 mol/L) of citric acid, malic acid and grape acid, uniformly stirring for 15min, putting the mixture into a hydrothermal reaction kettle, uniformly reacting for 24h at 160 ℃ (without stirring) to obtain a reaction solution, filtering the reaction solution by a suction filter, and drying the reaction solution for 10h at 70 ℃ in an oven to obtain the low-carbonization biochar.
(2) The low-carbonization biochar is subjected to heat treatment in a tube furnace, the sample is controlled under the protection of argon/nitrogen mixed gas, the nitrogen accounts for 20 percent, the temperature is raised to 1000 ℃ from room temperature at the heating rate of 10 ℃/min, the heat treatment is carried out for 3 hours at 1000 ℃, the product is washed with 20mL of hydrochloric acid (the concentration is 5 mol/L) and 50mL of water, the product is subjected to suction filtration for three times, and the product is dried for 12 hours at 60 ℃ in an oven to obtain the biochar.
(3) Mixing and grinding triphenyltin acetate and biochar (the mass ratio is 0.2:1), adding 50mL of acetone, stirring for 15min, placing into a hydrothermal reaction kettle, and uniformly reacting at 160 ℃ for 24h (stirring) to obtain a reactionFiltering the solution after reaction by a suction filter, and drying the solution for 12 hours at 60 ℃ in an oven to obtain SnO 2 Biochar composite.
(4) SnO is prepared 2 Heat treating biochar composite material in tubular furnace, and placing phenylsulfide in SnO according to the gas flow sequence 2 Before biochar composite material, snO 2 The mass ratio of the biochar composite material to the phenylsulfide is 1:0.5, controlling the sample to be heated from room temperature to 700 ℃ at a heating rate of 10 ℃/min under vacuum condition, and performing heat treatment for 3 hours at 700 ℃ to obtain SnS x Biochar composite.
(5) SnS is to be processed x Soaking biochar composite material in 100mL pectin water solution (40 mol/L concentration) for 7 hr, taking out, and drying at-50deg.C in freeze dryer for 20 hr to obtain polysaccharide coated SnS x Biochar composite.
(6) Coating polysaccharide with SnS x The biological carbon composite material is heat treated in a tube furnace, the sample is controlled under the condition of argon/hydrogen, the hydrogen ratio is 10 percent, the temperature is increased from room temperature to 500 ℃ at the heating rate of 10 ℃/min, and the heat treatment is carried out for 2 hours at the temperature, so as to obtain the carbon-coated SnS x Biochar composite.
(7) Dispersing 5.0g of sodium sulfide in 50mL of water solution and stirring for 15min to prepare sodium polysulfide solution, and coating SnS with carbon x Gradually adding biochar composite material into sodium polysulfide solution, stirring for 15min, slowly dripping 8mol/L dilute sulfuric acid (volume of 2.5 mL) until a large amount of yellow precipitate appears, standing for 18h, washing the mixed solution with water three times, and freeze drying at-50deg.C for 20h to obtain C@S/SnS x Biochar composite.
Example 4
(1) Taking 3.0g of Podocarpus arpus leaf in a beaker, adding 50mL of mixed solution (with concentration of 8 mol/L) of citric acid, malic acid and grape acid, uniformly stirring for 16min, placing in a hydrothermal reaction kettle, uniformly reacting for 18h at 150 ℃ (without stirring) to obtain a reaction solution, filtering the reaction solution with a suction filter, and drying for 11h at 65 ℃ in an oven to obtain the low-carbonization biochar.
(2) The low-carbonization biochar is subjected to heat treatment in a tube furnace, a sample is controlled to be heated from room temperature to 850 ℃ at a heating rate of 10 ℃/min under the protection of argon/nitrogen mixed gas (the nitrogen accounts for 30%), the product is subjected to heat treatment for 4 hours at 850 ℃, 20mL of hydrochloric acid (the concentration is 5 mol/L) and 50mL of water are used for cleaning and suction filtration for three times, and the biochar is obtained by drying for 12 hours at 60 ℃ in an oven.
(3) Mixing and grinding triethyltin acetate and biochar (the mass ratio is 0.5:1), adding 50mL of acetone, stirring for 12min, placing in a hydrothermal reaction kettle, uniformly reacting at 180 ℃ for 10h (stirring) to obtain a reaction solution, filtering the reaction solution with a suction filter, and drying at 60 ℃ for 12h in an oven to obtain SnO 2 Biochar composite.
(4) SnO is prepared 2 Heat treating biochar composite material in a tube furnace, and placing thiophenol in SnO according to the order of gas flow 2 Before biochar composite material, snO 2 The mass ratio of the biochar composite material to the thiophenol is 1:0.45, controlling the sample to be heated from room temperature to 500 ℃ at a heating rate of 10 ℃/min under vacuum condition, and performing heat treatment for 3 hours at 500 ℃ to obtain SnS x Biochar composite.
(5) SnS is to be processed x Soaking the biochar composite material in 100mL chondroitin sulfate aqueous solution (concentration of 50 mol/L) for 280min, taking out, and drying at-50deg.C in a freeze dryer for 14 hr to obtain polysaccharide coated SnS x Biochar composite.
(6) Coating polysaccharide with SnS x The biological carbon composite material is heat treated in a tube furnace, the sample is controlled under the condition of argon/hydrogen, the hydrogen ratio is 15 percent, the temperature is increased from room temperature to 450 ℃ at the heating rate of 10 ℃/min, and the heat treatment is carried out for 2 hours at the temperature, so as to obtain the carbon-coated SnS x Biochar composite.
(7) Dispersing 8.0g of sodium sulfide in 50mL of water solution and stirring for 15min to prepare sodium polysulfide solution, and coating SnS with carbon x Gradually adding biochar composite material into sodium polysulfide solution, stirring for 12min, slowly dripping 10mol/L dilute sulfuric acid (volume of 1 mL) until a large amount of yellow precipitate appears, standing for 16h, and finally flushing the mixed solution with waterWashing three times and freeze drying at-55deg.C for 17h to obtain C@S/SnS x Biochar composite.
Example 5
(1) Taking 4.0g of the qualit leaves in a beaker, adding 50mL of a mixed solution (the concentration is 4 mol/L) of citric acid, malic acid and grape acid, uniformly stirring for 15min, placing in a hydrothermal reaction kettle, uniformly reacting for 3h (without stirring) at 165 ℃ to obtain a reaction solution, filtering the reaction solution by a suction filter, and drying for 12h at 60 ℃ in an oven to obtain the low-carbonization biochar.
(2) The low-carbonization biochar is subjected to heat treatment in a tube furnace, a sample is controlled to be heated from room temperature to 950 ℃ at a heating rate of 10 ℃/min under the protection of an argon/nitrogen mixed gas (the nitrogen accounts for 25%), the product is subjected to heat treatment for 1.5 hours at 950 ℃, and the product is washed and suction filtered three times by 20mL of hydrochloric acid (the concentration is 5 mol/L) and 50mL of water, and is dried for 12 hours at 60 ℃ in an oven to obtain the biochar.
(3) Mixing and grinding triphenyltin and biochar (mass ratio of 0.6:1), adding 50mL of acetone, stirring for 20min, placing in a hydrothermal reaction kettle, uniformly reacting at 180 ℃ for 24h (stirring) to obtain a reaction solution, filtering the reaction solution with a suction filter, and drying at 60 ℃ for 12h in an oven to obtain SnO 2 Biochar composite.
(4) SnO is prepared 2 Heat treating biochar composite material in a tube furnace, and placing ethyl sulfide in SnO according to the gas flow sequence 2 Before biochar composite material, snO 2 The mass ratio of the biochar composite material to the ethylene sulfide is 1:0.55, controlling the sample to be heated from room temperature to 550 ℃ at a heating rate of 10 ℃/min under vacuum condition, and performing heat treatment for 3 hours at 550 ℃ to obtain SnS x Biochar composite.
(5) SnS is to be processed x Soaking biochar composite material in 100mL heparin water solution (30 mol/L concentration) for 12 hr, taking out, and drying at-40deg.C in freeze dryer for 12 hr to obtain polysaccharide coated SnS x Biochar composite.
(6) Coating polysaccharide with SnS x Thermal treatment of biochar composite material in tubular furnace and controlUnder the condition of argon/hydrogen, the hydrogen ratio of the sample is 18%, the temperature is increased from room temperature to 550 ℃ at the heating rate of 10 ℃/min, and the sample is heat treated for 1h at the temperature to obtain the carbon-coated SnS x Biochar composite.
(7) Dispersing 2.0g of sodium sulfide in 50mL of water solution and stirring for 15min to prepare sodium polysulfide solution, and coating SnS with carbon x Gradually adding biochar composite material into sodium polysulfide solution, stirring for 20min, slowly dripping 2mol/L dilute sulfuric acid until a large amount of yellow precipitate appears, standing for 16 hr, washing the mixed solution with water three times, and freeze drying at-60deg.C for 20 hr to obtain C@S/SnS x Biochar composite.
Example 6
(1) Taking 1.5g of cedar leaves in a beaker, adding 50mL of a mixed solution (the concentration is 7 mol/L) of citric acid, malic acid and grape acid, uniformly stirring for 19min, placing in a hydrothermal reaction kettle, uniformly reacting for 9h at 155 ℃ (without stirring) to obtain a reaction solution, filtering the reaction solution by a suction filter, and drying for 12h at 60 ℃ in an oven to obtain the low-carbonization biochar.
(2) The low-carbonization biochar is subjected to heat treatment in a tube furnace, a sample is controlled to be heated from room temperature to 920 ℃ at a heating rate of 10 ℃/min under the protection of an argon/nitrogen mixed gas (the nitrogen ratio is 15%), the product is subjected to heat treatment for 2 hours at 920 ℃, 20mL of hydrochloric acid (the concentration is 5 mol/L) and 50mL of water are used for cleaning and suction filtration for three times, and the biochar is obtained by drying for 12 hours at 60 ℃ in an oven.
(3) Mixing and grinding dioctyltin and biochar (mass ratio of 0.48:1), adding 50mL of acetone, stirring for 11min, placing in a hydrothermal reaction kettle, uniformly reacting at 185 ℃ for 5h (stirring) to obtain a reaction solution, filtering the reaction solution with a suction filter, and drying at 60 ℃ for 12h in an oven to obtain SnO 2 Biochar composite.
(4) SnO is prepared 2 Heat treating biochar composite material in a tube furnace, and placing ethanethiol in SnO according to the gas flow sequence 2 Before biochar composite material, snO 2 The mass ratio of the biochar composite material to the ethanethiol is 1:0.6,heating the sample from room temperature to 650 ℃ at a heating rate of 10 ℃/min under vacuum condition, and performing heat treatment at 650 ℃ for 2.5h to obtain SnS x Biochar composite.
(5) SnS is to be processed x Soaking biochar composite material in 100mL gum water solution (35 mol/L concentration) for 100min, taking out, and drying at-50deg.C in freeze dryer for 22 hr to obtain polysaccharide coated SnS x Biochar composite.
(6) Coating polysaccharide with SnS x The biological carbon composite material is heat treated in a tube furnace, the sample is controlled under the condition of argon/hydrogen, the hydrogen ratio is 8 percent, the temperature is increased from room temperature to 580 ℃ at the heating rate of 10 ℃/min, and the heat treatment is carried out for 2.2 hours at the temperature, thus obtaining the carbon-coated SnS x Biochar composite.
(7) Dispersing 7.8g of sodium sulfide in 50mL of water solution and stirring for 16min to prepare sodium polysulfide solution, and coating SnS with carbon x Gradually adding the biochar composite material into sodium polysulfide solution, continuously stirring for 17min, slowly dripping 4mol/L dilute sulfuric acid (volume of 2.5 mL) until a large amount of yellow precipitate appears, standing for 20h, washing the mixed solution with water three times, and drying at-52deg.C for 19h in freeze drying to obtain C@S/SnS x Biochar composite.
Example 7
The procedure of example 3 was followed except that the aqueous polysaccharide compound solution of (5) consisted of inulin, psyllium seed gum, and hyaluronic acid in a mass ratio of 1:1:1.
Example 8
The procedure of example 3 was repeated except that the organotin source in (3) was composed of tributyltin, triphenyltin and triethyltin acetate in a mass ratio of 1:1:1.
Example 9
The procedure of example 3 was repeated except that the organotin source in (3) was composed of triphenyltin acetate and dioctyltin in a mass ratio of 1:1.
Example 10
The procedure of example 3 was repeated except that the sulfur source in (4) consisted of ethanethiol, thiophenol, and ethanesulfide in a mass ratio of 1:1:1.
Example 11
The procedure of example 3 was repeated except that the sulfur source in (4) was composed of dimethyl sulfide and dimethyl sulfoxide in a mass ratio of 1:1.
Experimental example
C@S/SnS prepared in examples 1 to 11 x The electrochemical properties of the biochar composite were tested and the test results are shown in table 1.
Table 1 C@S/SnS prepared in examples x Electrochemical performance test results of biochar composite materials
Figure BDA0003381542240000131
As can be seen from the test results of examples 1 to 6, the carbonization temperature of the biochar and the coated carbon is controlled, which is favorable for improving the graphitization degree of the carbon material and the conductivity of the composite electrode; controlling SnS x Will effectively improve SnS x Crystallinity and SnS of (C) x Binding ability to biochar; snS (SnS) x The crystallinity regulation of (2) is beneficial to enhancing the capture capacity of polysulfide; snS (SnS) x The regulation of the binding capacity with biochar is beneficial to ensuring the stability of the composite structure in the circulation process.
From the test results of example 7 and example 3, it can be seen that: selecting a plurality of polysaccharide compounds as carbon sources, wherein the obtained coated carbon has a porous structure, good conductivity and structural stability; the porous structure is favorable for rapid diffusion of lithium ions, good conductivity lays a foundation for rapid transmission of electrons, and good structural stability ensures maintenance of electrode capacity in the circulation process.
From the test results of examples 8, 9 and 3, it is found that the selection of various organotin sources as raw materials is more favorable for the dispersion of tin oxide on the surface of biochar and the combination of the two, and ensures the stability of the composite structure.
As can be seen from the test results of examples 10, 11 and 3, the selection of various sulfur sources as raw materials is more beneficial to controlling the precipitation rate of sulfur, and improving the adsorption quantity of sulfur and the rapid adsorption capacity of the composite material to sulfur.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments. In particular, for system embodiments, since they are substantially similar to method embodiments, the description is relatively simple, as relevant to see a section of the description of method embodiments.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.

Claims (5)

1. C@S/SnS x The bionic construction method of the biochar composite material is characterized by comprising the following steps of:
s1: adding 50mL of acid mixed solution into 1.0 g-4.0 g needle-like tubular biomass, uniformly stirring, transferring to a hydrothermal reaction kettle, reacting for 2-24 h at 140-180 ℃, and carrying out suction filtration and drying on the obtained product to obtain low-carbonization biochar;
s2: transferring the low-carbonization biochar obtained in the step S1 into a tube furnace, heating to 800-1000 ℃ in a mixed atmosphere, preserving heat for 1-6 hours, and cleaning and drying the obtained product to obtain the biochar;
s3: the biochar obtained in S2 is mixed with an organotin source in a ratio of 1: (0.2-0.6), adding 50mL of acetone, uniformly mixing, transferring to a hydrothermal reaction kettle, reacting for 2-24 h at 160-200 ℃, filtering and drying the obtained product to obtain SnO 2 Biochar composite;
s4: snO obtained by S3 2 Biochar composite and sulfur source at 1: (0.38-0.64) is arranged in a tube furnace, and a sulfur source is arranged in SnO 2 Heating to 500-700 ℃ under vacuum between the biochar composite material and the furnace door of the tubular furnace, and preserving heat for 1-3 h to obtain SnS x The range of x of the biochar composite material is 1-2;
s5: will S4Obtained SnS x Placing the biochar composite material into 100mL of polysaccharide compound aqueous solution, soaking for 0.5-12 h, and drying the obtained product to obtain polysaccharide coated SnS x Biochar composite;
s6: coating the polysaccharide obtained in S5 with SnS x Transferring the biochar composite material into a tube furnace, heating to 400-600 ℃ in a mixed atmosphere, and preserving the temperature for 1-3 hours to obtain the carbon-coated SnS x Biochar composite;
s7: coating the carbon obtained in S6 with SnS x Gradually adding the biochar composite material into 50mL of sodium polysulfide solution containing 0.1 g-10.0 g of sodium polysulfide, stirring for 10min-20min, then dropwise adding 1 mL-10 mL of dilute sulfuric acid, standing for 12 h-24 h, washing the obtained product with water, and drying to obtain C@S/SnS x Biochar composite;
in S1, the needle-like tubular biomass comprises: any one of Albizia tree fluff, fructus Persicae fluff, radix et caulis Opuntiae Dillenii thorn, folium Cedar, folium et cacumen Sabinae chinensis, folium Arhat pine, and folium Cypress;
in the S1, the acidic mixed solution is formed by mixing citric acid, malic acid and grape acid in a molar ratio of (0.2-0.4): (0.1-0.7): (0.1-0.9); the concentration of the acidic mixed solution is 1 mol/L-10 mol/L;
s2, the mixed atmosphere consists of argon and nitrogen; the nitrogen accounts for 10-40% of the volume of the mixed atmosphere;
in S5, the aqueous polysaccharide compound solution includes: any one to three of inulin, gum, psyllium seed gum, pectin, heparin, chondroitin sulfate and hyaluronic acid; the concentration of the polysaccharide compound aqueous solution is 20mol/L-60mol/L;
in S6, the mixed atmosphere consists of argon and hydrogen, wherein the hydrogen accounts for 5-20% of the mixed atmosphere in percentage by volume.
2. A C@S/SnS method according to claim 1 x The bionic construction method of the biochar composite material is characterized in that in S3, the organic tin source comprises the following steps: tributyltin, triphenyltin, triethyltin acetate, triphenyltin acetate, dioctyltinAny one to three of (a) to (b).
3. A C@S/SnS method according to claim 1 x The bionic construction method of the biochar composite material is characterized in that in S4, the sulfur source comprises any one to three of ethanethiol, thiophenol, ethanesulfide, phenylsulfide and dimethyl sulfoxide.
4. A C@S/SnS method according to claim 1 x The bionic construction method of the biochar composite material is characterized in that in S7, the concentration of the dilute sulfuric acid is as follows: 1mol/L to 10mol/L.
5. C@S/SnS x A biochar composite material according to any one of claims 1 to 4, C@S/SnS x And preparing the biochar composite material by a bionic construction method.
CN202111435207.8A 2021-11-29 2021-11-29 C@S/SnS x Biochar composite material and bionic construction method thereof Active CN114220953B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111435207.8A CN114220953B (en) 2021-11-29 2021-11-29 C@S/SnS x Biochar composite material and bionic construction method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111435207.8A CN114220953B (en) 2021-11-29 2021-11-29 C@S/SnS x Biochar composite material and bionic construction method thereof

Publications (2)

Publication Number Publication Date
CN114220953A CN114220953A (en) 2022-03-22
CN114220953B true CN114220953B (en) 2023-06-16

Family

ID=80698901

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111435207.8A Active CN114220953B (en) 2021-11-29 2021-11-29 C@S/SnS x Biochar composite material and bionic construction method thereof

Country Status (1)

Country Link
CN (1) CN114220953B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114843462B (en) * 2022-04-19 2023-05-23 西安航空学院 Sulfur-loaded carbon-coated TiN-modified TiS 2 /SnS 2 Biochar composite material, preparation method and application
CN114725343B (en) * 2022-04-19 2023-08-29 西安航空学院 Nitrogen and sulfur co-doped biochar/SnO 2 SnS/S composite material, preparation method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099069A (en) * 2016-08-15 2016-11-09 华南理工大学 A kind of sodium-ion battery negative pole SnS/C composite and preparation method thereof
WO2018148090A1 (en) * 2017-02-13 2018-08-16 Nanotek Instruments, Inc. Alkali metal-sulfur secondary battery containing a nano sulfur-loaded cathode and manufacturing method
CN111682184A (en) * 2020-06-23 2020-09-18 欣旺达电动汽车电池有限公司 Tin-based composite material and preparation method thereof, negative plate and lithium ion battery
CN112234184A (en) * 2020-10-14 2021-01-15 桑顿新能源科技有限公司 SnS/CNTs/S composite material and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099069A (en) * 2016-08-15 2016-11-09 华南理工大学 A kind of sodium-ion battery negative pole SnS/C composite and preparation method thereof
WO2018148090A1 (en) * 2017-02-13 2018-08-16 Nanotek Instruments, Inc. Alkali metal-sulfur secondary battery containing a nano sulfur-loaded cathode and manufacturing method
CN111682184A (en) * 2020-06-23 2020-09-18 欣旺达电动汽车电池有限公司 Tin-based composite material and preparation method thereof, negative plate and lithium ion battery
CN112234184A (en) * 2020-10-14 2021-01-15 桑顿新能源科技有限公司 SnS/CNTs/S composite material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
花状SnS@CNTs/S复合正极材料用于高性能锂硫电池;蒋以号;杨青青;黄译锋;陈世霞;王珺;;南昌大学学报(工科版)(第02期);全文 *

Also Published As

Publication number Publication date
CN114220953A (en) 2022-03-22

Similar Documents

Publication Publication Date Title
CN114220953B (en) C@S/SnS x Biochar composite material and bionic construction method thereof
CN110164715B (en) Preparation method of wood-based flexible composite electrode material
CN104733700B (en) Preparation method of flexible anode of lithium-selenium battery
WO2021027100A1 (en) Nitrogen-doped porous carbon material, preparation method therefor and use thereof
CN106365163B (en) A kind of preparation method of sisal fiber activated carbon and the application of the sisal fiber activated carbon in lithium-ion capacitor
CN112391700B (en) MOF-modified cellulosic material interlayer for lithium sulfur battery and preparation method
CN104201392A (en) Preparation method of lithium-sulphur battery electrode
CN109767927A (en) A kind of preparation method of the supercapacitor biomass porous carbon of high-performance N doping
CN107910200A (en) A kind of preparation method of multi-stage porous nitrogen oxygen doping carbon supercapacitor electrode material
CN108002361B (en) Preparation method of high-sulfur-content nitrogen-sulfur co-doped asphalt-based carbon material
CN115092905B (en) Amorphous carbon material modified by carbon dots, and preparation method and application thereof
CN105084358A (en) Nitrogen and sulfur-co-doped active carbon for supercapacitor and preparation method for nitrogen and sulfur-co-doped active carbon for supercapacitor
CN109467082B (en) Preparation method of graphitized porous corncob derived carbon electrode material
CN107473215A (en) The preparation method of biomass porous carbon and carbon sulphur composite based on banana skin
CN111977651A (en) Preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon
CN113981673B (en) Growth 1T on carbon fiberPhase MoS 2 Preparation method and application of composite material @ rGO
CN105914058B (en) A kind of combination electrode material and preparation method thereof
CN107681092B (en) A kind of porous Carbon composites of nanometer hydroxyapatite and the preparation method and application thereof
CN112479205A (en) Narrow-pore bamboo sheath activated carbon and preparation method thereof
Zhao et al. Renewable biomass-derived carbon-based hosts for lithium–sulfur batteries
CN115943121A (en) Energy composite material for lithium battery and preparation method thereof
CN109360739B (en) Preparation method of nickel/nickel oxide loaded carbon nanofiber electrode material
CN111968863A (en) Preparation method of rare earth composite biomass-based capacitance carbon material
CN111863462A (en) Ferroferric oxide/nitrogen-doped hollow carbon sphere composite material for supercapacitor and preparation method thereof
CN116514239A (en) Activated composite biochar electrode and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant