CN111009651B - Sulfur-containing composite material and preparation method and application thereof - Google Patents

Sulfur-containing composite material and preparation method and application thereof Download PDF

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CN111009651B
CN111009651B CN201911221890.8A CN201911221890A CN111009651B CN 111009651 B CN111009651 B CN 111009651B CN 201911221890 A CN201911221890 A CN 201911221890A CN 111009651 B CN111009651 B CN 111009651B
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CN111009651A (en
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潘跃德
李素丽
李俊义
徐延铭
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Zhuhai Cosmx Battery Co Ltd
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Abstract

A sulfur-containing composite material, a preparation method and application thereof, belonging to the technical field of lithium-sulfur batteries. The sulfur-containing composite material contains graphene layer and XMn2O4Nanosheets, sulfur, wherein X ═ Co, Zn, or Mg; the graphene layer and XMn2O4The nano-sheet layers are alternately stacked, and the graphene layer and the XMn are2O4The interlayer of the nanosheet layer contains sulfur. The sulfur-containing composite material is applied to the positive electrode of the lithium-sulfur battery. The invention has the advantages that: the graphene/XMn is obtained by a simple solution method2O4The synthesis method of the nano-sheet compound is easy to enlarge, is suitable for industrial production, and can be used for preparing the composite material in a large scale. When the composite material is used as a positive electrode material of a lithium-sulfur battery, the high conductivity of graphene is utilized, and due to the fact that the bimetallic oxide XMn2O4The absorption effect of polysulfide ions is considered, the rate capability, capacity exertion and cycling stability of the lithium-sulfur battery are considered, and the high-performance lithium-sulfur battery can be obtained.

Description

Sulfur-containing composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a sulfur-containing composite material and a preparation method and application thereof.
Background
A lithium sulfur battery includes a positive electrode containing electroactive sulfur, a negative electrode containing lithium, an electrolyte, and a separator. The theoretical specific energy of the lithium-sulfur battery is as high as 2600Wh/kg, and the actual specific energy is higher than that of the current commercial lithium ion battery. The obvious advantage of the specific energy makes the lithium-sulfur battery have wide potential application in special power supplies, electric automobiles, high-altitude aircrafts and the like.
The positive electrode material of the lithium-sulfur battery is a key technology of the lithium-sulfur battery. Metal oxides are an important support material for sulfur (adv. mater.2017,29,1601759). Oxidation by oxygenMagnesium, nickel oxide, cobalt oxide, zinc oxide, ferric oxide and the like can be used for compounding with sulfur to obtain the positive electrode material of the lithium-sulfur battery (CN 108063224A). However, poor conductivity of metal oxide can result in severe polarization of the battery, insufficient rate capability, and poor cycle performance. Subsequently, through further research, researchers found that the metal oxide/carbon/sulfur ternary composite material is more beneficial to the improvement of various electrochemical performances of the lithium-sulfur battery. Cr is obtained by taking chromium skin as a raw material2O3the/C composite material is compounded with sulfur to obtain the positive electrode material of the lithium-sulfur battery (CN 108666536A). However, chromium is an element which causes serious environmental pollution, and if it is used in a large amount for a battery material, it has a bad influence on the environment. Therefore, in order to obtain a high-performance lithium sulfur battery, development of a new cathode material and a method for preparing the same is urgently needed.
Disclosure of Invention
The invention aims to solve the problem that the existing sulfur positive electrode of a lithium-sulfur battery does not have a suitable carrier material, and provides a sulfur-containing composite material, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a sulfur-containing composite characterized by: the sulfur-containing composite material contains graphene layer and XMn2O4Nanosheets, sulfur, wherein X ═ Co, Zn, or Mg;
the graphene layer and XMn2O4The nano-sheet layers are alternately stacked, and the graphene layer and the XMn are2O4The interlayer of the nanosheet layer contains sulfur.
The application of the sulfur-containing composite material is to apply the sulfur-containing composite material to a positive electrode of a lithium-sulfur battery.
A preparation method of the sulfur-containing composite material comprises the following steps:
s1: preparing amorphous manganese dioxide nanosheets: adding a potassium permanganate aqueous solution into an alkane solution of an organic matter, reducing potassium permanganate into amorphous manganese dioxide nanosheets to obtain a brown colloidal solution, separating out solids, heating the solids to remove a solvent, and obtaining intermediate amorphous manganese dioxide nanosheets;
s2: graphene/XMn2O4Preparation of a nanosheet composite, wherein X ═ Co, Zn, Mg: dispersing amorphous manganese dioxide nanosheets and graphene oxide into an alcohol-water mixed solvent, carrying out ultrasonic treatment, then carrying out heating treatment at 50-80 ℃, reducing solvent volatilization, and adding XCl2Stirring the solution and the reducing agent solution at the temperature of 20-80 ℃ for 0.1-24 h, and performing centrifugal separation to obtain the product graphene/CoMn2O4A nanosheet composite;
s3: preparing a sulfur-containing composite material: mixing sulfur and graphene/XMn2O4The nano-sheet compound is prepared from 1-9: 1 to obtain the graphene/XMn2O4And (3) obtaining the sulfur-containing composite material by using the nano-sheet/sulfur ternary composite material.
Compared with the prior art, the invention has the beneficial effects that:
(1) the graphene/XMn is obtained by a simple solution method2O4The (X ═ Co, Zn, Mg) nanosheet composite is easy to scale up, industrial production is realized, and the composite material can be prepared on a large scale.
(2) graphene/XMn prepared by the invention2O4(X ═ Co, Zn, Mg) nanosheet/sulfur ternary composite material, when used as a lithium-sulfur battery cathode material, not only utilizes the high conductivity of graphene, but also is due to the bimetallic oxide XMn2O4The absorption effect of polysulfide ions is considered, the rate capability, capacity exertion and cycling stability of the lithium-sulfur battery are considered, and the high-performance lithium-sulfur battery can be obtained.
(3) The sulfur is positioned between the double metal oxide and the graphene sheet layer, and the volume expansion caused by the conversion from the sulfur to the lithium sulfide in the electrochemical reaction process can be absorbed by the layered structure, so that the stability of the electrode material is effectively improved.
(4)XMn2O4The transition metal in the electrolyte is mainly manganese, the manganese is wide in source and low in cost, and the electrolyte has a wide application prospect in the field of batteries.
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FIG. 1 is a graphene/XMn2O4The (X ═ Co, Zn, Mg) nanosheet/sulfur ternary composite material has a structural schematic diagram.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention. The reagents, materials and instruments used in the following description are all conventional reagents, conventional materials and conventional instruments, which are commercially available, and the reagents may be synthesized by a conventional synthesis method, if not specifically described.
The first embodiment is as follows: the present embodiment describes a sulfur-containing composite material containing a graphene layer and XMn2O4Nanosheets, sulfur, wherein X ═ Co, Zn, or Mg;
the graphene layer and XMn2O4The nano-sheet layers are alternately stacked, and the graphene layer and the XMn are2O4The lamellae of the nanosheets contain sulfur between them, as shown in fig. 1.
The second embodiment is as follows: the sulfur-containing composite material of embodiment one, said XMn2O4The crystal structure of (a) is spinel.
The third concrete implementation mode: the sulfur-containing composite material according to the first or second embodiment is used in a positive electrode of a lithium-sulfur battery.
The fourth concrete implementation mode: a method for preparing a sulfur-containing composite material according to the first or second embodiment, the method comprising:
s1: preparing amorphous manganese dioxide nanosheets: adding a potassium permanganate aqueous solution into an alkane solution of an organic matter, reducing potassium permanganate into amorphous manganese dioxide nanosheets to obtain a brown colloidal solution, separating out solids, heating the solids to remove a solvent, and obtaining intermediate amorphous manganese dioxide nanosheets; the separation method can be centrifugation, suction filtration or standing precipitation;
s2: graphene/XMn2O4Preparation of a nanosheet composite, wherein X ═ Co, Zn, Mg: dispersing amorphous manganese dioxide nanosheets and graphene oxide into an alcohol-water mixed solvent, carrying out ultrasonic treatment, then carrying out heating treatment at 50-80 ℃, reducing solvent volatilization, and adding XCl2Stirring the solution and the reducing agent solution at the temperature of 20-80 ℃ for 0.1-24 h, and performing centrifugal separation to obtain the product graphene/CoMn2O4A nanosheet composite; the rotating speed of the centrifugation is 100-10000 rpm, preferably 6000 rpm;
in the process of solvent volatilization, two-dimensional materials of graphene oxide and amorphous manganese dioxide are self-assembled and compounded and stacked mutually. Under the action of a reducing agent, X2+Reacting with amorphous manganese dioxide to form spinel type XMn2O4Simultaneously, reducing the graphene oxide by a reducing agent to form graphene; the graphene oxide used may be synthesized by Hummers method or may be purchased commercially directly.
S3: preparing a sulfur-containing composite material: mixing sulfur and graphene/XMn2O4The nano-sheet compound is prepared from 1-9: 1 to obtain the graphene/XMn2O4And (3) obtaining the sulfur-containing composite material by using the nano-sheet/sulfur ternary composite material. The method adopted by the compounding is a heating melting method or a solution method.
The fifth concrete implementation mode: in S1, the molar concentration N1 of the aqueous potassium permanganate solution is 0.01 to 3mol/L, and the volume is V1; the molar concentration N2 of the alkane solution of the organic matter is 0.01-3 mol/L, and the volume is V2; v2: v1 is 5-50: 1, N2 XV 2: n1 XV 1 is 1 ~ 5.
The sixth specific implementation mode: in the preparation method of the sulfur-containing composite material according to the fourth specific embodiment, in S1, the organic matter is an organic matter that can be oxidized by potassium permanganate; the organic matter capable of being oxidized by potassium permanganate is alkene, alkyne, alcohol, aldehyde, aromatic hydrocarbon or heterocyclic aromatic hydrocarbon; the alkane has a boiling point above 20 ℃ and a melting point below 20 ℃.
The seventh embodiment: a method for preparing a sulfur-containing composite material, as described in embodiment four, in S2,
the ratio of the mass M1 of the amorphous manganese dioxide nanosheet to the mass M2 of the graphene oxide is 1-20: 1;
the mixing volume ratio of alcohol to water in the mixed solvent is 1-10: 1, the alcohol is ethanol or isopropanol;
the ratio of the total mass M1+ M2 of the amorphous manganese dioxide nanosheets and the graphene oxide to the volume V3 of the alcohol-water mixed solvent is 1-100 g: 1L;
the ratio of the volume of the volatilized solvent V4 to the volume of the alcohol-water mixed solvent V3 is 1: 2 to 100 parts;
said XCl2The molar concentration of the solution N3 is 0.01-1 mol/L, the volume is V5, the unit is L, N3 xV 5 is M1: 20-2000 parts;
the molar concentration N4 of the reducing agent solution is 0.01-3 mol/L, the volume V6, the unit L, N4 xV 6 is M1: 20 to 200 parts.
The specific implementation mode is eight: in the method for preparing a sulfur-containing composite material according to the fourth embodiment, in S2, the ultrasonic treatment conditions are as follows: ultrasonic frequency of 0.01-1W/cm2Ultrasonic treatment is carried out for 10-60 min, and the temperature of the solution is controlled at 10-80 ℃.
The specific implementation method nine: a method for preparing a sulfur-containing composite material, in S2, the XCl2Replacement by X (NO)3)2Or XSO4。
The detailed implementation mode is ten: in S2, the reducing agent is sodium borohydride, sodium hypophosphite, or hydrazine hydrate; the reducing agent solution is neutral or alkaline, and the pH range is 9-12 in the alkaline state.
Example 1:
(1) amorphous manganese dioxide nanosheet: dispersing 200ml of potassium permanganate aqueous solution (0.1mol/L) into 100ml of isooctane solution (0.1mol/L) of sodium sulfosuccinate, carrying out ultrasonic treatment for 30min to obtain brown colloid solution, separating out solids at the centrifugal speed of 6000rpm, and heating to remove the solvent to obtain amorphous manganese dioxide nanosheets.
(2) graphene/CoMn2O4Nanosheet composite: graphene oxide (174mg) purchased directly commercially and the obtained amorphous manganese dioxide nanosheet (174mg) were dispersed in 500ml of an ethanol/water mixed solvent (volume ratio 1: 1) under ultrasonic conditions. The dispersion solution was heat-treated at 80 ℃ to volatilize the solvent until the volume of the solution became 150 ml. Then, CoCl was added simultaneously2·6H2O (256mg) and aqueous sodium borohydride (0.1M, adjusted to pH 11 with NaOH, 50ml) were stirred at 60 ℃ for 2h, centrifuged and dried to give the product. The drying operation can be performed by a person skilled in the art in a conventional manner.
(3) graphene/CoMn2O4Nanosheet/sulfur ternary composite: 100mg of graphene/CoMn2O4Dispersing the nanosheet composite in 200ml of aqueous solution, adding 20ml of sulfur-containing ethylenediamine dispersion liquid (400mg of sulfur), dropwise adding dilute nitric acid (0.1mol) until the pH value is 7, performing suction filtration, washing and drying to obtain graphene/CoMn2O4A nanosheet/sulfur ternary composite. The operations of suction filtration, washing and drying can be carried out by the person skilled in the art.
Comparative example 1-1:
graphene/sulfur composite: dispersing 100mg of graphene in 200ml of water solution, adding 20ml of sulfur ethylenediamine dispersion liquid (400mg of sulfur), dropwise adding dilute nitric acid (0.1mol) until the pH value is 7, performing suction filtration, washing and drying to obtain the graphene/sulfur composite material.
Comparative examples 1 to 2:
(1) amorphous manganese dioxide nanosheet: dispersing 200ml of potassium permanganate aqueous solution (0.1mol/L) into 100ml of isooctane solution (0.1mol/L) of sodium sulfosuccinate, carrying out ultrasonic treatment for 30min to obtain brown colloid solution, separating out solids at the centrifugal speed of 6000rpm, and heating to remove the solvent to obtain amorphous manganese dioxide nanosheets.
(2)CoMn2O4Nanosheet: under ultrasonic conditions, the obtained amorphousManganese dioxide type (174mg) was dispersed in 500ml of an ethanol/water mixed solvent (volume ratio 1: 1). The dispersion solution was heat-treated at 80 ℃ to volatilize the solvent until the volume of the solution became 150 ml. Then, CoCl was added simultaneously2·6H2O (256mg) and aqueous sodium borohydride (0.1M, adjusted to pH 11 with NaOH, 50ml) were stirred at 60 ℃ for 2h, centrifuged and dried to give the product.
(3)CoMn2O4Nanosheet/sulfur composite: 100mg of CoMn2O4Dispersing the nano-sheets in 200ml of aqueous solution, adding 20ml of sulfur ethylenediamine dispersion (400mg of sulfur), dropwise adding dilute nitric acid (0.1mol) until the pH value is 7, carrying out suction filtration, washing and drying to obtain CoMn2O4A nanosheet/sulfur composite.
Example 2:
(1) the positive electrode materials and binders described in example 1, comparative examples 1 to 1 and comparative examples 1 to 2 (SBR/CMC 1: 1) and the conductive agent (Super P) were mixed at a ratio of 80: 10: 10, deionized water is used as a solvent to prepare slurry, the slurry is coated on a carbon-coated aluminum foil and dried to obtain the sulfur-carrying amount of 2mg/cm2The positive electrode sheet of (1).
(2) Lithium sulfur battery assembly and testing: the above-described positive electrode sheet was assembled into a laminated battery with a negative electrode (100 μ M metal lithium foil) and an electrolyte (1M LiTFSI dissolved in a DOL/DME mixed solvent in a volume ratio of 1:1, with an additive of 0.1M LiNO3) at a mass ratio of electrolyte to sulfur of 3.5, and charge and discharge tests (0.2C/0.2C) were performed with a battery test apparatus to compare the initial gram capacity and cycle performance (the number of cycles for which the capacity was reduced to 80% of the initial capacity) of each positive electrode material. The data obtained are shown in table 1. As can be seen from the battery performance of the cathode materials obtained in the examples and comparative examples in table 1, the cathode material and the synthesis method thereof disclosed by the invention can obtain higher gram capacity and better cycle performance. The sulfur is arranged between the bimetallic oxide nanosheets and the graphene sheet layers, so that the adsorption performance of the bimetallic oxide on polysulfide ions generated in the electrochemical reaction process is exerted, the graphene has good conductivity, and the interlayer structure can accommodate volume expansion of the sulfur in the electrochemical reaction process, so that the gram capacity and the cycle performance are effectively improved.
Table 1 comparative battery performance table described in example 2
Figure BDA0002301081660000051
Figure BDA0002301081660000061
Example 3:
(1) amorphous manganese dioxide nanosheet: dispersing 200ml of potassium permanganate aqueous solution (0.5mol/L) into 100ml of toluene isooctane solution (0.1mol/L), carrying out ultrasonic treatment for 30min to obtain brown colloid solution, separating out solids at the centrifugal rotation speed of 6000rpm, and heating to remove the solvent to obtain amorphous manganese dioxide nanosheets.
(2) graphene/ZnMn2O4Nanosheet composite: graphene oxide (174mg) and amorphous manganese dioxide (174mg) obtained as purchased commercially directly were dispersed in 500ml of an ethanol/water mixed solvent (volume ratio 2:1) under ultrasonic conditions. The dispersion solution was heat-treated at 50 ℃ to volatilize the solvent until the volume of the solution became 150 ml. Then, ZnCl is added simultaneously2(136mg) and aqueous sodium borohydride (0.05M, pH 11 with NaOH, 100ml), stirred at 80 ℃ for 2h, centrifuged and dried to give the product.
(3) graphene/ZnMn2O4Nanosheet/sulfur ternary composite: 100mg of graphene/ZnMn2O4Dispersing the nanosheet composite in 200ml of aqueous solution, adding 20ml of sulfur-containing ethylenediamine dispersion liquid (300mg of sulfur), dropwise adding dilute nitric acid (0.1mol) until the pH value is 7, performing suction filtration, washing and drying to obtain graphene/ZnMn2O4A nanosheet/sulfur ternary composite.
Example 4:
(1) amorphous manganese dioxide nanosheet: dispersing 200ml of potassium permanganate aqueous solution (0.5mol/L) into 100ml of butyraldehyde or ethanol isooctane solution (0.1mol/L), carrying out ultrasonic treatment for 30min to obtain brown colloid solution, separating out solids at the centrifugal speed of 6000rpm, and heating to remove the solvent to obtain amorphous manganese dioxide nanosheets.
(2) graphene/ZnMn2O4Nanosheet composite: graphene oxide (174mg) and amorphous manganese dioxide (174mg) obtained as purchased commercially directly were dispersed in 500ml of an ethanol/water mixed solvent (volume ratio 2:1) under ultrasonic conditions. The dispersion solution was heat-treated at 50 ℃ to volatilize the solvent until the volume of the solution became 150 ml. Then, ZnCl is added simultaneously2(136mg) and aqueous sodium borohydride (0.05M, pH 10 with NaOH, 100ml), stirred at 70 ℃ for 3h, centrifuged and dried to give the product.
(3) graphene/ZnMn2O4Nanosheet/sulfur ternary composite: 100mg of graphene/ZnMn2O4Dispersing the nanosheet composite in 200ml of aqueous solution, adding 20ml of sulfur-containing ethylenediamine dispersion liquid (300mg of sulfur), dropwise adding dilute nitric acid (0.1mol) until the pH value is 7, performing suction filtration, washing and drying to obtain graphene/ZnMn2O4A nanosheet/sulfur ternary composite.
Example 5:
(1) amorphous manganese dioxide nanosheet: dispersing 200ml of potassium permanganate aqueous solution (0.2mol/L) into 100ml of 1-pentene or 1-hexyne isooctane solution (0.1mol/L), carrying out ultrasonic treatment for 30min to obtain brown colloid solution, separating out solids at the centrifugal rotation speed of 10000rpm, and heating to remove the solvent to obtain the amorphous manganese dioxide nanosheet.
(2) graphene/MgMn2O4Nanosheet composite: graphene oxide (174mg) and amorphous manganese dioxide (174mg) obtained as purchased commercially directly were dispersed in 500ml of an isopropanol/water mixed solvent (volume ratio 1: 2) under ultrasonic conditions. The dispersion solution was heat-treated at 60 ℃ to volatilize the solvent until the volume of the solution became 150 ml. Then, MgCl was added simultaneously2(95mg) and an aqueous solution of sodium hydrogenphosphinate (0.1M, pH 12 adjusted with NaOH, 70ml), stirred at room temperature for 6h, centrifuged, and dried to give the product.
(3) graphene/MgMn2O4Nanosheet/sulfur ternary composite: 100mg of graphene/MgMn2O4Dispersing the nanosheet composite in 200ml of aqueous solution, adding 20ml of sulfur ethylenediamine dispersion liquid (500mg of sulfur), dropwise adding dilute nitric acid (0.05mol) until the pH value is 7, performing suction filtration, washing and drying to obtain graphene/MgMn2O4A nanosheet/sulfur ternary composite.
Example 6:
(1) amorphous manganese dioxide nanosheet: dispersing 200ml of potassium permanganate aqueous solution (0.2mol/L) into 100ml of isooctane solution (0.1mol/L) of beta-methylpyridine, carrying out ultrasonic treatment for 30min to obtain brown colloid solution, separating out solids at the centrifugal speed of 10000rpm, and heating to remove the solvent to obtain amorphous manganese dioxide nanosheets.
(2) graphene/MgMn2O4Nanosheet composite: graphene oxide (174mg) and amorphous manganese dioxide (174mg) obtained as purchased commercially directly were dispersed in 500ml of an isopropanol/water mixed solvent (volume ratio 1: 2) under ultrasonic conditions. The dispersion solution was heat-treated at 60 ℃ to volatilize the solvent until the volume of the solution became 150 ml. Then, MgCl was added simultaneously2(95mg) and aqueous hydrazine hydrate (0.1M, pH 9 with NaOH, 70ml), stirred at 40 ℃ for 5h, centrifuged and dried to give the product.
(3) graphene/MgMn2O4Nanosheet/sulfur ternary composite: 100mg of graphene/MgMn2O4Grinding and mixing the nano sheet compound and 500mg of sulfur, heating the mixture at 155 ℃ for 12h in a sealed manner, and then heating the mixture at 300 ℃ for 2h to remove excessive sulfur to obtain graphene/MgMn2O4A nanosheet/sulfur ternary composite.

Claims (10)

1. A sulfur-containing composite characterized by: the sulfur-containing composite material contains graphene layer and XMn2O4Nanosheets, sulfur, wherein X ═ Co, Zn, or Mg;
the graphene layer and XMn2O4The nano-sheet layers are alternately stacked, and the stoneGraphene layer and XMn2O4The interlayer of the nanosheet layer contains sulfur.
2. The sulfur-containing composite material of claim 1, wherein: the XMn2O4The crystal structure of (a) is spinel.
3. Use of a sulfur-containing composite material according to claim 1 or 2, wherein: the sulfur-containing composite material is applied to the positive electrode of the lithium-sulfur battery.
4. A method for preparing a sulfur-containing composite material according to claim 1 or 2, characterized in that: the method comprises the following steps:
s1: preparing amorphous manganese dioxide nanosheets: adding a potassium permanganate aqueous solution into an alkane solution of an organic matter, reducing potassium permanganate into amorphous manganese dioxide nanosheets to obtain a brown colloidal solution, separating out solids, heating the solids to remove a solvent, and obtaining intermediate amorphous manganese dioxide nanosheets;
s2: graphene/XMn2O4Preparation of a nanosheet composite, wherein X ═ Co, Zn, Mg: dispersing amorphous manganese dioxide nanosheets and graphene oxide into an alcohol-water mixed solvent, carrying out ultrasonic treatment, then carrying out heating treatment at 50-80 ℃, reducing solvent volatilization, and adding XCl2Stirring the solution and the reducing agent solution at the temperature of 20-80 ℃ for 0.1-24 h, and performing centrifugal separation to obtain the product graphene/XMn2O4A nanosheet composite;
s3: preparing a sulfur-containing composite material: mixing sulfur and graphene/XMn2O4The nano-sheet compound is prepared from 1-9: 1 to obtain the graphene/XMn2O4And (3) obtaining the sulfur-containing composite material by using the nano-sheet/sulfur ternary composite material.
5. The method of claim 4, wherein the sulfur-containing composite material is prepared by: in S1, the molar concentration N1 of the potassium permanganate aqueous solution is 0.01-3 mol/L, and the volume is V1; the molar concentration N2 of the alkane solution of the organic matter is 0.01-3 mol/L, and the volume is V2; v2: v1 is 5-50: 1, N2 XV 2: n1 XV 1 is 1 ~ 5.
6. The method of claim 4, wherein the sulfur-containing composite material is prepared by: in S1, the organic matter is an organic matter which can be oxidized by potassium permanganate; the organic matter capable of being oxidized by potassium permanganate is alkene, alkyne, alcohol, aldehyde or aromatic hydrocarbon; the alkane has a boiling point above 20 ℃ and a melting point below 20 ℃.
7. The method of claim 4, wherein the sulfur-containing composite material is prepared by: in the step S2, the first step,
the ratio of the mass M1 of the amorphous manganese dioxide nanosheet to the mass M2 of the graphene oxide is 1-20: 1;
the mixing volume ratio of alcohol to water in the mixed solvent is 1-10: 1, the alcohol is ethanol or isopropanol;
the ratio of the total mass M1+ M2 of the amorphous manganese dioxide nanosheets and the graphene oxide to the volume V3 of the alcohol-water mixed solvent is 1-100 g: 1L;
the ratio of the volume of the volatilized solvent V4 to the volume of the alcohol-water mixed solvent V3 is 1: 2 to 100 parts;
said XCl2The molar concentration of the solution N3 is 0.01-1 mol/L, the volume is V5, the unit is L, N3 xV 5 is M1: 20-2000 parts;
the molar concentration N4 of the reducing agent solution is 0.01-3 mol/L, the volume V6, the unit L, N4 xV 6 is M1: 20 to 200 parts.
8. The method of claim 4, wherein the sulfur-containing composite material is prepared by: in S2, the ultrasonic treatment conditions are: ultrasonic frequency of 0.01-1W/cm2Ultrasonic treatment is carried out for 10-60 min, and the temperature of the solution is controlled at 10-80 ℃.
9. The method of claim 4, wherein the sulfur-containing composite material is prepared by: in S2, the XCl2Replacement by X (NO)3)2Or XSO4。
10. The method of claim 4, wherein the sulfur-containing composite material is prepared by: in S2, the reducing agent is sodium borohydride, sodium hypophosphite or hydrazine hydrate; the reducing agent solution is neutral or alkaline, and the pH range is 9-12 in the alkaline state.
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