CN114695854A - CNTs-SnS-SnS2@ GO heterostructure composite material and preparation method and application thereof - Google Patents
CNTs-SnS-SnS2@ GO heterostructure composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
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- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 91
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- 239000002253 acid Substances 0.000 claims description 32
- 239000002041 carbon nanotube Substances 0.000 claims description 27
- 229910052718 tin Inorganic materials 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 229910001415 sodium ion Inorganic materials 0.000 claims description 21
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 12
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 235000015165 citric acid Nutrition 0.000 claims description 7
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
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- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 63
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
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- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention discloses CNTs-SnS2The preparation method comprises the steps of uniformly mixing a tin source solution and a graphene dispersion solution, adding a pretreated multi-walled carbon nanotube and a surfactant, uniformly mixing, adding a sulfur source solution, stirring until the tin source and the sulfur source fully react and are fully and uniformly mixed, then carrying out ultrasonic dispersion to uniformly mix the obtained solution, fully reacting the solution in a solvothermal kettle at 140-180 ℃, filtering to obtain a gray black precipitate, washing and drying the gray black precipitate to obtain the CNTs-SnS2@ GO heterostructure composites; the composite material of the invention has high specific energy and excellent performanceThe electrochemical performance of the material can be simultaneously synthesized by a one-step solvothermal method, and the process is simple.
Description
Technical Field
The invention relates to the field of new energy material preparation, in particular to CNTs-SnS2@ GO heterostructure composite material and preparation method and application thereof.
Background
The sodium ion battery is considered as one of the substitutes of the lithium ion battery, some lithium resources exist in the form of salt lake brine, the Mg/Li content is high, and the cost of the lithium extraction technology is high. The price of the metal lithium is relatively high, and a novel lithium ion battery substitute product is urgently needed to be found. The development of sodium ion batteries can ensure that the development of the sodium ion batteries is not influenced by resource reserves due to sufficient sodium resources, and the advantages of similarity of electrochemical principles of the sodium ion batteries and the lithium ion batteries, proper electrochemical window, high safety and stability and the like become a new star in the field of new energy. But do not
Ratio of
Large radius, larger ionic radius makes Na+The material is difficult to migrate in the electrochemical process, and the structure of the material is collapsed or even pulverized in the process of sodium intercalation and deintercalation, so that the problems of slow electrochemical reaction kinetics, poor reversibility, short cycle life and the like of the sodium ion battery are caused, and the research of an excellent electrode material is particularly important for improving the energy density and the cycle performance of the sodium ion battery.
The negative electrode material of the sodium ion battery largely determines the working voltage, capacity, rate capability, cycle performance and the like of the battery, and at present, researches on the negative electrode material of the sodium ion battery are mainly divided into three main categories: the materials are embedded, alloy and conversion materials, but the materials generally face the problems of low specific capacity, fast capacity attenuation and the like, and can not meet the development requirements of batteries with high energy storage and long service life. However, there are also many materials which are worthy of further investigation, e.g. SnS, SnS2Equal alloy section barThe material is regarded as one of the promising sodium ion battery cathode materials, and has better development potential due to high specific capacity, and the specific reasons are as follows: first nano-scale SnS2Can provide more active sites for the storage of sodium ions, and then SnS in the form of nano particles or flaky layers2The direct contact between the electrolyte and the electrode can be effectively avoided. This particular layered structure favors Na+Can be rapidly de-embedded during the charging and discharging process. However, during the electrochemical reaction, SnS2The material has large volume change along with the desorption of sodium ions, internal stress is continuously accumulated to generate cracks and diffuse, active substances are further separated from a current collector, charge transfer is damaged, the cycle performance is poor, and the capacity is rapidly attenuated.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide CNTs-SnS2The @ GO heterostructure composite material has high specific energy and excellent electrochemical performance, and can be synthesized by a one-step solvothermal method, and the process is simple.
The purpose of the invention is realized by the following technical scheme:
CNTs-SnS-SnS2the preparation method of the @ GO heterostructure composite material comprises the following steps:
uniformly mixing a tin source solution and a graphene dispersion solution, adding a pretreated multi-walled carbon nanotube and a surfactant, uniformly mixing, adding a sulfur source solution, stirring until a tin source and a sulfur source are fully reacted and uniformly mixed, then performing ultrasonic dispersion to uniformly mix the obtained solution, fully reacting the solution in a solvent hot kettle at 140-180 ℃, filtering to obtain a gray black precipitate, washing and drying the gray black precipitate to obtain the CNTs-SnS2@ GO heterostructure composites;
wherein the preparation process of the pretreated multi-walled carbon nanotube comprises the following steps: carrying out acid washing and ultrasonic treatment on the multi-walled carbon nano tube, and washing and drying the acid-washed multi-walled carbon nano tube to obtain a pretreated multi-walled carbon nano tube;
the tin source solution comprises a tin source, reducing acid and an alcohol solvent, and the pH value of the tin source solution is-1-0;
the sulfur source solution adopts a glycol solution of a sulfur source;
the CNTs-SnS2In the @ GO heterostructure composite, CNTs, Sn, S: the mole ratio of GO is 1: (0.8-1.2): (0.8-1.2): 1.
preferably, when the pretreated multi-walled carbon nanotube is prepared, the multi-walled carbon nanotube is subjected to acid cleaning by using an acidic solution, wherein the acidic solution is formed by using 98% by mass of H2SO468 percent of HNO3And deionized water according to the volume ratio of (0.9-1) to 8.
Preferably, when acid washing is carried out on the multi-walled carbon nanotubes by adopting an acid solution, 40-80mg of the multi-walled carbon nanotubes are correspondingly added into every 50ml of the acid solution, and then the stirring is continued for 1-2h, so that the acid washing is completed.
Preferably, the mixed solution after the completion of the acid cleaning is subjected to ultrasonic treatment for 30-60 minutes, the ultrasonic power is 470-480W, and the ultrasonic frequency is 30-40 KHZ.
Preferably, the reaction time of the solution in the solvothermal kettle is 12-36 h.
Preferably, the tin source adopts SnCl2·2H2O、SnCl4·5H2O、SnSO4Or tin acetate; the reducing acid is citric acid, ascorbic acid or oxalic acid; the alcohol solvent in the tin source solution is one or a mixture of more of ethylene glycol, polyethylene glycol and PEG-500.
Preferably, the sulfur source is sodium sulfide, ammonium sulfide, thioacetamide or thiourea.
Preferably, the surfactant is CTAB, PVB or TAG-500.
The invention also provides CNTs-SnS2The @ GO heterostructure composite material is prepared by adopting the preparation method disclosed by the invention.
The invention relates to CNTs-SnS2@ GO heterojunctionThe composite material is used for preparing a negative electrode of a sodium ion battery.
Compared with the prior art, the invention has the following advantages and technical effects:
the invention CNTs-SnS2The preparation method of the @ GO heterostructure composite material is characterized in that SnS-SnS is adopted in a one-step solvothermal process2The heterostructure grows on a Graphene Oxide (GO) material in situ, and secondary composite modification is carried out by utilizing the special morphology structure of the pretreated multi-walled Carbon Nanotubes (CNTs), compared with the traditional method, the CNTs-SnS is prepared by a one-step solvothermal method2The @ GO heterostructure composite material avoids the step of high-temperature annealing in the later period, and the method is simple, convenient and environment-friendly. CNTs-SnS synthesized by the method2The composite material with the @ GO heterostructure has more stable cycle performance, effectively relieves the volume effect of the material, induces an internal electric field, promotes charge transfer, improves the electronic and ionic conductivity of the material, and finally improves the electrochemical performance of the material, so the synthesized CNTs-SnS has the advantages of improving the electrochemical performance of the material2The @ GO heterostructure composite material is made into a sodium ion battery cathode, and shows high cycle stability and excellent electrochemical performance.
Drawings
FIG. 1 shows a graph in which Sn: CNTs-SnS under the condition of S being 0.8:12The XRD pattern of @ GO heterostructure composites;
FIG. 2(a) shows the Sn: CNTs-SnS under the condition of S being 0.8:12SEM image of @ GO heterostructure composite (magnification 20000 times);
FIG. 2(b) shows the Sn: CNTs-SnS under the condition of S being 0.8:12SEM image of @ GO heterostructure composite (magnification 20000 times);
FIG. 3 shows a graph in which Sn: CNTs-SnS under the condition of S being 0.8:12A plot of the cyclic performance of the @ GO heterostructure composite;
FIG. 4 shows a graph in which Sn: 1:1 lower CNTs-SnS2The XRD pattern of @ GO heterostructure composites;
FIG. 5(a) shows a graph in which Sn: 1:1 lower CNTs-SnS2SEM image of @ GO heterostructure composite (magnification 20000 times);
FIG. 5(b) shows the Sn: 1:1 lower CNTs-SnS2SEM image of @ GO heterostructure composite (magnification 40000 times);
FIG. 5(c) shows the Sn: 1:1 lower CNTs-SnS2EDS energy spectra of @ GO heterostructure composites;
FIG. 6 shows a graph in which Sn: 1:1 lower CNTs-SnS2A plot of the cyclic performance of the @ GO heterostructure composite;
FIG. 7 shows a graph in which Sn: 1:1.2 CNTs-SnS2The XRD pattern of @ GO heterostructure composites;
FIG. 8(a) shows a graph in which Sn: 1:1.2 CNTs-SnS2SEM image of @ GO heterostructure composite (magnification 20000 times);
FIG. 8(b) shows the Sn: 1:1.2 CNTs-SnS2SEM image of @ GO heterostructure composite (magnification 20000 times);
FIG. 9 shows a graph in which Sn: 1:1.2 CNTs-SnS2Graph of cyclic performance of @ GO heterostructure composite.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The invention CNTs-SnS2The preparation method of the @ GO heterostructure composite material comprises the following steps:
step (1), weighing 40-80mg of multi-walled Carbon Nanotubes (CNTs) for acid washing treatment, wherein the acid solution is H with the mass fraction of 98%2SO468 percent of HNO3And deionized water is prepared according to the volume ratio of (0.9-1):8, the time of the acid cleaning treatment is 1-2h, ultrasonic treatment is carried out for 30-60min after the acid cleaning treatment is finished, the ultrasonic power is 470-480W, and the ultrasonic frequency is 30-40 KHZ. And washing and drying the treated CNTs.
Step (2), taking 4-6mDissolving a mol tin source and reducing acid in an alcohol solvent, regulating the pH value by adopting the reducing acid when needed, regulating the pH value to be under an acidic condition, fully stirring for 5-60min to completely dissolve the tin source, and taking the obtained mixed solution as solution A, wherein the pH value of the solution A is-1-0. Taking 15-30ml of a commercially available graphene solution with the concentration of 2mg/ml, and performing ultrasonic dispersion for a period of time to obtain a uniform graphene dispersion liquid, wherein the graphene dispersion liquid is used as a liquid B. Wherein the alcohol solvent is one or more of ethylene glycol, polyethylene glycol and PEG-500; the tin source adopts SnCl2·2H2O、SnCl4·5H2O、SnSO4Or tin acetate; the reducing acid is citric acid, ascorbic acid or oxalic acid.
And (3) dissolving 4-6mmol of sulfur source in the ethylene glycol solution to obtain solution C. Wherein the sulfur source is sodium sulfide, ammonium sulfide, thioacetamide or thiourea.
And (4) mixing the solution A and the solution B, adding 40-80mg of CNTs (subjected to acid washing treatment in the step (1)) into the mixed solution, adding a surfactant, stirring for 0.5-2.5 hours to fully stir the solution A, the solution B and the CNTs until the materials are completely dissolved to obtain a solution D, then adding the solution C into the solution D, stirring for 0.5-2.5 hours to fully react and fully mix tin and sulfur, performing ultrasonic dispersion for 0.5-2.5 hours to further promote uniform mixing, then adding the whole mixed solution system into a solvothermal kettle, reacting for 12-36 hours at 140-180 ℃ to fully react the materials, and filtering to obtain a grey-black precipitate. Wherein the surfactant is CTAB, PVB or TAG-500.
And (5) fully washing the obtained gray black precipitate, and then adding the gray black precipitate into a vacuum drying oven to dry for 8-12h at the temperature of 60-80 ℃. The CNTs-SnS can be obtained subsequently2@ GO heterostructure composites, CNTs-SnS2In the @ GO heterostructure composite, CNTs, Sn, S: the mole ratio of GO is 1: (0.8-1.2): (0.8-1.2): 1.
CNTs-SnS prepared by the invention2The @ GO heterostructure composite material has the characteristics of nanoscale, high purity and special morphology; the specific nanostructure can be Na+Providing a larger electrolyte/electrode contact areaAnd shorter diffusion paths;
the following examples of the present invention are prepared by using a mixed solution of ethylene glycol and PEG-500 as a solvent and citric acid as a pH modifier. In the process of one-step solvothermal process, Sn is increased along with the temperature2+And Sn4+And the coordination reaction is carried out with the solvent and is used as a Sn source in the subsequent reaction process. S is released along with Thioacetamide (TAA), thiourea and other materials in the later period in the solvothermal process2-Of with Sn2+And Sn4+Combining to form crystal nucleus, and further aggregating to form amorphous nanospheres along with the increase of the density of the crystal nucleus to generate so-called class 1 aggregation growth, specifically, in a low-restriction system, a grain recrystallization reaction generated in order to reduce the total surface free energy of the system transfers materials from one part of grains to the other part of grains, so that the grain size of the system is increased, and the crystallinity is better;
the CNTs-SnS is successfully prepared by the one-step solvothermal method provided by the invention2The method for the @ GO heterostructure composite material is simple in process, convenient to operate and high in yield, can avoid the step of high-temperature annealing in the traditional method, and shows high specific energy and excellent electrochemical performance. In the experimental process, alcohol solution is selected as solvent to avoid SnCl2·2H2Hydrolyzing O, and then combining with the graphene solution to react at high temperature to primarily form SnS-SnS2Then, the material is coated and modified for the second time by a multi-wall Carbon Nano Tube (CNTs), so that the material integrally forms a net structure, the conductivity of the material is promoted, the specific surface area of the material is increased, and then the CNTs-SnS is formed2@ GO heterostructure composites.
In the following embodiments of the invention, stannous chloride dihydrate is used as a tin source, thioacetamide is used as a sulfur source, graphene is used as a composite carrier and also used as a carbon source, multi-walled Carbon Nanotubes (CNTs) are used as a secondary composite modified material, a solvent is a mixed solution of ethylene glycol or other alcohols, and the solvent is prepared by one-step solvothermal method after a surfactant is added. For other alternative materials, the following method is equally applicable.
Example 1
Selection of the embodimentSn: CNTs-SnS is prepared by solvent thermal method under the condition that S is 0.8:12The @ GO heterostructure composite material is prepared by the following specific steps:
step (1) weighing 50mgCNTs (purity)>98 wt.%) is subjected to acid pickling for 1H, and the acid solution is 98 wt.% of H2SO468 percent of HNO3And deionized water according to the volume ratio of 0.9:1:8, and then carrying out ultrasonic treatment for 30min, wherein the ultrasonic power is 470W, and the ultrasonic frequency is 30 KHZ. And washing and drying the treated CNTs.
Respectively measuring 20ml of mixed solution of ethylene glycol and 20ml of PEG-500 as a solvent in the step (2), stirring for 60 minutes, carrying out ultrasonic dispersion for 30 minutes, and adding 4mmol of SnCl2·2H2O and 5mmol of citric acid are added into the solution, the pH value is controlled to be-1-0, and the solution is stirred for 60 minutes to be used as solution A. A commercially available graphene solution having a concentration of 2mg/ml was measured in an amount of 16ml, and ultrasonically dispersed for 1 hour to obtain a B solution.
And (3) weighing 5mmol of thioacetamide and dissolving the thioacetamide in 10ml of glycol solution to obtain solution C.
And (4) mixing the solution A and the solution B, adding 40mg of CNTs (after acid treatment) into the mixed solution, adding a surfactant, stirring for 0.5h to fully stir the solution A, the solution B and the CNTS to obtain a solution D, adding the solution C into the solution D, stirring for 1h to fully react and fully mix tin and sulfur, performing ultrasonic dispersion for 1.5h to further promote uniform mixing, adding the whole mixed solution system into a solvothermal kettle, reacting for a period of time at 180 ℃ to fully react materials, and filtering to obtain a gray-black precipitate. Wherein the surfactant adopts CTAB.
And (5) fully washing the obtained gray black precipitate, adding the gray black precipitate into a vacuum drying oven, and drying the gray black precipitate for 8 hours at the temperature of 60 ℃ to obtain the CNTs-SnS2@ GO heterostructure composites.
Then weighing the prepared active material (CNTs-SnS) according to the proportion of 7:2:12@ GO), conductive carbon black, binder. Firstly, grinding and mixing the active material, the conductive carbon black and the binder uniformly in a mortar, and then gradually grinding and mixingAnd dropwise adding NMP solution to prepare slurry. And uniformly coating the obtained slurry on a copper foil, and putting the coated battery pole piece into a vacuum drying oven to be dried for 12 hours at the temperature of 60 ℃. And cutting the dried pole piece into a small 12mm round pole piece. And (3) preparing a sodium ion battery, namely assembling a CR2032 type button experiment battery in a glove box filled with argon by using a metal sodium sheet as a counter electrode, a glass fiber type as a diaphragm and 1.0M NaCF3SO 3-DEGDME as electrolyte.
After the analysis of the composite material prepared in example 1, it was found that, by the XRD analysis, and as can be seen from fig. 1, the Sn: CNTs-SnS prepared under the condition that S is 0.8:12@ GO heterostructure composites, by XRD analysis, and from FIG. 1, CNTs-SnS prepared 30min ahead of time after sonication2@ GO heterostructure composite with SnS and SnS2Peaks of the two phases, and for SnS, diffraction peaks appear at 2 θ ═ 22.1 °, 26.1 °, 27.5 °, 30.5 °, 31.6 °, 31.7 °, 32 °, 39.4 °, corresponding to the (011), (012), (102), (110), (111), (013), (004), and (113) crystal planes, respectively. For SnS2Diffraction peaks appear at 2 θ ═ 15 °, 28.3 °, 30.6 °, 32.1 °, 41.9 °, 52.4 °, and 54.9 °, and the corresponding crystal planes are (001), (100), (002), (101), (102), (110), (111), and (103), so that it is known that a composite material in which two phases exist simultaneously can be successfully prepared by a one-step solvothermal method. Subsequently, as can be seen from fig. 2(a) and 2(b), the material has a nano-sheet structure, and the surface of the material is interwoven by the network structure of CNTs, but the overall agglomeration of the material is serious, which may be caused by that the CNTs are not completely treated by the mechanical effect of ultrasound after being subjected to ultrasound for 30min, so that the overall agglomeration of the composite material is caused. As can be seen from FIG. 3, CNTs-SnS2The specific discharge capacity of the first ring of the @ GO heterostructure composite material is 981.4mAh g-1The coulombic efficiency of the first circle is 65.09 percent, and the coulombic efficiency reaches 237.9mAh g after 50 circles of circulation-1，SnS-SnS2The specific discharge capacity of the first coil of the material is 568.3mAh g-1The coulombic efficiency of the first circle is 72.1 percent, and after 50 circles of circulation, the capacity is rapidly attenuated to 152.9 mAh.g-1CNTs-SnS can be found2@ GO heterostructure composite materialMaterial to SnS-SnS2And the capacity is improved, and the cycle stability is also improved to a certain extent.
Example 2
In this example, Sn: preparation of CNTS-SnS by solvothermal method under the condition that S is 1:12The @ GO heterostructure composite material is prepared by the following specific steps:
step (1) weighing 50mgCNTs (purity)>98 wt.%) is subjected to acid pickling for 1.5H, and the acid solution is 98 wt.% of H2SO468 percent of HNO3And deionized water according to the volume ratio of 1:1:8, and then carrying out ultrasonic treatment for 60min, wherein the ultrasonic power is 475W, and the ultrasonic frequency is 35 KHZ. And washing and drying the treated CNTs.
Respectively measuring a mixed solution of 20ml of ethylene glycol and 20ml of PEG-500 as a solvent in the step (2), stirring for 60 minutes, and carrying out ultrasonic dispersion for 30 minutes, wherein 5mmol of SnCl2·2H2O and 5mmol of citric acid are added into the solution, the pH value is controlled to be-1-0, and the solution is stirred for 60 minutes to be used as solution A. A commercially available graphene solution having a concentration of 2mg/ml was measured in an amount of 16ml, and ultrasonically dispersed for 1 hour to obtain a B solution.
And (3) weighing 5mmol of thioacetamide and dissolving the thioacetamide in 10ml of glycol solution to obtain solution C.
And (4) mixing the solution A and the solution B, adding 40mg of CNTs (after acid treatment) into the mixed solution, adding a surfactant, stirring for 2 hours to fully stir the solution A, the solution B and the CNTs to obtain a solution D, then adding the solution C into the solution D, stirring for 2.5 hours to fully react and fully mix tin and sulfur, then performing ultrasonic dispersion for 2.5 hours to further promote uniform mixing, then adding the whole mixed solution system into a solvothermal kettle, reacting for a period of time at 180 ℃ to fully react the materials, and then filtering to obtain a gray-black precipitate. Wherein the surfactant adopts CTAB.
And (5) fully washing the obtained gray black precipitate, adding the gray black precipitate into a vacuum drying oven, and drying the gray black precipitate for 8 hours at the temperature of 60 ℃ to obtain the CNTs-SnS2@ GO heterostructure composite.
Then, the prepared active material, conductive carbon black and binder are weighed according to the ratio of 7:2: 1. Firstly, grinding and uniformly mixing an active material, conductive carbon black and a binder in a mortar, and then dropwise adding an NMP solution to prepare slurry. And uniformly coating the obtained slurry on a copper foil, and putting the coated battery pole piece into a vacuum drying oven to be dried for 12 hours at the temperature of 60 ℃. And cutting the dried pole piece into a small 12mm round pole piece. The preparation of sodium ion battery, which uses metal sodium sheet as counter electrode and glass fiber type as diaphragm, 1.0M NaCF3SO3DEGDME is electrolyte and assembled in a glove box filled with argon to obtain the CR2032 type button experiment battery.
According to example 2, in the case of Sn: CNTs-SnS prepared under the condition that S is 1:12@ GO heterostructure composite, analyzed by XRD and it can be seen from FIG. 4 that CNTs-SnS prepared after ultrasonication 60min in advance2@ GO heterostructure composites with SnS and SnS2Peaks of the two phases, and for SnS, diffraction peaks appear at 2 θ ═ 22.1 °, 26.1 °, 27.5 °, 30.5 °, 31.6 °, 31.7 °, 32 °, 39.4 °, corresponding to the (011), (012), (102), (110), (111), (013), (004), and (113) crystal planes, respectively. For SnS2Diffraction peaks appear at 2 θ ═ 15 °, 28.3 °, 30.6 °, 32.1 °, 41.9 °, 52.4 °, and 54.9 °, and the corresponding crystal planes are (001), (100), (002), (101), (102), (110), (111), and (103), so that it is known that a composite material in which two phases exist simultaneously can be successfully prepared by a one-step solvothermal method. As can be seen from FIGS. 5(a) and 5(b), the material has a sheet structure, the diameter of the sheet structure is in the range of 1-5um, and the surfaces of the sheet structure are intertwined with CNTs, but the agglomeration phenomenon does not occur, so that it can be inferred that the length of the multi-walled carbon nanotube is shortened to about 5-10um after the ultrasonic treatment for 60min, and the agglomeration phenomenon of the material is effectively avoided. As shown in the EDS spectrum of FIG. 5(C), S, Sn and C are uniformly distributed in the material, and the success of the carbon-based material and SnS-SnS is preliminarily determined2And (4) compounding. Then, as can be seen from FIG. 6, CNTs-SnS2The specific discharge capacity of the first coil of the @ GO material is 762.5mAh g-1The coulombic efficiency of the first circle is 76.8 percent, after 50 circles of circulation,reach 612.2mAh g-1. By reaction with SnS-SnS2The materials are compared, and the attenuation performance of the capacity of the material is improved, and the integral specific capacity of the material is improved. The specific reason is that firstly, the composite modification of the graphene oxide can form a coating with a three-dimensional cross-linked structure, an effective continuous electronic conductive network is provided, electrode reaction kinetics is promoted, and SnS-SnS can be surrounded2Pores are generated around the heterostructure, indirectly preventing the volume expansion of the material, preventing the active material from being exposed to the electrolyte, and promoting the cycle stability of the material. Finally, through secondary composite modification of multi-wall Carbon Nanotubes (CNTs), the electronic conductivity is further improved, and the electrochemical performance of the material is improved.
Example 3
In this example, Sn: the preparation method of the composite material with the heterostructure CNTs-SnS-SnS2@ GO by a solvothermal method under the condition that S is 1:1.2 comprises the following specific steps:
step (1) weighing 50mg of CNTs (purity)>98 wt%) is subjected to acid cleaning for 2H, and the acid solution is H with the mass fraction of 98%2SO468 percent of HNO3And deionized water according to the volume ratio of 1:0.9:8, and then carrying out ultrasonic treatment for 90min, wherein the ultrasonic power is 480W, and the ultrasonic frequency is 40 KHZ. And washing and drying the treated CNTs.
Respectively measuring a mixed solution of 20ml of ethylene glycol and 20ml of PEG-500 as a solvent in the step (2), stirring for 60 minutes, and carrying out ultrasonic dispersion for 30 minutes, wherein 5mmol of SnCl2·2H2O and 5mmol of citric acid are added into the solution, the pH value is controlled to be-1-0, and the solution is stirred for 60 minutes to be used as solution A. A commercially available graphene solution having a concentration of 2mg/ml was measured in an amount of 16ml, and ultrasonically dispersed for 1 hour to obtain a B solution.
And (3) weighing 4mmol of thioacetamide, and dissolving the thioacetamide in 10ml of glycol solution to obtain solution C.
And (4) mixing the solution A and the solution B, adding 40mg of CNTs (after acid treatment) into the mixed solution, adding a surfactant, stirring for 2.5 hours to fully stir the solution A, the solution B and the CNTs to obtain a solution D, adding the solution C into the solution D, stirring for 1 hour to fully react and fully mix tin and sulfur, performing ultrasonic dispersion for 0.5 hour to further promote uniform mixing, adding the whole mixed solution system into a solvothermal kettle, reacting for a period of time at 180 ℃ to fully react materials, and filtering to obtain a gray-black precipitate. Wherein the surfactant adopts CTAB.
And (5) fully washing the obtained gray black precipitate, adding the gray black precipitate into a vacuum drying oven, and drying the gray black precipitate for 8 hours at the temperature of 60 ℃ to obtain the CNTs-SnS2@ GO heterostructure composites.
Then, the prepared active material, conductive carbon black and binder are weighed according to the ratio of 7:2: 1. Firstly, grinding and uniformly mixing an active material, conductive carbon black and a binder in a mortar, and then dropwise adding an NMP solution to prepare slurry. And uniformly coating the obtained slurry on a copper foil, and putting the coated battery pole piece into a vacuum drying oven to be dried for 12 hours at the temperature of 60 ℃. And cutting the dried pole piece into a small 12mm round pole piece. The sodium ion battery is prepared by taking a metal sodium sheet as a counter electrode and a glass fiber type as a diaphragm and 1.0M NaCF3SO3DEGDME is electrolyte and assembled in a glove box filled with argon to obtain the CR2032 type button experiment battery.
According to example 3, in the case of Sn: CNTs-SnS prepared under the condition of 1:1.2 of S ═ 12@ GO heterostructure composites, by XRD analysis, and from FIG. 7, it can be seen that CNTs-SnS prepared after sonication 60min in advance2@ GO heterostructure composites with SnS and SnS2Peaks of the two phases, and for SnS, diffraction peaks appear at 2 θ ═ 22.1 °, 26.1 °, 27.5 °, 30.5 °, 31.6 °, 31.7 °, 32 °, 39.4 °, corresponding to the (011), (012), (102), (110), (111), (013), (004), and (113) crystal planes, respectively. For SnS2Diffraction peaks appear at 2 θ ═ 15 °, 28.3 °, 30.6 °, 32.1 °, 41.9 °, 52.4 °, and 54.9 °, and the corresponding crystal planes are (001), (100), (002), (101), (102), (110), (111), and (103), so that it is known that a composite material in which two phases exist simultaneously can be successfully prepared by a one-step solvothermal method. Furthermore, as can be seen from FIGS. 8(a) and 8(b), CNTs-Sn was found after the analysis of scanning electron microscopeS-SnS2The @ GO heterostructure composite material is subjected to ultrasonic treatment for 90min, the size of the material is reduced, the diameter of the material is in a nanometer level, and after secondary modification of CNTs, the whole material is in a flower-shaped structure, so that the specific surface area of the material can be increased, the volume effect of the material can be prevented to a certain extent, and the circulation stability of the material is ensured. Then, as can be seen from FIG. 9, CNTs-SnS2The specific discharge capacity of the first coil of the @ GO material is 1078.7mAh g-1The coulombic efficiency of the first circle is 82.05 percent, and after 50 circles of circulation, the coulombic efficiency reaches 402.8 mAh.g-1. By reaction with SnS-SnS2And comparing the materials, and finding that the capacity of the material is not seriously attenuated after the material is cycled for 50 circles, and the integral specific capacity of the material is improved. The specific reason is as follows: successfully utilizes Graphene Oxide (GO) and SnS-SnS2The combined advantages of the heterostructures are used for enhancing the electrochemical performance and further reducing the motor current problem of a single material, firstly, the graphene oxide improves partial capacity and chemical function and allows SnS-SnS2Simple electrochemical treatment is carried out, more importantly, due to the size effect and the interaction of the interface, and the existence of the multi-wall carbon nano-tube improves the whole conductivity of the material, so the CNTs-SnS2The @ GO can finally show a remarkable synergistic effect, and compared with an intrinsic material, the composite material is found to have excellent electrochemical performance.
According to the scheme, the CNTs-SnS prepared by the one-step solvothermal method is utilized2The advantages of the @ GO heterostructure composite are: first, a reaction system in a solution is heated in a sealed container to generate a high-temperature and high-pressure reaction environment, so that a material crystal grows to form a specific nanostructure. Generally, the generated product has higher purity, good crystallinity and higher yield, and the shape and the crystal growth characteristics of the product are controlled by adjusting various reaction parameters to ensure that the product forms a nano structure with special shape and crystal structure, namely nano SnS-SnS2The particles can be further prevented from agglomerating, and the volume effect of the material can be buffered. Second SnS-SnS2The heterostructure can induce an internal electric field, further generate charge driving force,the problem of lower material conductivity is solved. Secondly, compounding with Graphene Oxide (GO) with excellent conductivity can make the material have a larger specific surface area and excellent mechanical flexibility, not only can effectively promote the transmission of electrons and ions, but also can effectively help to relieve the volume expansion in the process of sodium ion deintercalation, maintain stable structure, and then make the reaction process GO on more quickly and smoothly. Finally, the Carbon Nanotubes (CNTs) are utilized to carry out secondary composite modification on the material, because the multi-walled Carbon Nanotubes (CNTs) have the advantages of high electronic conductivity, high specific surface area utilization rate and the like, and the special tubular structure of the multi-walled Carbon Nanotubes (CNTs) can be used for SnS-SnS2The net structure is formed in the @ GO sheet structure, and the transmission of electrons and ions serves as the bridge, so that the transmission efficiency is improved. The double-layer carbon modification not only can solve the problem of SnS-SnS2The problem of the volume effect can further improve the electronic conductivity of the material on the basis of the heterostructure, and better ensure the electrochemical performance of the material.
Specific embodiments of the present invention have been described above in detail. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions that can be obtained by a person skilled in the art through logic analysis, reasoning or limited experiments based on the prior art according to the concept of the present invention should be within the scope of the claims of the present invention.
Claims (10)
1.CNTs-SnS-SnS2A preparation method of the @ GO heterostructure composite material is characterized by comprising the following steps:
uniformly mixing a tin source solution and a graphene dispersion solution, adding a pretreated multi-walled carbon nanotube and a surfactant, uniformly mixing, adding a sulfur source solution, stirring until a tin source and a sulfur source are fully reacted and uniformly mixed, then performing ultrasonic dispersion to uniformly mix the obtained solution, fully reacting the solution in a solvent hot kettle at 140-180 ℃, filtering to obtain a gray black precipitate, washing and drying the gray black precipitate to obtain the CNTs-SnS2@ GO heterostructure composite materialFeeding;
wherein the preparation process of the pretreated multi-walled carbon nanotube comprises the following steps: carrying out acid washing and ultrasonic treatment on the multi-walled carbon nano tube, and washing and drying the acid-washed multi-walled carbon nano tube to obtain a pretreated multi-walled carbon nano tube;
the tin source solution comprises a tin source, reducing acid and an alcohol solvent, and the pH value of the tin source solution is-1-0;
the sulfur source solution adopts a glycol solution of a sulfur source;
the CNTs-SnS2In the @ GO heterostructure composite, CNTs, Sn, S: the mole ratio of GO is 1: (0.8-1.2): (0.8-1.2): 1.
2. the CNTs-SnS of claim 12The preparation method of the @ GO heterostructure composite material is characterized in that when the pretreated multi-walled carbon nanotube is prepared, an acidic solution is adopted to carry out acid washing on the multi-walled carbon nanotube, and the acidic solution adopts 98% H in mass fraction2SO468 percent of HNO3And deionized water according to the volume ratio of (0.9-1) to 8.
3. The CNTs-SnS of claim 22The preparation method of the @ GO heterostructure composite material is characterized in that when acid solution is adopted to carry out acid washing on the multi-walled carbon nanotubes, 40-80mg of the multi-walled carbon nanotubes are correspondingly added into every 50ml of the acid solution, and then the acid washing is finished after the mixture is continuously stirred for 1-2 hours.
4. The CNTs-SnS of claim 32The preparation method of the @ GO heterostructure composite material is characterized in that the mixed solution after acid cleaning is subjected to ultrasonic treatment for 30-60 minutes, the ultrasonic power is 470-480W, and the ultrasonic frequency is 30-40 KHZ.
5. The CNTs-SnS of claim 12A preparation method of a @ GO heterostructure composite material is characterized in that the solution is subjected to reverse reaction in a solvothermal kettleThe reaction time is 12-36 h.
6. The CNTs-SnS of claim 12The preparation method of the @ GO heterostructure composite material is characterized in that the tin source adopts SnCl2·2H2O、SnCl4·5H2O、SnSO4Or tin acetate; the reducing acid is citric acid, ascorbic acid or oxalic acid; the alcohol solvent in the tin source solution is one or a mixture of more of ethylene glycol, polyethylene glycol and PEG-500.
7. The CNTs-SnS of claim 12The preparation method of the @ GO heterostructure composite material is characterized in that the sulfur source is sodium sulfide, ammonium sulfide, thioacetamide or thiourea.
8. The CNTs-SnS of claim 12The preparation method of the @ GO heterostructure composite material is characterized in that the surfactant adopts CTAB, PVB or TAG-500.
9. CNTs-SnS prepared by the preparation method of any one of claims 1 to 82@ GO heterostructure composite.
10. The CNTs-SnS of claim 92Application of @ GO heterostructure composite material, characterized in that the CNTs-SnS2The @ GO heterostructure composite material is used for preparing the cathode of the sodium ion battery.
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