CN106058198A - Method for preparing SnS2/CNTs (carbon nano-tubes) cathode materials for sodium-ion batteries in in-situ manner - Google Patents

Method for preparing SnS2/CNTs (carbon nano-tubes) cathode materials for sodium-ion batteries in in-situ manner Download PDF

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CN106058198A
CN106058198A CN201610595712.1A CN201610595712A CN106058198A CN 106058198 A CN106058198 A CN 106058198A CN 201610595712 A CN201610595712 A CN 201610595712A CN 106058198 A CN106058198 A CN 106058198A
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cnts
sns
sodium
situ
tubes
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黄剑锋
程娅伊
李嘉胤
许占位
曹丽云
郭玲
席乔
齐慧
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Shaanxi University of Science and Technology
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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
    • H01M4/581—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • 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

Abstract

The invention discloses a method for preparing SnS2/CNTs (carbon nano-tubes) cathode materials for sodium-ion batteries in an in-situ manner. The method includes adding carboxylated multi-walled carbon nano-tubes into deionized water, uniformly dispersing the carboxylated multi-walled carbon nano-tubes, then adding SnCl2 2H2O into the deionized water and uniformly dispersing the SnCl2 2H2O to obtain mixed liquid B; adding thioacetamide into the mixed liquid B and uniformly stirring the thioacetamide to obtain mixed liquid C; transferring the mixed liquid C into a hydrothermal kettle and carrying out reaction at the temperatures of 150-230 DEG C for 2-10 h to obtain the SnS2/CNTs cathode materials prepared for the sodium-ion batteries in the in-situ manner. The method has the advantages that the carboxylated multi-walled carbon nano-tubes are used as matrixes and can be effectively dispersed in water; a large quantity of Sn<2+> can be adsorbed by oxygen-containing functional groups on the surfaces of the carboxylated multi-walled carbon nano-tubes, and accordingly the method is beneficial to in-situ vulcanization; sulfur ions can be quickly released by the thioacetamide, accordingly, SnS2 is high in nucleation and growth speed, the reaction time can be shortened to a great extent, the reaction temperatures can be lowered to a great extent, and the method is applicable to requirements of large-scale production and preparation.

Description

A kind of sodium-ion battery prepares SnS in situ2The method of/CNTs negative material
Technical field
The present invention relates to a kind of sodium-ion battery negative pole SnS2The preparation of composite, is specifically related to a kind of sodium ion electricity SnS is prepared in situ in pond2The method of/CNTs negative material.
Background technology
It is known that the research of negative material is particularly significant for the development of sodium-ion battery.As described above, metal oxygen Compound and sulfide, because theoretical capacity is higher, up to about 1000mAh/g, electrochemical stability and security performance relatively Height becomes study hotspot in the past few years.The most many scholars are absorbed in research SnO2And SnS2Negative material.Although SnS2As The negative material theoretical capacity of sodium-ion battery is less than SnO2(645mAh/g), but the SnS of nano-scale2Have and preferably follow Ring stability, because sulfide change in volume during charging and discharging is little makes its mechanical stability resulting improvement.Additionally, The reversibility of sulfide is generally more preferable than oxide, causes cycle efficieny first higher than oxide material, and these all originate from SnS2 Layer structure.Therefore SnS is prepared2Anode material of lithium-ion battery is necessary.
SnS2Although have a preferable reversibility, but and SnO2Similar, solution is needed in the volumetric expansion during embedding sodium badly. Conventional method mainly compound, because Graphene and CNT have the knot of excellence with Graphene and CNT Structure stability, high conductivity, SnS can be effectively improved using it as matrix2Chemical property.
Li Haomiao etc. use the method for sintering to be prepared for SnS2/ CNTs composite, as sodium-ion battery negative pole Material, at 100mA g-1Electric current density under, 300 times circulation after capacity be maintained at 758mAh g-1。(H.M.Li, M.Zhou,W.Li,K.L.Wang,S.J.Cheng,K.Jiang.Layered SnS2cross-linked by carbon nanotubes as a high performance anode for sodium ion batteries.Rsc Advances.6 (2016) 35197-35202.) but use the product structure prepared of physical method to be difficult to control to be unfavorable for large-scale production.
Chuanxin Zhai etc. add NaCl, NH in water solution system4Cl also uses the method for layer assembly to be prepared for SnS2/ CNTs composite, encloses capacity circulation after as lithium ion battery negative material 50 using it and is about～400mAh g-1(Chuanxin Zhai,Ning Du,Hui Zhang,Jingxue Yu,and Deren Yang.Multiwalled Carbon Nanotubes Anchored with SnS2Nanosheets as High-Performance Anode Materials of Lithium-Ion Batteries[J].ACS Applied Materials&Interfaces.2011, 3,4067-4074.).Although being greatly promoted with CNT composite electrochemical performance, but preparation process adds a lot of template Agent, makes preparation process relatively complicated.Therefore, a kind of preparation process of exploitation is simple, it is not necessary to add template, and can be with Effective Regulation SnS2The method of/CNTs structure has great importance.
Summary of the invention
For overcoming the problems of the prior art, it is an object of the invention to provide a kind of sodium-ion battery and prepare in situ SnS2The method of/CNTs negative material, technique is simple, without any template, reaction temperature is low, the cycle is short, repeated height, energy Consume low, be suitable for large-scale production, prepared SnS2/ CNTs combination electrode material, its SnS2For hexagonal flake structure, in situ life Long on the surface of CNTs.
For reaching above-mentioned purpose, present invention employs techniques below scheme:
A kind of sodium-ion battery prepares SnS in situ2The method of/CNTs negative material, comprises the following steps:
1) carboxylated multi-walled carbon nano-tubes is joined in deionized water, be uniformly dispersed, obtain mixed liquor A；To mixing Liquid A adds SnCl2·2H2O, is uniformly dispersed, and obtains mixed liquid B；Then adding thioacetamide in mixed liquid B, stirring is all After even, obtain mixed liquor C；Wherein, carboxylated multi-walled carbon nano-tubes, SnCl2·2H2The ratio of O and thioacetamide be 30～ 160mg:0.15～3g:0.15～6g；
2) being transferred in water heating kettle by mixed liquor C, then react 2～10h at 150～230 DEG C, reaction cools down after terminating To room temperature, then separated by the centrifugal powder body that reaction is obtained, be dried after cyclic washing, obtain sodium-ion battery system in situ Standby SnS2/ CNTs negative material.
The present invention is further improved by, and the internal diameter of described carboxylated multi-walled carbon nano-tubes is 5～15nm, and external diameter is 20～100nm, a length of 10～30 μm.
The present invention is further improved by, and first stirs after being joined in deionized water by carboxylated multi-walled carbon nano-tubes Supersound process 10～180min under rear 50～100W, obtains mixed liquor A.
The present invention is further improved by, and the ratio of carboxylated multi-walled carbon nano-tubes and deionized water is 30～160mg: 30～80mL.
The present invention is further improved by, and adds SnCl in mixed liquor A2·2H240～70 after stirring after O DEG C, 50～100W under supersound process 1～5h, obtain mixed liquid B.
The present invention is further improved by, and reaction is carried out in homogeneous reactor；With 10 DEG C of min-1Intensification Ramp is to 150～230 DEG C.
The present invention is further improved by, and it is 30～80% that the volume compactedness of described water heating kettle controls.
The present invention is further improved by, and is dried and specifically uses lyophilization.
The present invention is further improved by, the SnS of preparation2SnS in/CNTs composite2For hexagonal flake structure, SnS2Growth in situ is on the surface of CNTs.
Compared with prior art, beneficial effects of the present invention is embodied in:
The present invention is using water as solvent, and thioacetamide is sulfur source, uses one step hydro thermal method to be prepared for SnS2/ CNTs is combined Material, and SnS2For hexagonal flake structure, growth in situ is on the surface of CNTs.Reason is that the present invention uses carboxylated carbon to receive Mitron, as matrix, can be effectively dispersed in water, and the oxygen-containing functional group on surface can adsorb more Sn2+, contribute to In-situ sulphiding, the thioacetamide that the further present invention uses can quickly discharge sulphion so that SnS2Nucleating growth Speed, than very fast, substantially reduces response time and temperature, needs prepared by applicable large-scale production.CNTs in this composite There is preferable structural stability, higher conductivity, and SnS2For nanoscale hexagonal flake structure, growth in situ is CNT's The transmission on surface, beneficially electronics, therefore, using it as anode material of lithium-ion battery, has the chemical property (example of excellence As, higher capacity and preferable high rate performance)；The preparation method that the present invention uses is simple, and reaction temperature is low, the cycle is short, energy Consume low, therefore in sodium-ion battery application aspect, there is the biggest scientific meaning.
Accompanying drawing explanation
Fig. 1 is the SnS prepared by embodiment 22X-ray diffraction (XRD) collection of illustrative plates of/CNTs composite；
Fig. 2 is the SnS prepared by embodiment 22Scanning electron microscope (SEM) photo of/CNTs composite；
Fig. 3 is the SnS prepared by embodiment 22The chemical property figure of/CNTs composite；Wherein, Cycle Number: cycle-index；Capacity: capacity.
Detailed description of the invention
With embodiment, the present invention is elaborated below in conjunction with the accompanying drawings.In the present invention, CNTs is CNT.
Embodiment 1
1) multi-walled carbon nano-tubes carboxylated for 30mg is added in 30mL deionized water, ultrasonic after stirring (100W) place Reason 40min obtains mixed liquor A；0.15g SnCl is added in described mixed liquor A2·2H2O, ultrasonic in 40 DEG C after stirring (100W) process 1h and obtain mixed liquid B；Solution B adds 0.3g thioacetamide the most again, after stirring, obtains mixed liquor C；
2) being transferred in politef water heating kettle by described mixed liquor C, the volume compactedness of water heating kettle controls 30%, Then politef water heating kettle is placed in homogeneous reactor and with 10 DEG C of min-1Heating rate be warming up to 150 DEG C, instead Answer 5h, reaction to cool to room temperature with the furnace after terminating, then separated by the centrifugal powder body that reaction is obtained, freezing after cyclic washing It is dried to obtain SnS2/ CNTs combination electrode material.
Embodiment 2
1) multi-walled carbon nano-tubes carboxylated for 30mg is added in 50mL deionized water, ultrasonic after stirring (60W) place Reason 60min obtains mixed liquor A；0.3g SnCl is added in described mixed liquor A2·2H2O, ultrasonic in 60 DEG C after stirring (60W) process 2h and obtain mixed liquid B；Solution B adds 0.75g thioacetamide the most again, after stirring, obtains mixed liquor C；
2) being transferred in politef water heating kettle by described mixed liquor C, the volume compactedness of water heating kettle controls 50%, Then politef water heating kettle is placed in homogeneous reactor and with 10 DEG C of min-1Heating rate be warming up to 180 DEG C, instead Answer 3h, reaction to cool to room temperature with the furnace after terminating, then separated by the centrifugal powder body that reaction is obtained, freezing after cyclic washing It is dried to obtain SnS2/ CNTs combination electrode material.
See Fig. 1, analyze sample (SnS with Rigaku D/max2000PCX-x ray diffractometer x2/ CNTs complex powder Body), find the SnS of sample and the hexagonal crystal system of the numbered 23-0677 of JCPDS2Structure is consistent.
See Fig. 2, this sample field emission scanning electron microscope (FESEM) of FEI Co. of U.S. S-4800 type is entered Row is observed, it can be seen that prepared SnS2For uniform hexagonal flake structure, growth in situ is on the surface of CNTs.
With prepared SnS2/ CNTs composite, as anode material of lithium-ion battery, is assembled into battery, uses BTS Its charge-discharge performance tested by battery charging and discharging tester.
See Fig. 3, it can be seen that SnS2/ CNTs negative material, compared to simple SnS2There is higher capacity with preferable High rate performance.
Embodiment 3
1) multi-walled carbon nano-tubes carboxylated for 50mg is added in 80mL deionized water, ultrasonic after stirring (80W) place Reason 120min obtains mixed liquor A；0.3g SnCl is added in described mixed liquor A2·2H2O, ultrasonic in 80 DEG C after stirring (80W) process 3h and obtain mixed liquid B；Solution B adds 1.5g thioacetamide the most again, after stirring, obtains mixed liquor C；
2) being transferred in politef water heating kettle by described mixed liquor C, the volume compactedness of water heating kettle controls 80%, Then politef water heating kettle is placed in homogeneous reactor and with 10 DEG C of min-1Heating rate be warming up to 210 DEG C, instead Answer 2h, reaction to cool to room temperature with the furnace after terminating, then separated by the centrifugal powder body that reaction is obtained, freezing after cyclic washing It is dried to obtain SnS2/ CNTs combination electrode material.
Embodiment 4
1) multi-walled carbon nano-tubes carboxylated for 80mg is added in 80mL deionized water, ultrasonic after stirring (80W) place Reason 150min obtains mixed liquor A；0.675g SnCl is added in described mixed liquor A2·2H2O, ultrasonic in 80 DEG C after stirring (80W) process 3h and obtain mixed liquid B；Solution B adds 1.35g thioacetamide the most again, after stirring, obtains mixed liquor C；
2) being transferred in politef water heating kettle by described mixed liquor C, the volume compactedness of water heating kettle controls 80%, Then politef water heating kettle is placed in homogeneous reactor and with 10 DEG C of min-1Heating rate be warming up to 180 DEG C, instead Answer 6h, reaction to cool to room temperature with the furnace after terminating, then separated by the centrifugal powder body that reaction is obtained, freezing after cyclic washing It is dried to obtain SnS2/ CNTs combination electrode material.
Embodiment 5
1) multi-walled carbon nano-tubes carboxylated for 80mg is added in 50mL deionized water, ultrasonic after stirring (80W) place Reason 120min obtains mixed liquor A；0.375g SnCl is added in described mixed liquor A2·2H2O, ultrasonic in 70 DEG C after stirring (80W) process 2h and obtain mixed liquid B；Solution B adds 1.125g thioacetamide the most again, after stirring, obtains mixed liquor C；
2) being transferred in politef water heating kettle by described mixed liquor C, the volume compactedness of water heating kettle controls 50%, Then politef water heating kettle is placed in homogeneous reactor and with 10 DEG C of min-1Heating rate be warming up to 200 DEG C, instead Answer 2h, reaction to cool to room temperature with the furnace after terminating, then separated by the centrifugal powder body that reaction is obtained, freezing after cyclic washing It is dried to obtain SnS2/ CNTs combination electrode material.
Embodiment 6
A kind of sodium-ion battery prepares SnS in situ2The method of/CNTs negative material, comprises the following steps:
1) joining in deionized water by carboxylated multi-walled carbon nano-tubes, ultrasonic after first stirring (50W) processes 10min, obtains mixed liquor A；SnCl is added in mixed liquor A2·2H2O, ultrasonic at 50 DEG C (50W) processes 5h, is mixed Liquid B；Then in mixed liquid B, add thioacetamide, after stirring, obtain mixed liquor C；Wherein, carboxylated many walls carbon Nanotube, SnCl2·2H2The ratio of O and thioacetamide is 160mg:0.15g:0.15g；Carboxylated multi-walled carbon nano-tubes with go The ratio of ionized water is 160mg:80mL；The internal diameter of carboxylated multi-walled carbon nano-tubes is 5～15nm, and external diameter is 20～100nm, long Degree is 10～30 μm.
2) being transferred in water heating kettle by mixed liquor C, it is 40% that the volume compactedness of water heating kettle controls, then in homogeneous reaction With 10 DEG C of min in device-1Heating rate be warming up to 230 DEG C, react 2h, reaction terminate after cool to room temperature with the furnace, then lead to Cross centrifugal powder body reaction obtained to separate, cyclic washing postlyophilization, obtain sodium-ion battery and prepare SnS in situ2/ CNTs negative material.
Embodiment 7
A kind of sodium-ion battery prepares SnS in situ2The method of/CNTs negative material, comprises the following steps:
1) joining in deionized water by carboxylated multi-walled carbon nano-tubes, ultrasonic after first stirring (70W) processes 100min, obtains mixed liquor A；SnCl is added in mixed liquor A2·2H2O, ultrasonic at 60 DEG C (70W) processes 4h, is mixed Liquid B；Then in mixed liquid B, add thioacetamide, after stirring, obtain mixed liquor C；Wherein, carboxylated many walls carbon Nanotube, SnCl2·2H2The ratio of O and thioacetamide is 120mg:3g:4g；Carboxylated multi-walled carbon nano-tubes and deionized water Ratio be 120mg:60mL；The internal diameter of carboxylated multi-walled carbon nano-tubes is 5～15nm, and external diameter is 20～100nm, a length of 10 ～30 μm.
2) being transferred in water heating kettle by mixed liquor C, it is 50% that the volume compactedness of water heating kettle controls, then in homogeneous reaction With 10 DEG C of min in device-1Heating rate be warming up to 170 DEG C, react 8h, reaction terminate after cool to room temperature with the furnace, then lead to Cross centrifugal powder body reaction obtained to separate, cyclic washing postlyophilization, obtain sodium-ion battery and prepare SnS in situ2/ CNTs negative material.
Embodiment 8
A kind of sodium-ion battery prepares SnS in situ2The method of/CNTs negative material, comprises the following steps:
1) joining in deionized water by carboxylated multi-walled carbon nano-tubes, ultrasonic after first stirring (100W) processes 180min, obtains mixed liquor A；SnCl is added in mixed liquor A2·2H2O, ultrasonic at 70 DEG C (100W) processes 1h, is mixed Close liquid B；Then in mixed liquid B, add thioacetamide, after stirring, obtain mixed liquor C；Wherein, carboxylated many walls CNT, SnCl2·2H2The ratio of O and thioacetamide is 100mg:2g:6g；Carboxylated multi-walled carbon nano-tubes and deionization The ratio of water is 100mg:40mL；The internal diameter of carboxylated multi-walled carbon nano-tubes is 5～15nm, and external diameter is 20～100nm, a length of 10～30 μm.
2) being transferred in water heating kettle by mixed liquor C, it is 60% that the volume compactedness of water heating kettle controls, then in homogeneous reaction With 10 DEG C of min in device-1Heating rate be warming up to 150 DEG C, react 10h, reaction terminate after cool to room temperature with the furnace, then lead to Cross centrifugal powder body reaction obtained to separate, cyclic washing postlyophilization, obtain sodium-ion battery and prepare SnS in situ2/ CNTs negative material.
In above-described embodiment, selected from carboxylated multi-walled carbon nano-tubes TNM5, (internal diameter is 5 to carboxylated multi-walled carbon nano-tubes ～10nm, external diameter is 20～30nm, a length of 10～30 μm), carboxylated multi-walled carbon nano-tubes, except TNM5, also includes TNM7、TNM8。
The present invention is sulfur source using water as solvent, thioacetamide, uses simple one step hydro thermal method to be prepared for SnS2/ CNTs composite, in this composite, CNTs has preferable structural stability, higher conductivity, and SnS2For nanoscale Hexagonal flake structure, growth in situ is in the transmission on the surface of CNT, beneficially electronics, therefore, using it as sodium-ion battery negative pole Material, has the chemical property (such as, higher capacity and preferable high rate performance) of excellence；The preparation side that the present invention uses Method is simple, and reaction temperature is low, the cycle is short, energy consumption is low, therefore has the biggest scientific meaning in sodium-ion battery application aspect.

Claims (9)

1. a sodium-ion battery prepares SnS in situ2The method of/CNTs negative material, it is characterised in that comprise the following steps:
1) carboxylated multi-walled carbon nano-tubes is joined in deionized water, be uniformly dispersed, obtain mixed liquor A；In mixed liquor A Add SnCl2·2H2O, is uniformly dispersed, and obtains mixed liquid B；Then in mixed liquid B, add thioacetamide, after stirring, Obtain mixed liquor C；Wherein, carboxylated multi-walled carbon nano-tubes, SnCl2·2H2The ratio of O and thioacetamide is 30～160mg: 0.15～3g:0.15～6g；
2) being transferred in water heating kettle by mixed liquor C, then react 2～10h at 150～230 DEG C, reaction is cooled to room after terminating Temperature, is then separated by centrifugal powder body reaction obtained, is dried after cyclic washing, obtains sodium-ion battery and prepares in situ SnS2/ CNTs negative material.
A kind of sodium-ion battery the most according to claim 1 prepares SnS in situ2The method of/CNTs negative material, it is special Levying and be, the internal diameter of described carboxylated multi-walled carbon nano-tubes is 5～15nm, and external diameter is 20～100nm, a length of 10～30 μ m。
A kind of sodium-ion battery the most according to claim 1 prepares SnS in situ2The method of/CNTs negative material, it is special Levy and be, supersound process under 50～100W after first stirring after carboxylated multi-walled carbon nano-tubes is joined in deionized water 10～180min, obtain mixed liquor A.
A kind of sodium-ion battery the most according to claim 1 prepares SnS in situ2The method of/CNTs negative material, it is special Levying and be, the ratio of carboxylated multi-walled carbon nano-tubes and deionized water is 30～160mg:30～80mL.
A kind of sodium-ion battery the most according to claim 1 prepares SnS in situ2The method of/CNTs negative material, it is special Levy and be, in mixed liquor A, add SnCl2·2H2After stirring after O under 40～70 DEG C, 50～100W supersound process 1～ 5h, obtains mixed liquid B.
A kind of sodium-ion battery the most according to claim 1 prepares SnS in situ2The method of/CNTs negative material, it is special Levying and be, reaction is carried out in homogeneous reactor；With 10 DEG C of min-1Heating rate be warming up to 150～230 DEG C.
A kind of sodium-ion battery the most according to claim 1 prepares SnS in situ2The method of/CNTs negative material, it is special Levying and be, it is 30～80% that the volume compactedness of described water heating kettle controls.
A kind of sodium-ion battery the most according to claim 1 prepares SnS in situ2The method of/CNTs negative material, it is special Levy and be, be dried and specifically use lyophilization.
A kind of sodium-ion battery the most according to claim 1 prepares SnS in situ2The method of/CNTs negative material, it is special Levy and be, the SnS of preparation2SnS in/CNTs composite2For hexagonal flake structure, SnS2Growth in situ is on the surface of CNTs.
CN201610595712.1A 2016-07-26 2016-07-26 Method for preparing SnS2/CNTs (carbon nano-tubes) cathode materials for sodium-ion batteries in in-situ manner Pending CN106058198A (en)

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CN107394129A (en) * 2017-06-20 2017-11-24 陕西科技大学 A kind of preparation method of stannic disulfide carbon nano-tube combination electrode material
CN108461726A (en) * 2018-03-12 2018-08-28 陕西科技大学 A kind of polycrystalline manganese dioxide/carbon nanotube composite material and its preparation method and application
CN108878885A (en) * 2018-07-03 2018-11-23 西南交通大学 SnS2The preparation method of-CNTs composite material and preparation method and composite positive pole
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CN109360950A (en) * 2018-09-17 2019-02-19 陕西科技大学 A kind of cobalt sulfide/carbon composite and preparation method thereof
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CN113346074A (en) * 2020-03-03 2021-09-03 香港科技大学 Electrode material with multilayer structure and preparation method thereof
CN113346074B (en) * 2020-03-03 2024-03-15 香港科技大学 Electrode material with multilayer structure and preparation method thereof
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CN114420926A (en) * 2022-01-19 2022-04-29 湖北亿纬动力有限公司 Positive host material and preparation method and application thereof
CN114420926B (en) * 2022-01-19 2024-03-15 湖北亿纬动力有限公司 Positive electrode host material and preparation method and application thereof
CN114695854A (en) * 2022-03-23 2022-07-01 西安建筑科技大学 CNTs-SnS-SnS2@ GO heterostructure composite material and preparation method and application thereof

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