CN111943256A - Preparation method and application of flexible self-supporting tin-based sulfide-carbon composite material - Google Patents
Preparation method and application of flexible self-supporting tin-based sulfide-carbon composite material Download PDFInfo
- Publication number
- CN111943256A CN111943256A CN202010648817.5A CN202010648817A CN111943256A CN 111943256 A CN111943256 A CN 111943256A CN 202010648817 A CN202010648817 A CN 202010648817A CN 111943256 A CN111943256 A CN 111943256A
- Authority
- CN
- China
- Prior art keywords
- tin
- flexible
- temperature
- composite material
- carbon composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of a flexible self-supporting tin-based sulfide-carbon composite material. According to the invention, the tin-based sulfide-carbon composite material self-supporting electrode with good flexibility and conductivity is prepared by a simple electrostatic spinning technology, the volume expansion of tin-based sulfide is slowed down by titanium dioxide and carbon radicals, the overall conductivity of the electrode is enhanced by carbon, and a high-performance flexible negative electrode is provided for a lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of organic materials, and particularly relates to a preparation method and application of a flexible self-supporting tin-based sulfide-carbon composite material.
Background
At present, lithium ion batteries are widely applied in the field of portable electronic devices such as mobile phones, cameras, notebook computers and the like, and commercial negative electrode materials of the lithium ion batteries mainly comprise carbon groups such as graphite and the like, and the specific capacity of the lithium ion batteries is only 372mAh/g, so that the lithium ion batteries are difficult to meet the increasing battery capacity requirement. Novel active materials such as silicon base and tin base can form an alloy with lithium, and have higher theoretical specific capacity, but the volume expansion and the change of the active materials are extremely large (300%) in the charging and discharging process, and the electrode materials are easily pulverized and fall off from a current collector after repeated circulation, so that the practical application is influenced. In addition, the conductivity of the material is poor, and therefore, how to improve the conductivity of the novel active materials and effectively utilize the high specific capacity of the novel active materials becomes a research hotspot. Meanwhile, with the wide application of flexible foldable electronic products and wearable devices, the market demand for fully flexible electronic devices is increasing. In order to adapt to ergonomics and motion mechanics and realize bending of a foldable wearable product with a large degree of freedom, light, thin and flexible energy storage devices such as flexible batteries, supercapacitors and the like are urgently needed in the industry, electrodes and active materials in the flexible batteries and the capacitors are extremely easy to be subjected to mechanical stress in a complex deformation process, and therefore, in order to relieve energy storage performance loss caused by strain and deformation, the design and preparation process of the flexible electrodes need to be optimized so as to realize high load capacity of the active materials and overall flexibility of the electrodes.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a flexible self-supporting tin-based sulfide-carbon composite material.
The invention also aims to provide application of the flexible self-supporting tin-based sulfide-carbon composite material prepared by the preparation method.
The technical scheme of the invention is as follows:
a preparation method of a flexible self-supporting tin-based sulfide-carbon composite material comprises the following steps:
(1) uniformly mixing polyacrylonitrile and N, N-dimethylformamide to obtain a solution (namely a precursor solution) with the concentration of 5-10 wt% of polyacrylonitrile; carrying out electrostatic spinning on the precursor solution to prepare nano flexible fibers (fibers are self-assembled into interwoven flaky films in the spinning process, and the area of the films can reach dozens of square centimeters); sequentially carrying out pre-oxidation treatment under an air atmosphere and annealing treatment under a nitrogen atmosphere on the flexible fiber to obtain a flexible carbon nanofiber membrane;
(2) fully dispersing a tin source and a sulfur source in absolute ethyl alcohol to obtain a mixed solution, wherein the molar ratio of sulfur to tin is 1-4:1, and the concentration of tin ions is 0.1-0.5M; soaking the flexible carbon nanofiber membrane obtained in the step (1) in the mixed solution, performing hydrothermal reaction, naturally cooling to room temperature, washing and drying to obtain a substrate loaded with an active material; the temperature of the hydrothermal reaction is 160-240 ℃, and the time is 15-36 h;
(3) and depositing titanium dioxide particles on the substrate by using an Atomic Layer Deposition (ALD) method to obtain the flexible self-supporting tin-based sulfide-carbon composite material. (titanium dioxide is an ideal structure stabilizer with little volume change during the process of lithium deintercalation, Li formed during the initial charge-discharge cyclexTiO2The thin conductive layer can promote the rapid transfer of electrons and ions, and the thickness of the titanium dioxide is regulated and controlled by adjusting the cycle number in the atomic layer deposition process. )
In a preferred embodiment of the present invention, the concentration of polyacrylonitrile in the precursor solution is 7-8 wt%.
In a preferred embodiment of the present invention, the temperature of the pre-oxidation treatment is 200-400 ℃ and the time is 1-5 h.
Further preferably, the temperature of the pre-oxidation treatment is 250-280 ℃ and the time is 1-2 h.
In a preferred embodiment of the present invention, the temperature of the annealing treatment is 700-900 ℃ and the time is 1-5 h.
Further preferably, the temperature of the annealing treatment is 700-800 ℃, and the time is 1-2 h.
In a preferred embodiment of the present invention, the temperature of the hydrothermal reaction is 180-200 ℃ and the time is 20-24 h.
In a preferred embodiment of the invention, the sulphur source is thioacetamide and/or thiourea.
In a preferred embodiment of the present invention, the tin source is at least one of tin sulfate, tin tetrachloride pentahydrate, tin chloride dihydrate and sodium stannate.
The other technical scheme of the invention is as follows:
the flexible self-supporting tin-based sulfide-carbon composite material prepared by the preparation method is applied to preparing a negative electrode for a lithium ion battery.
The invention has the beneficial effects that:
1. the invention adopts a nanoscale sheet structure to slow down the volume expansion of an active material, and is compounded with a flexible carbon-based substrate with high stability and high conductivity and a titanium dioxide material to prepare the flexible self-supporting tin-based sulfide-carbon composite material.
2. The flexible self-supporting tin-based sulfide-carbon composite material prepared by the invention has good flexibility and conductivity, and solves the problems of poor conductivity of tin-based sulfide and poor flexibility and freedom degree of the conventional cathode structure through a simple electrostatic spinning technology.
3. The flexible self-supporting tin-based sulfide-carbon composite material prepared by the invention introduces high-capacity tin-based sulfide, realizes large load capacity in an electrostatic spinning mode, and further improves the battery capacity.
4. The flexible tin-based sulfide-carbon composite material prepared by the invention is used for preparing the self-supporting electrode with high flexibility, high conductivity, high stability, high capacity and high load capacity by introducing the tin-based oxide with high stability, and can be applied to the wearable field.
Drawings
FIG. 1 is an XRD pattern of a pure phase tin disulfide material prepared in comparative example 1 and a flexible self-supporting tin sulfide-carbon composite obtained in example 1 according to the present invention.
Figure 2 is an SEM image of a pure phase tin disulfide material prepared in comparative example 1 and a flexible self-supporting tin sulfide-carbon composite obtained in example 1 according to the present invention. Wherein 1 is flexible Carbon Nanofiber (CNF), 2 and 3 are CNF @ SnS2(ii) a 4 is CNF @ SnS2@TiO2And 5 is pure SnS2。
Figure 3 is a graph of rate performance for cells made of the pure phase tin disulfide material from comparative example 1 and the flexible self-supporting tin sulfide-carbon composite from example 1 of the present invention.
Fig. 4 is a diagram showing a flexible self-supporting tin sulfide-carbon composite material obtained in example 1 of the present invention in a bent state.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Comparative example 1
Preparing a pure-phase tin disulfide anode material by a hydrothermal method:
preparation of pure phase sulfide: dispersing 1.08g of tin tetrachloride pentahydrate and 0.92g of thioacetamide in 60mL of absolute ethyl alcohol to prepare a mixed solution, then transferring the mixed solution into a 100mL reaction kettle, preserving heat for 20h at 180 ℃, washing the prepared material with deionized water for three times, drying for 12h at 60 ℃ to obtain yellow powder, grinding for 1h by using a mortar to obtain a pure-phase tin disulfide material (pure SnS) as shown in 5 in figure 1 and 22)。
Assembling the battery: the battery model used for the electrochemical performance test is a button cell CR 2025. Mixing the pure-phase tin disulfide material, acetylene black and sodium carboxymethyl cellulose according to the mass ratio of 8: 1, and adding a proper amount of deionized water to prepare the slurry. The prepared slurry is coated on a current collector copper foil, and the slurry is naturally dried and then transferred to a vacuum oven at 80 ℃ for further drying for 12 hours. To be coated with active materialThe copper foil was cut into uniform size 12mm diameter disks and the weight of the disks was weighed. The battery preparation process is carried out in a glove box, and the electrolyte component is LiPF with 1mol/L6Dissolved in an equal volume ratio of Ethylene Carbonate (EC) and diethyl carbonate (DEC), with a septum type selected as Celgard 2400. The rate performance curve of this cell is shown in fig. 3.
Example 1
(1) Preparing flexible carbon nanofiber: 0.4-0.5g of polyacrylonitrile and 5-6mL of N, N-dimethylformamide are mixed and stirred for 12 hours. Subjecting the obtained solution to electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the inner diameter of a needle is 0.42mm, the spinning voltage is 9kV, the receiving mode is roller receiving, the flow rate of a precursor solution is 0.3-0.4mL/h, the receiving distance is 12-15cm, the spinning temperature is 35 ℃, the spinning time is 17h, the obtained nano fiber is dried in a vacuum drying oven at 60 ℃ for 12h, and the dried nano fiber is subjected to pre-oxidation treatment: keeping the temperature at 280 ℃ for 2h, and then carrying out annealing treatment: and (3) keeping the temperature at 800 ℃ for 2h in an argon atmosphere, wherein the heating rate is 1 ℃/min, and then cooling to room temperature to obtain the flexible carbon nanofiber membrane shown as 1 in figure 2.
(2) In-situ loading of sulfide: dispersing 1.08g of pentahydrate stannic chloride and 0.92g of thioacetamide in 60mL of ethanol, carrying out ultrasonic treatment for 5min to prepare a mixed solution, soaking 30mg of the flexible carbon nanofiber membrane obtained in the step (1) in the mixed solution, transferring the mixed solution into a 100mL reaction kettle (a stainless steel reaction kettle with a polytetrafluoroethylene lining), preserving the heat for 20h at 180 ℃, taking out the fiber membrane (loaded with sulfide), washing the fiber membrane with deionized water for three times, and drying the fiber membrane at 60 ℃ for 12h to obtain CNF @ SnS shown in 2 and 3 in figures 1 and 22。
(3) Deposition of titanium dioxide: the fiber membrane CNF @ SnS obtained in the step (2) is treated2Depositing titanium dioxide with the thickness of 2mm by using an ALD method to obtain the flexible self-supporting tin-based sulfide-carbon composite material (CNF @ SnS) shown in figure 1, 4 in figure 2 and 42@TiO2). The specific parameters of ALD are as follows: the temperature is 200 ℃, the nitrogen flow is 200SCCM, the titanium tetrachloride is a titanium source precursor, the pulse time is 200ms, the purging time is 1s, the water vapor is an oxygen source precursor, and the pulseTime 100ms, purge time 1s500 ms.
The battery assembly is different from that of comparative example 1, and the self-supporting material CNF @ SnS is directly mixed2@TiO2And CNF @ SnS2Cutting into wafers with the uniform specification and the diameter of 12mm, and weighing the weight of the pole piece without preparing slurry or using a conductive agent and an adhesive. The rate performance curve of this cell is shown in fig. 3.
Example 2:
(1) preparing flexible carbon nanofiber: 0.4-0.5g of polyacrylonitrile and 5-6mL of N, N-dimethylformamide are mixed and stirred for 12 hours. Subjecting the obtained solution to electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the inner diameter of a needle is 0.42mm, the spinning voltage is 9kV, the receiving mode is roller receiving, the flow rate of a precursor solution is 0.3-0.4mL/h, the receiving distance is 12-15cm, the spinning temperature is 35 ℃, the spinning time is 17h, the obtained nano fiber is dried in a vacuum drying oven at 60 ℃ for 12h, and the dried nano fiber is subjected to pre-oxidation treatment: keeping the temperature at 250 ℃ for 2h, and then carrying out annealing treatment: and (3) keeping the temperature of the nitrogen-containing flexible nanofiber membrane at 700 ℃ for 2h in an argon atmosphere, wherein the heating rate is 1 ℃/min, and then cooling the nitrogen-containing flexible nanofiber membrane to room temperature to obtain the nitrogen-containing flexible nanofiber membrane.
(2) In-situ loading of sulfide: dispersing 1.08g of tin tetrachloride pentahydrate and 0.92g of thioacetamide in 60mL of ethanol, carrying out ultrasonic treatment for 5min to prepare a mixed solution, soaking the 60mg of flexible carbon nanofiber membrane obtained in the step (1) in the mixed solution, transferring the mixed solution to a 100mL reaction kettle (a stainless steel reaction kettle with a polytetrafluoroethylene lining), carrying out heat preservation for 24h at 180 ℃, taking out the fiber membrane (loaded with sulfide), washing the fiber membrane with deionized water for three times, and drying the fiber membrane for 12h at 60 ℃.
(3) Deposition of titanium dioxide: and (3) depositing 2nm titanium dioxide on the fiber membrane obtained in the step (2) by using an ALD method (the specific parameters are the same as those of the example 1) to obtain the flexible self-supporting tin-based sulfide-carbon composite material.
Example 3:
(1) preparing flexible carbon nanofiber: 0.4-0.5g of polyacrylonitrile, 5-6ml of LN and N-dimethylformamide are mixed and stirred for 12 hours. Subjecting the obtained solution to electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the inner diameter of a needle is 0.42mm, the spinning voltage is 9kV, the receiving mode is roller receiving, the flow rate of a precursor solution is 0.3-0.4mL/h, the receiving distance is 12-15cm, the spinning temperature is 35 ℃, the spinning time is 17h, the obtained nano fiber is dried in a vacuum drying oven at 60 ℃ for 12h, and the dried nano fiber is subjected to pre-oxidation treatment: keeping the temperature at 300 ℃ for 2h, and then carrying out annealing treatment: and (3) preserving the heat for 2h in an argon atmosphere at the temperature of 900 ℃, wherein the heating rate is 1 ℃/min, and then cooling to the room temperature to obtain the flexible carbon nanofiber membrane.
(2) In-situ loading of sulfide: dispersing 1.08g of tin tetrachloride pentahydrate and 0.92g of thioacetamide in 60mL of ethanol, carrying out ultrasonic treatment for 5min to prepare a mixed solution, soaking 90mg of the flexible carbon nanofiber membrane obtained in the step (1) in the mixed solution, transferring the mixed solution to a 100mL reaction kettle (a stainless steel reaction kettle with a polytetrafluoroethylene lining), carrying out heat preservation at 180 ℃ for 28h, taking out the fiber membrane (loaded with sulfide), washing the fiber membrane with deionized water for three times, and drying the fiber membrane at 60 ℃ for 12 h.
(3) Deposition of titanium dioxide: and (3) depositing 2nm titanium dioxide on the fiber membrane obtained in the step (2) by using an ALD method (the specific parameters are the same as those of the example 1) to obtain the flexible self-supporting tin-based sulfide-carbon composite material.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A preparation method of a flexible self-supporting tin-based sulfide-carbon composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing polyacrylonitrile and N, N-dimethylformamide to obtain a precursor solution with the concentration of 5-10 wt% of polyacrylonitrile; carrying out electrostatic spinning on the precursor solution to prepare the nano flexible fiber; sequentially carrying out pre-oxidation treatment under an air atmosphere and annealing treatment under a nitrogen atmosphere on the flexible fiber to obtain a flexible carbon nanofiber membrane;
(2) fully dispersing a tin source and a sulfur source in absolute ethyl alcohol to obtain a mixed solution, wherein the molar ratio of sulfur ions to tin ions is 1-4:1, and the concentration of tin ions is 0.1-0.5M; soaking the flexible carbon nanofiber membrane obtained in the step (1) in the mixed solution, performing hydrothermal reaction, naturally cooling to room temperature, washing and drying to obtain a substrate loaded with an active material; the temperature of the hydrothermal reaction is 160-240 ℃, and the time is 15-36 h;
(3) depositing titanium dioxide particles on the substrate by using an atomic layer deposition method to obtain the flexible self-supporting tin-based sulfide-carbon composite material.
2. The method of claim 1, wherein: the concentration of polyacrylonitrile in the precursor solution is 7-8 wt%.
3. The method of claim 1, wherein: the temperature of the pre-oxidation treatment is 200-400 ℃, and the time is 1-5 h.
4. The method of claim 3, wherein: the temperature of the pre-oxidation treatment is 250-280 ℃, and the time is 1-2 h.
5. The method of claim 1, wherein: the temperature of the annealing treatment is 700-900 ℃, and the time is 1-5 h.
6. The method of claim 5, wherein: the temperature of the annealing treatment is 700-800 ℃, and the time is 1-2 h.
7. The method of claim 1, wherein: the temperature of the hydrothermal reaction is 180-200 ℃, and the time is 20-24 h.
8. The production method according to any one of claims 1 to 7, characterized in that: the sulfur source is thioacetamide or thiourea.
9. The production method according to any one of claims 1 to 7, characterized in that: the tin source is at least one of tin sulfate, tin tetrachloride pentahydrate, tin chloride dihydrate and sodium stannate.
10. Use of the flexible self-supporting tin-based sulfide-carbon composite material prepared by the preparation method of any one of claims 1 to 9 in the preparation of a negative electrode for a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010648817.5A CN111943256A (en) | 2020-07-07 | 2020-07-07 | Preparation method and application of flexible self-supporting tin-based sulfide-carbon composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010648817.5A CN111943256A (en) | 2020-07-07 | 2020-07-07 | Preparation method and application of flexible self-supporting tin-based sulfide-carbon composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111943256A true CN111943256A (en) | 2020-11-17 |
Family
ID=73340339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010648817.5A Pending CN111943256A (en) | 2020-07-07 | 2020-07-07 | Preparation method and application of flexible self-supporting tin-based sulfide-carbon composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111943256A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113745477A (en) * | 2021-08-25 | 2021-12-03 | 福建师范大学 | Preparation method and application of sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material |
| CN113823782A (en) * | 2021-08-25 | 2021-12-21 | 福建师范大学 | Preparation method and application of sulfur-doped polyacrylonitrile-chlorella derived carbon composite sodium ion battery negative electrode material |
| CN113998740A (en) * | 2021-10-25 | 2022-02-01 | 同济大学 | C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method |
| CN114094073A (en) * | 2021-11-12 | 2022-02-25 | 中博龙辉装备集团股份有限公司 | Tin dioxide @ carbon foam self-supporting composite material and preparation method and application thereof |
| CN114551891A (en) * | 2022-04-27 | 2022-05-27 | 潍坊科技学院 | Tin disulfide/titanium dioxide/carbon composite material and preparation method and application thereof |
| CN115101719A (en) * | 2022-05-27 | 2022-09-23 | 长虹三杰新能源有限公司 | Preparation method and application of flexible electrode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109192952A (en) * | 2018-09-06 | 2019-01-11 | 中国科学技术大学 | A kind of cobalt disulfide/carbon nano-fiber composite material and preparation method thereof |
-
2020
- 2020-07-07 CN CN202010648817.5A patent/CN111943256A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109192952A (en) * | 2018-09-06 | 2019-01-11 | 中国科学技术大学 | A kind of cobalt disulfide/carbon nano-fiber composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| BHAVANA JOSHI ET AL.: ""Atomic-layer-deposited TiO2-SnZnO/carbon nanofiber composite as highly stable,flexible and freestanding anode material for lithium-ion batteries"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| YUNLEI ZHONG ET AL.: ""Flexible Electrospun Carbon Nanofiber/Tin(IV) Sulfide Core/Sheath Membranes for Photocatalytically Treating Chromium(VI)-Containing Wastewater"", 《ACS APPL. MATER. INTERFACES》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113745477A (en) * | 2021-08-25 | 2021-12-03 | 福建师范大学 | Preparation method and application of sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material |
| CN113823782A (en) * | 2021-08-25 | 2021-12-21 | 福建师范大学 | Preparation method and application of sulfur-doped polyacrylonitrile-chlorella derived carbon composite sodium ion battery negative electrode material |
| CN113823782B (en) * | 2021-08-25 | 2023-08-04 | 福建师范大学 | Preparation method and application of sulfur-doped polyacrylonitrile-chlorella-derived carbon composite sodium ion battery anode material |
| CN113745477B (en) * | 2021-08-25 | 2023-08-04 | 福建师范大学 | Preparation method and application of sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material |
| CN113998740A (en) * | 2021-10-25 | 2022-02-01 | 同济大学 | C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method |
| CN113998740B (en) * | 2021-10-25 | 2022-10-14 | 同济大学 | C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method |
| CN114094073A (en) * | 2021-11-12 | 2022-02-25 | 中博龙辉装备集团股份有限公司 | Tin dioxide @ carbon foam self-supporting composite material and preparation method and application thereof |
| CN114551891A (en) * | 2022-04-27 | 2022-05-27 | 潍坊科技学院 | Tin disulfide/titanium dioxide/carbon composite material and preparation method and application thereof |
| CN114551891B (en) * | 2022-04-27 | 2022-06-24 | 潍坊科技学院 | Tin disulfide/titanium dioxide/carbon composite material and preparation method and application thereof |
| CN115101719A (en) * | 2022-05-27 | 2022-09-23 | 长虹三杰新能源有限公司 | Preparation method and application of flexible electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111943256A (en) | Preparation method and application of flexible self-supporting tin-based sulfide-carbon composite material | |
| CN107799757B (en) | MoS2Nitrogen-doped carbon tube composite material and preparation method and application thereof | |
| CN111048763B (en) | Nano tin-silicon composite anode material and preparation method and application thereof | |
| CN108232115B (en) | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery | |
| WO2021120155A1 (en) | Nano-tin-silicon composite negative electrode material, and preparation method therefor and use thereof | |
| CN107069001B (en) | Honeycomb zinc sulfide/carbon composite negative electrode material and preparation method thereof | |
| CN108281627B (en) | Germanium-carbon composite negative electrode material for lithium ion battery and preparation method thereof | |
| Huang et al. | Outstanding electrochemical performance of N/S co-doped carbon/Na3V2 (PO4) 3 hybrid as the cathode of a sodium-ion battery | |
| CN110808368A (en) | SnS/TiO for potassium ion battery cathode2rGO composite material, preparation method and electrolyte matched with same | |
| CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
| CN112038614B (en) | Negative electrode material for sodium ion battery and preparation method thereof | |
| CN112010291B (en) | Preparation method and application of nickel-doped molybdenum disulfide/graphene three-dimensional composite material | |
| CN108598405B (en) | Preparation method of three-dimensional graphene tin oxide carbon composite negative electrode material | |
| CN114291796A (en) | Potassium ion battery negative electrode material and preparation method and application thereof | |
| CN111943259A (en) | Carbon-coated mesoporous dual-phase titanium dioxide and preparation method and energy storage application thereof | |
| CN111531181A (en) | Preparation method of high-performance porous honeycomb tin-carbon lithium battery cathode material | |
| CN113488343B (en) | MOFs porous carbon-based multi-component flexible electrode, preparation method and application | |
| CN109192938B (en) | Flexible material and preparation method and application thereof | |
| CN110311111A (en) | N adulterates CNT in-stiu coating Co nano particle composite material and preparation and application | |
| CN108110231B (en) | Carbon-coated Fe4N nano composite material, preparation method and application thereof | |
| CN111416124B (en) | Self-standing Sn-SnS/CNTs @ C flexible film and preparation and application thereof | |
| WO2023236575A1 (en) | Carbon matrix composite vanadium nitride nano array, and preparation method therefor and use thereof | |
| CN111320207B (en) | Preparation and application of molybdenum sulfide material | |
| CN110783542A (en) | Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery | |
| CN112186165B (en) | Protein fiber loaded with Ni nanoparticles and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201117 |
|
| WD01 | Invention patent application deemed withdrawn after publication |