CN111416124B - Self-standing Sn-SnS/CNTs @ C flexible film and preparation and application thereof - Google Patents

Self-standing Sn-SnS/CNTs @ C flexible film and preparation and application thereof Download PDF

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CN111416124B
CN111416124B CN202010230244.4A CN202010230244A CN111416124B CN 111416124 B CN111416124 B CN 111416124B CN 202010230244 A CN202010230244 A CN 202010230244A CN 111416124 B CN111416124 B CN 111416124B
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cnts
film
spinning
flexible film
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CN111416124A (en
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杨艳玲
孙瑜
陈志刚
朱建锋
陈华军
锁国权
冯雷
叶晓慧
张荔
侯小江
邹鑫鑫
和茹梅
毕雅欣
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0422—Cells or battery with cylindrical casing
    • H01M10/0427—Button cells
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/022—Electrodes made of one single microscopic fiber
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a self-supporting Sn-SnS/CNTs @ C flexible film, and a preparation method and application thereof. The synthesized flexible Sn-SnS/CNTs @ C film is a conductive network, electrons can be freely transmitted through the high-conductivity carbon fibers and the CNT, and the problem of poor conductivity caused by agglomeration of Sn-SnS nano particles is greatly relieved. Furthermore, carbon fibers outside the Sn-SnS/CNTs can effectively prevent particles from falling off, and the electrochemical cycle life of the film is prolonged.

Description

Self-standing Sn-SnS/CNTs @ C flexible film and preparation and application thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a self-supporting Sn-SnS/CNTs @ C flexible film, and preparation and application thereof.
Background
The lithium ion battery has the advantages of high energy density, high average output voltage, small self-discharge, excellent cycle stability and the like, and is widely applied to the fields of mobile phones, notebook computers, power automobiles and the like. At present, the theoretical capacity of the commercialized graphite cathode material is only 372mAh/g, the demand of future high-capacity batteries cannot be met, and the long-term development of lithium ion batteries is restricted by the shortage of lithium resources. The sodium reserves are abundant, the cost is cheap, and the sodium ion battery has gradually become the research make internal disorder or usurp hotspot in the energy field in recent years. The radius of sodium ions is about 1.4 times that of lithium ions relative to lithium ions, which makes reversible oxidation/reduction reactions of typical intercalation-based lithium ion electrode materials difficult.
At present, intensive research into novel electrode materials for sodium ion batteries has been carried out. The sodium ion battery cathode material stores energy by utilizing an alloying/dealloying process of sodium ion storage. Theoretical prediction shows that Ge, Sn, Pb and the like can perform alloying/dealloying reaction with sodium, and therefore can be used as anode materials of sodium-ion batteries. Of these materials, Sn is due to its high theoretical capacity (847mA h g)-1) And has attracted great interest to researchers. Sn may be based on chemical transformation and reversible Na alloying reactions. On the other hand, a large number of changes range from Sn to Na15Sn4The volume expansion ratio of the alloy was calculated to be 424%. This can lead to particle breakage and growth of unstable solid-electrolyte interphase (SEI film), which in turn can lead to rapid capacity loss of Sn-based sodium ion anodes. Therefore, the selection of a suitable battery electrode material has great significance for developing a novel sodium ion battery which is environment-friendly, stable in structure, suitable in electrochemical platform and large in specific capacity.
Disclosure of Invention
The invention aims to solve the technical problem of providing a self-supporting Sn-SnS/CNTs @ C flexible film and preparation and application thereof aiming at the defects in the prior art, and overcoming the defects of large volume change, poor conductivity and poor electrode stability of Sn in the charging and discharging processes.
The invention adopts the following technical scheme:
a preparation method of a self-supporting Sn-SnS/CNTs @ C flexible film comprises the following steps:
s1, carrying out high-energy ball milling on the Sn particles and the S powder to obtain Sn-SnS composite powder A; then, mixing the Sn-SnS composite powder A with CNTs, and then carrying out ball milling to obtain Sn-SnS/CNTs composite powder B;
s2, blending carbon precursor polyacrylonitrile and a pyrolytic polymer polymethyl methacrylate solution by using DMF as a solvent to obtain a spinning solution C; then, adding the Sn-SnS/CNTs composite powder B prepared in the step S1 into the spinning solution C, and stirring to obtain a spinning solution D; then carrying out electrostatic spinning to obtain a spinning film E;
s3, drying the spinning film E under the vacuum condition to remove residual DMF, and carrying out heat treatment and annealing treatment to obtain the free-standing Sn-SnS/CNTs @ C flexible film.
Specifically, in step S1, the weight ratio of Sn particles to S powder is 1:0.5, the weight ratio of steel balls to particles in the high-energy ball milling treatment is 15:1, and the ball milling time is 6-10 hours.
Specifically, in step S1, the weight ratio of the Sn-SnS composite powder a to the CNTs is (3-9): (2-1) the ball milling time is 2-3 h.
Specifically, in step S2, the mass ratio of the carbon precursor polyacrylonitrile to the pyrolyzed polymer polymethyl methacrylate is (7-9): (3-1).
Specifically, in step S2, the mass fraction of the Sn-SnS/CNTs composite powder B in the spinning solution C is 20-30%, and the spinning solution D is obtained by stirring at 70-90 ℃ for 2-3 h.
Specifically, in step S2, the electrostatic spinning specifically includes: the speed is 1-3 mL/h, the voltage is 20kV, the distance between a needle head and a rotary collector is 10-20 cm, the temperature in an electrostatic spinning chamber is 25 +/-5 ℃, and the humidity is 50 +/-5%.
Specifically, in step S3, the step of removing residual DMF specifically includes: drying for 1-2 hours at the temperature of 60-80 ℃.
Specifically, in step S3, the heat treatment specifically includes: heat treatment is carried out for 2 hours at the temperature of 250-300 ℃; the annealing treatment specifically comprises the following steps: and (3) in a high-purity nitrogen atmosphere, the temperature is 600-800 ℃, and the time is 2-3 hours.
The invention also discloses a self-supporting Sn-SnS/CNTs @ C flexible film prepared by the method.
The invention also provides a button cell, which is characterized in that the self-supporting Sn-SnS/CNTs @ C flexible film prepared by the method or prepared by the method is used as a negative electrode material of a sodium ion battery, and metal sodium is used as a counter electrode; mixing ethyl carbonate and dimethyl carbonate solution of NaPF6 as electrolyte in the volume ratio of 1 to 1; the diaphragm is a celgard2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides a preparation method of a self-supporting Sn-SnS/CNTs @ C flexible film, which is prepared by adopting a high-energy ball milling technology and an electrostatic spinning technology, and has the advantages of simple synthesis process and easy operation. And the carbonized spinning product can be directly used as a self-supporting substrate for a battery cathode material, so that the influence of a binder in the traditional battery assembly process is avoided.
Furthermore, SnS can be used as a buffer matrix to relieve the agglomeration of the nano-particles. The flexibility and the ultrahigh conductivity of the carbon nano tube can greatly relieve the problem of poor internal conductivity of the Sn-SnS caused by agglomeration.
Further, the carbonized conductive carbon fibers can further limit the breakage of the material, and can increase the conductivity of the whole electrode.
Further, the conductive carbon fiber network can be free-standing as a film while enhancing the transport of electrons across the film.
A free-standing Sn-SnS/CNTs @ C flexible film.
A button cell can avoid the film coating process of the cell and greatly shorten the manufacturing process of the cell. In addition, the influence of the binder on the conductivity of the electrode is avoided, and the active substance of the electrode plays the most role, so that the electrochemical performance of the whole electrode is in the optimal state.
In conclusion, the material disclosed by the invention is easy to obtain and synthesize, simple in process, easy to operate and capable of being produced and applied in a large scale. The synthesized flexible Sn-SnS/CNTs @ C film is self-formed into a conductive network, and the transmission of electrons is fast. The carbon fibers outside the Sn-SnS/CNTs can effectively prevent particles from falling off and prolong the cycle life of the film.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is an SEM image of the present invention, wherein (a) is an XRD image of a prepared flexible film; (b) is Roman; (c) is SEM picture of Sn-SnS/CNTs; (d) is the particle size distribution of Sn-SnS/CNTs particles in the graph c; (e) SEM image of 50 μm Sn-SnS/CNTs @ C carbon fiber network; (f) is an SEM picture of a 2 mu m Sn-SnS/CNTs @ C carbon fiber network; (g) is SEM picture of 500nm Sn-SnS/CNTs @ C carbon fiber network; FIG. h is a particle diameter distribution diagram of the fiber tube diameter in FIG. e;
FIG. 2 is TEM images of Sn-SnS/CNTs at different magnifications, wherein (a) is a TEM image of 1 μm Sn-SnS/CNTs, (b) is a TEM image of 100nm Sn-SnS/CNTs, (c) is a TEM image of 10nm Sn-SnS/CNTs, and (d) is a Mapping image of Sn-SnS/CNTs; (e) TEM images at different magnifications of a 1 μm Sn-SnS/CNTs @ C carbon fiber network; (f) TEM images at different magnifications of a 500nm Sn-SnS/CNTs @ C carbon fiber network; (g) is Roll; (h) is Fold; (i) is a flexible display of a film; (j) is a free-standing display of the film;
FIG. 3 is a comparative graph in which (a) is a thin film electrode at a high current density of 1A g-1Electrochemical performance diagram of 1000 cycles of lower cycle. And (b and c) are SEM images of the thin film electrode after 100 circles and 500 circles respectively.
Detailed Description
The invention relates to a preparation method of a self-supporting Sn-SnS/CNTs @ C flexible film, which comprises the following steps:
s1, and preparation of the Sn-SnS/CNTs composite material:
firstly, carrying out high-energy ball milling on Sn particles and S powder at a weight ratio of 1:0.5 (the weight ratio of steel balls to particles is 15:1), and carrying out ball milling for 6-10 hours to obtain Sn-SnS composite powder A; then, mixing and ball-milling the A and the CNTs for 2-3 hours according to the weight ratio of 3: 2-9: 1 to obtain Sn-SnS/CNTs composite powder B;
s2, preparing a free-standing Sn-SnS/CNTs flexible film:
using DMF as a solvent, and blending carbon precursor Polyacrylonitrile (PAN) and a pyrolytic polymer polymethyl methacrylate (PMMA) solution to obtain a spinning stock solution C (the mass ratio of PAN/PMMA is 7: 3-9: 1); then, adding the prepared B into a spinning solution C (mass fraction: 20-30%), and stirring for 2-3 hours at 70-90 ℃ to obtain a spinning solution D; then carrying out electrostatic spinning on the spinning solution D at the speed of 1-3 mL/h and the voltage of 20kV and the distance between a needle head and a rotary collector of 10-20 cm, and controlling the temperature and the humidity in an electrostatic spinning chamber at 25 +/-5 ℃ and 50 +/-5% respectively to obtain a spinning film E;
s3, preparation of a free-standing Sn-SnS/CNTs @ C flexible film:
drying the spinning film E for 1-2 hours at 60-80 ℃ in vacuum to completely remove residual DMF, carrying out heat treatment on the film E for 2 hours at 250-300 ℃ to pre-oxidize PAN, and then annealing the film E for 2-3 hours at 600-800 ℃ under high-purity nitrogen (99.99%) to obtain the final self-standing Sn-SnS/CNTs @ C flexible film.
The free-standing Sn-SnS/CNTs @ C flexible film is prepared based on the high-energy ball milling technology and the electrostatic spinning technology, and is used as a negative electrode material of a sodium ion battery to be assembled into a button battery.
The specific method for assembling the button cell is as follows: the free-standing Sn-SnS/CNTs @ C flexible film is directly used as a self-supporting substrate and is cut into a negative plate with the diameter of 10mm for the experimental battery by a cutting machine.
Taking metal sodium as a counter electrode; mixing ethyl carbonate and dimethyl carbonate solution of NaPF6 as electrolyte in the volume ratio of 1 to 1; the diaphragm is a celgard2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Step 1, preparing the Sn-SnS/CNTs composite material:
firstly, carrying out high-energy ball milling on Sn particles and S powder at a weight ratio of 1:0.5 (the weight ratio of steel balls to particles is 15:1), and carrying out ball milling for 6 hours to obtain Sn-SnS composite powder A; then, mixing and ball-milling the A and the CNTs for 2 hours according to the weight ratio of 3:2 to obtain Sn-SnS/CNTs composite powder B;
step 2, preparing the self-supporting Sn-SnS/CNTs flexible film:
blending a carbon precursor Polyacrylonitrile (PAN) with a pyrolyzed polymer polymethyl methacrylate (PMMA) solution using DMF as a solvent to obtain a dope C (PAN/PMMA mass ratio of 7: 3); then, the above-prepared B was added to the mixed solution C (mass fraction: 20%) and stirred at 70 ℃ for 2 hours to obtain a spinning solution D; then carrying out electrostatic spinning on the spinning solution D at the speed of 1mL/h, the voltage of 20kV and the distance between the needle head and the rotary collector being 10, and respectively controlling the temperature and the humidity in an electrostatic spinning chamber at 25 +/-5 ℃ and 50 +/-5% to obtain a spinning film E;
step 3, preparing a self-supporting Sn-SnS/CNTs @ C flexible film:
finally, the spun film E was dried under vacuum at 60 ℃ for 1 hour to completely remove residual DMF, the film E was heat treated at 250 ℃ for 2 hours to pre-oxidize PAN and then annealed at 600 ℃ for 2 hours under high purity nitrogen (99.99%) to obtain the final free-standing Sn-SnS/CNTs @ C flexible film.
The self-supporting Sn-SnS/CNTs @ C flexible film is prepared based on the high-energy ball milling technology and the electrostatic spinning technology, and is used as a negative electrode material of a sodium ion battery to be assembled into a button battery.
The specific method for assembling the button cell is as follows: the free-standing Sn-SnS/CNTs @ C flexible film is directly used as a self-supporting substrate and is cut into a negative plate with the diameter of 10mm for the experimental battery by a cutting machine.
Taking metal sodium as a counter electrode; mixing ethyl carbonate and dimethyl carbonate solution of NaPF6 as electrolyte in the volume ratio of 1 to 1; the diaphragm is a celgard2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Example 2
Step 1, preparing the Sn-SnS/CNTs composite material:
firstly, carrying out high-energy ball milling on Sn particles and S powder at a weight ratio of 1:0.5 (the weight ratio of steel balls to particles is 15:1), and carrying out ball milling for 7 hours to obtain Sn-SnS composite powder A; then, mixing and ball-milling the A and the CNTs for 2 hours according to the weight ratio of 7:3 to obtain Sn-SnS/CNTs composite powder B;
step 2, preparing the self-supporting Sn-SnS/CNTs flexible film:
blending a carbon precursor Polyacrylonitrile (PAN) with a pyrolyzed polymer polymethyl methacrylate (PMMA) solution using DMF as a solvent to obtain a dope C (PAN/PMMA mass ratio of 7: 3); then, the above-prepared B was added to the mixed solution C (mass fraction: 25%) and stirred at 80 ℃ for 2 hours to obtain a spinning solution D; then carrying out electrostatic spinning on the spinning solution D at the speed of 1mL/h, the voltage of 20kV and the distance between the needle head and the rotary collector being 15cm, and respectively controlling the temperature and the humidity in an electrostatic spinning chamber at 25 +/-5 ℃ and 50 +/-5% to obtain a spinning film E;
step 3, preparing a self-supporting Sn-SnS/CNTs @ C flexible film:
finally, the spun film E was dried under vacuum at 60 ℃ for 1 hour to completely remove residual DMF, the film E was heat treated at 280 ℃ for 2 hours to pre-oxidize PAN and then annealed at 700 ℃ for 2 hours under high purity nitrogen (99.99%) to obtain the final free-standing Sn-SnS/CNTs @ C flexible film.
The self-supporting Sn-SnS/CNTs @ C flexible film is prepared based on the high-energy ball milling technology and the electrostatic spinning technology, and is used as a negative electrode material of a sodium ion battery to be assembled into a button battery.
The specific method for assembling the button cell is as follows: the free-standing Sn-SnS/CNTs @ C flexible film is directly used as a self-supporting substrate and is cut into a negative plate with the diameter of 10mm for the experimental battery by a cutting machine.
Taking metal sodium as a counter electrode; mixing ethyl carbonate and dimethyl carbonate solution of NaPF6 as electrolyte in the volume ratio of 1 to 1; the diaphragm is a celgard2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Example 3
Step 1, preparing the Sn-SnS/CNTs composite material:
firstly, carrying out high-energy ball milling on Sn particles and S powder at a weight ratio of 1:0.5 (the weight ratio of steel balls to particles is 15:1), and carrying out ball milling for 8 hours to obtain Sn-SnS composite powder A; then, mixing and ball-milling the A and the CNTs for 3 hours according to the weight ratio of 4:1 to obtain Sn-SnS/CNTs composite powder B;
step 2, preparing the self-supporting Sn-SnS/CNTs flexible film:
blending a carbon precursor Polyacrylonitrile (PAN) with a pyrolyzed polymer polymethyl methacrylate (PMMA) solution using DMF as a solvent to obtain a dope C (PAN/PMMA mass ratio of 7: 3); then, the above-prepared B was added to the mixed solution C (mass fraction: 25%) and stirred at 70 ℃ for 3 hours to obtain a spinning solution D; then carrying out electrostatic spinning on the spinning solution D at the speed of 1.5mL/h, the voltage of 20kV and the distance between the needle head and the rotary collector being 18cm, and respectively controlling the temperature and the humidity in an electrostatic spinning chamber at 25 +/-5 ℃ and 50 +/-5% to obtain a spinning film E;
step 3, preparing a self-supporting Sn-SnS/CNTs @ C flexible film:
finally, spun film E was dried under vacuum at 60 ℃ for 1.5 hours to completely remove residual DMF, film E was heat treated at 280 ℃ for 2 hours to pre-oxidize PAN and then annealed at 800 ℃ for 2 hours under high purity nitrogen (99.99%) to obtain the final free-standing Sn-SnS/CNTs @ C flexible film.
The self-supporting Sn-SnS/CNTs @ C flexible film is prepared based on the high-energy ball milling technology and the electrostatic spinning technology, and is used as a negative electrode material of a sodium ion battery to be assembled into a button battery.
The specific method for assembling the button cell is as follows: the free-standing Sn-SnS/CNTs @ C flexible film is directly used as a self-supporting substrate and is cut into a negative plate with the diameter of 10mm for the experimental battery by a cutting machine.
Taking metal sodium as a counter electrode; mixing ethyl carbonate and dimethyl carbonate solution of NaPF6 as electrolyte in the volume ratio of 1 to 1; the diaphragm is a celgard2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Example 4
Step 1, preparing the Sn-SnS/CNTs composite material:
firstly, carrying out high-energy ball milling on Sn particles and S powder at a weight ratio of 1:0.5 (the weight ratio of steel balls to particles is 15:1), and carrying out ball milling for 8 hours to obtain Sn-SnS composite powder A; then, mixing and ball-milling the A and the CNTs for 3 hours according to the weight ratio of 4:1 to obtain Sn-SnS/CNTs composite powder B;
step 2, preparing the self-supporting Sn-SnS/CNTs flexible film:
blending a carbon precursor Polyacrylonitrile (PAN) with a pyrolyzed polymer polymethyl methacrylate (PMMA) solution using DMF as a solvent to obtain a dope C (PAN/PMMA mass ratio of 4: 1); then, the above-prepared B was added to the mixed solution C (mass fraction: 25%) and stirred at 80 ℃ for 3 hours to obtain a spinning solution D; then carrying out electrostatic spinning on the spinning solution D at the speed of 1.5mL/h, the voltage of 20kV and the distance between the needle head and the rotary collector being 15cm, and respectively controlling the temperature and the humidity in an electrostatic spinning chamber at 25 +/-5 ℃ and 50 +/-5% to obtain a spinning film E;
step 3, preparing a self-supporting Sn-SnS/CNTs @ C flexible film:
finally, the spun film E was dried under vacuum at 60 ℃ for 2 hours to completely remove residual DMF, the film E was heat treated at 280 ℃ for 2 hours to pre-oxidize PAN and then annealed at 800 ℃ for 2 hours under high purity nitrogen (99.99%) to obtain the final free-standing Sn-SnS/CNTs @ C flexible film.
The self-supporting Sn-SnS/CNTs @ C flexible film is prepared based on the high-energy ball milling technology and the electrostatic spinning technology, and is used as a negative electrode material of a sodium ion battery to be assembled into a button battery.
The specific method for assembling the button cell is as follows: the free-standing Sn-SnS/CNTs @ C flexible film is directly used as a self-supporting substrate and is cut into a negative plate with the diameter of 10mm for the experimental battery by a cutting machine.
Taking metal sodium as a counter electrode; mixing ethyl carbonate and dimethyl carbonate solution of NaPF6 as electrolyte in the volume ratio of 1 to 1; the diaphragm is a celgard2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Example 5
Step 1, preparing the Sn-SnS/CNTs composite material:
firstly, carrying out high-energy ball milling on Sn particles and S powder at a weight ratio of 1:0.5 (the weight ratio of steel balls to particles is 15:1), and carrying out ball milling for 8 hours to obtain Sn-SnS composite powder A; then, mixing and ball-milling the A and the CNTs for 2 hours according to the weight ratio of 9:1 to obtain Sn-SnS/CNTs composite powder B;
step 2, preparing the self-supporting Sn-SnS/CNTs flexible film:
blending a carbon precursor Polyacrylonitrile (PAN) with a pyrolyzed polymer polymethyl methacrylate (PMMA) solution using DMF as a solvent to obtain a dope C (PAN/PMMA mass ratio 9: 1); then, the above-prepared B was added to the mixed solution C (mass fraction: 20%) and stirred at 70 ℃ for 2 hours to obtain a spinning solution D; then carrying out electrostatic spinning on the spinning solution D at the speed of 3mL/h and the voltage of 20kV and the distance between a needle head and a rotary collector being 20cm, and respectively controlling the temperature and the humidity in an electrostatic spinning chamber at 25 +/-5 ℃ and 50 +/-5% to obtain a spinning film E;
step 3, preparing a self-supporting Sn-SnS/CNTs @ C flexible film:
and finally, drying the spinning film E at 70 ℃ for 2 hours in vacuum to completely remove residual DMF, carrying out heat treatment on the film E at 250 ℃ for 2 hours to pre-oxidize PAN, and annealing at 750 ℃ for 2-3 hours under high-purity nitrogen (99.99%) to obtain the final free-standing Sn-SnS/CNTs @ C flexible film.
The self-supporting Sn-SnS/CNTs @ C flexible film is prepared based on the high-energy ball milling technology and the electrostatic spinning technology, and is used as a negative electrode material of a sodium ion battery to be assembled into a button battery.
The specific method for assembling the button cell is as follows: the free-standing Sn-SnS/CNTs @ C flexible film is directly used as a self-supporting substrate and is cut into a negative plate with the diameter of 10mm for the experimental battery by a cutting machine.
Taking metal sodium as a counter electrode; mixing ethyl carbonate and dimethyl carbonate solution of NaPF6 as electrolyte in the volume ratio of 1 to 1; the diaphragm is a celgard2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Example 6
Step 1, preparing the Sn-SnS/CNTs composite material:
firstly, carrying out high-energy ball milling on Sn particles and S powder at a weight ratio of 1:0.5 (the weight ratio of steel balls to particles is 15:1), and carrying out ball milling for 8 hours to obtain Sn-SnS composite powder A; then, mixing and ball-milling the A and the CNTs for 3 hours according to the weight ratio of 9:1 to obtain Sn-SnS/CNTs composite powder B;
step 2, preparing the self-supporting Sn-SnS/CNTs flexible film:
blending a carbon precursor Polyacrylonitrile (PAN) with a pyrolyzed polymer polymethyl methacrylate (PMMA) solution using DMF as a solvent to obtain a dope C (PAN/PMMA mass ratio of 7: 3); then, the above-prepared B was added to the mixed solution C (mass fraction: 25%) and stirred at 90 ℃ for 2 hours to obtain a spinning solution D; then carrying out electrostatic spinning on the spinning solution D at the speed of 2.5mL/h and the voltage of 20kV and the distance between the needle head and the rotary collector being 20cm, and respectively controlling the temperature and the humidity in an electrostatic spinning chamber at 25 +/-5 ℃ and 50 +/-5% to obtain a spinning film E;
step 3, preparing a self-supporting Sn-SnS/CNTs @ C flexible film:
finally, the spun film E was dried under vacuum at 80 ℃ for 2 hours to completely remove residual DMF, the film E was heat treated at 300 ℃ for 2 hours to pre-oxidize PAN and then annealed at 800 ℃ for 2 hours under high purity nitrogen (99.99%) to obtain the final free-standing Sn-SnS/CNTs @ C flexible film.
The self-supporting Sn-SnS/CNTs @ C flexible film is prepared based on the high-energy ball milling technology and the electrostatic spinning technology, and is used as a negative electrode material of a sodium ion battery to be assembled into a button battery.
The specific method for assembling the button cell is as follows: the free-standing Sn-SnS/CNTs @ C flexible film is directly used as a self-supporting substrate and is cut into a negative plate with the diameter of 10mm for the experimental battery by a cutting machine.
Taking metal sodium as a counter electrode; mixing ethyl carbonate and dimethyl carbonate solution of NaPF6 as electrolyte in the volume ratio of 1 to 1; the diaphragm is a celgard2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Example 7
Step 1, preparing the Sn-SnS/CNTs composite material:
firstly, carrying out high-energy ball milling on Sn particles and S powder at a weight ratio of 1:0.5 (the weight ratio of steel balls to particles is 15:1), and carrying out ball milling for 10 hours to obtain Sn-SnS composite powder A; then, mixing and ball-milling the A and the CNTs for 3 hours according to the weight ratio of 9:1 to obtain Sn-SnS/CNTs composite powder B;
step 2, preparing the self-supporting Sn-SnS/CNTs flexible film:
blending a carbon precursor Polyacrylonitrile (PAN) with a pyrolyzed polymer polymethyl methacrylate (PMMA) solution using DMF as a solvent to obtain a dope C (PAN/PMMA mass ratio 9: 1); then, the above-prepared B was added to the mixed solution C (mass fraction: 30%) and stirred at 90 ℃ for 3 hours to obtain a spinning solution D; then carrying out electrostatic spinning on the spinning solution D at the speed of 3mL/h and the voltage of 20kV and the distance between a needle head and a rotary collector being 20cm, and respectively controlling the temperature and the humidity in an electrostatic spinning chamber at 25 +/-5 ℃ and 50 +/-5% to obtain a spinning film E;
step 3, preparing a self-supporting Sn-SnS/CNTs @ C flexible film:
finally, the spun film E was dried under vacuum at 80 ℃ for 2 hours to completely remove residual DMF, the film E was heat treated at 300 ℃ for 2 hours to pre-oxidize PAN and then annealed at 800 ℃ for 3 hours under high purity nitrogen (99.99%) to obtain the final free-standing Sn-SnS/CNTs @ C flexible film.
The self-supporting Sn-SnS/CNTs @ C flexible film is prepared based on the high-energy ball milling technology and the electrostatic spinning technology, and is used as a negative electrode material of a sodium ion battery to be assembled into a button battery.
The specific method for assembling the button cell is as follows: the free-standing Sn-SnS/CNTs @ C flexible film is directly used as a self-supporting substrate and is cut into a negative plate with the diameter of 10mm for the experimental battery by a cutting machine.
Taking metal sodium as a counter electrode; mixing ethyl carbonate and dimethyl carbonate solution of NaPF6 as electrolyte in the volume ratio of 1 to 1; the diaphragm is a celgard2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Referring to fig. 1, (a) is an XRD pattern of the prepared flexible thin film; (b) is Roman; (c) is SEM picture of Sn-SnS/CNTs; (d) is the particle size distribution of Sn-SnS/CNTs particles in the graph c; (e) SEM image of 50 μm Sn-SnS/CNTs @ C carbon fiber network; (f) is an SEM picture of a 2 mu m Sn-SnS/CNTs @ C carbon fiber network; (g) is SEM picture of 500nm Sn-SnS/CNTs @ C carbon fiber network; and the graph h is the particle diameter distribution diagram of the fiber tube diameter in the graph e.
Referring to FIG. 2, (a) is a TEM image of 1 μm Sn-SnS/CNTs, (b) is a TEM image of 100nm Sn-SnS/CNTs, (c) is a TEM image of 10nm Sn-SnS/CNTs, and (d) is a Mapping image of Sn-SnS/CNTs; (e) TEM images at different magnifications of a 1 μm Sn-SnS/CNTs @ C carbon fiber network; (f) TEM images at different magnifications of a 500nm Sn-SnS/CNTs @ C carbon fiber network; (g) is Roll; (h) is Fold; (i) is a flexible display of a film; (j) is a free-standing display of the film.
Referring to FIG. 3, (a) is a thin film electrode at a high current density of 1A g-1Electrochemical performance diagram of 1000 cycles of lower cycle. And (b and c) are SEM images of the thin film electrode after 100 circles and 500 circles respectively.
In conclusion, the structure of the invention uses the carbon fiber to limit Sn-SnS/CNTs so as to improve the cycling stability of the electrode. To address the low conductivity inside the large agglomerates due to inter-particle adhesion, we interlaced Sn-SnS agglomerates with Carbon Nanotubes (CNTs) with excellent flexibility and conductivity. Moreover, the carbon fiber design has multi-level advantages:
1) the carbon fiber can effectively adapt to the expansion of Sn-SnS in the oxygenation/deoxidation process, and the integrity and stability of the electrode are enhanced, so that excellent cycle performance is realized;
2) the carbon fibers as a conductive matrix provide a large accessible area for the electrolyte, which is further interconnected to form an effective 3D conductive network, thereby having excellent electronic conductivity;
3) to avoid the Sn-SnS nanoparticles from detaching from the CNTs due to volume changes during cycling and further maximize the contact area between the agglomerates and the conductive carbon, the carbon fibers have volume expansion spaces to encapsulate Sn-SnS/CNTs agglomerates (Sn-SnS/CNTs @ C). Sn-SnS/CNTs @ C has an extended cycle life and excellent sodium storage properties, benefiting from the unique functionality described above.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (5)

1. A preparation method of a self-supporting Sn-SnS/CNTs @ C flexible film is characterized by comprising the following steps:
s1, carrying out high-energy ball milling on the Sn particles and the S powder to obtain Sn-SnS composite powder A, wherein the weight ratio of the Sn particles to the S powder is 1:0.5, the weight ratio of steel balls to the particles in the high-energy ball milling treatment is 15:1, and the ball milling time is 6-10 h; and then mixing the Sn-SnS composite powder A with CNTs, and then performing ball milling to obtain Sn-SnS/CNTs composite powder B, wherein the weight ratio of the Sn-SnS composite powder A to the CNTs is (3-9): (2-1), ball milling for 2-3 h;
s2, using DMF as a solvent, and blending carbon precursor polyacrylonitrile and a pyrolytic polymer polymethyl methacrylate solution to obtain a spinning stock solution C, wherein the mass ratio of the carbon precursor polyacrylonitrile to the pyrolytic polymer polymethyl methacrylate is (7-9): (3-1), stirring the Sn-SnS/CNTs composite powder B in the spinning stock solution C for 2-3 h at 70-90 ℃ for 20-30% by mass to obtain a spinning solution D; then, adding the Sn-SnS/CNTs composite powder B prepared in the step S1 into the spinning solution C, and stirring to obtain a spinning solution D; then carrying out electrostatic spinning to obtain a spinning film E;
s3, drying the spinning film E under a vacuum condition to remove residual DMF, and carrying out heat treatment and annealing treatment to obtain the free-standing Sn-SnS/CNTs @ C flexible film, wherein the heat treatment specifically comprises the following steps: heat treatment is carried out for 2 hours at the temperature of 250-300 ℃; the annealing treatment specifically comprises the following steps: and (3) in a high-purity nitrogen atmosphere, the temperature is 600-800 ℃, and the time is 2-3 hours.
2. The method according to claim 1, wherein in step S2, the electrospinning is specifically: the speed is 1-3 mL/h, the voltage is 20kV, the distance between a needle head and a rotary collector is 10-20 cm, the temperature in an electrostatic spinning chamber is 25 +/-5 ℃, and the humidity is 50 +/-5%.
3. The method of claim 1, wherein the step S3, the removing of the residual DMF comprises: drying for 1-2 hours at the temperature of 60-80 ℃.
4.A free-standing Sn-SnS/CNTs @ C flexible film, characterized by using claims 1 to 3Any one of the above methods.
5. Button cell, characterized in that the free-standing Sn-SnS/CNTs @ C flexible film prepared by the process of any one of claims 1 to 3 or claim 4 is used as the negative electrode material of sodium ion battery, with metallic sodium as the counter electrode; mixing ethyl carbonate and dimethyl carbonate solution of NaPF6 as electrolyte in the volume ratio of 1 to 1; the diaphragm is a celgard2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
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