CN107316989B - Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof - Google Patents

Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof Download PDF

Info

Publication number
CN107316989B
CN107316989B CN201710348570.3A CN201710348570A CN107316989B CN 107316989 B CN107316989 B CN 107316989B CN 201710348570 A CN201710348570 A CN 201710348570A CN 107316989 B CN107316989 B CN 107316989B
Authority
CN
China
Prior art keywords
ball milling
sulfur
composite material
powder
few
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.)
Active
Application number
CN201710348570.3A
Other languages
Chinese (zh)
Other versions
CN107316989A (en
Inventor
朱敏
程得亮
杨黎春
胡仁宗
曾美琴
鲁忠臣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201710348570.3A priority Critical patent/CN107316989B/en
Publication of CN107316989A publication Critical patent/CN107316989A/en
Priority to PCT/CN2017/111342 priority patent/WO2018209912A1/en
Application granted granted Critical
Publication of CN107316989B publication Critical patent/CN107316989B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—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
    • H01M4/38—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
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 tin sulfide/sulfur/few-layer graphene composite material and a preparation method and application thereof, and the preparation method comprises the following steps: adding tin powder, sulfur powder and expanded graphite into a ball milling tank, mixing, and performing ball milling by adopting a dielectric barrier discharge plasma assisted high-energy ball milling method to obtain the tin sulfide/sulfur/few-layer graphene composite material; in the mixture of tin powder, sulfur powder and expanded graphite, the mass fraction of the expanded graphite is 20-80%, the molar ratio of the tin powder to the sulfur powder is 1: 1-1: 4, the ball-to-material ratio of ball milling is 30: 1-70: 1, and the ball milling time is 10-40 h. The composite material is used as a lithium/sodium ion battery cathode material, shows excellent electrochemical performance, and has high capacity, excellent cycle performance and rate capability. The invention has the advantages of wide raw material source, simple preparation method, low cost, easy large-scale production and no pollution to the environment.

Description

Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof
Technical Field
The invention relates to the field of new energy materials, in particular to a tin sulfide/sulfur/few-layer graphene composite material, a preparation method thereof and application thereof in a lithium/sodium ion battery.
Background
Lithium ion batteries are widely used as power sources for various electronic products including mobile phones, notebook computers, and digital cameras, and as power batteries for mobile equipment including electric vehicles, because of their advantages such as high energy density and long cycle life. Along with the wide application of lithium ion batteries, on one hand, people put forward higher requirements on the performance of lithium ion batteries, including the requirements of higher capacity, higher power, longer cycle life and the like. At present, the lithium ion battery cathode material widely used in commercialization is mainly a graphite carbon material, the theoretical specific capacity of the lithium ion battery cathode material is low, and the development requirements of secondary batteries with high capacity, high power and long service life cannot be met, so that the development and research of the cathode material with high capacity are key points for promoting the further development of the lithium ion battery. On the other hand, global lithium resources are not abundant and the cost is high, which greatly restricts the large-scale application of lithium ion batteries. Compared with lithium resources, sodium resources are very rich and low in cost, and the sodium resources and the lithium resources are the same main group elements and have similar chemical properties, so that the development of the sodium-ion battery by using sodium to replace lithium has very wide application prospects. However, commercial lithium ion negative electrode graphite materials are difficult to intercalate sodium ions due to their larger ionic radius, which severely limits the development of sodium ion batteries.
Tin sulfide has higher theoretical specific capacity of lithium/sodium deintercalation (such as SnS)2The theoretical specific capacities of the lithium and the sodium which are deintercalated and intercalated are respectively 1230mAh g-1And 1135mAh g-1) And the method is widely concerned. However, research shows that when a single tin sulfide is used as a lithium/sodium ion electrode negative electrode material, huge volume expansion is generated in the lithium/sodium desorption process, so that electrode materials are pulverized, the electrode materials are separated from a current collector, and good electrochemical performance cannot be obtained.
Disclosure of Invention
The invention aims to provide a tin sulfide/sulfur/few-layer graphene composite material with simple method and excellent performance and a preparation method thereof. The obtained composite material has high capacity and excellent cycle performance and rate performance, and is particularly suitable for being used as a negative electrode material of a lithium/sodium ion battery.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a tin sulfide/sulfur/few-layer graphene composite material comprises the following steps: adding tin powder, sulfur powder and expanded graphite into a ball milling tank, mixing, and performing ball milling by adopting a dielectric barrier discharge plasma assisted high-energy ball milling method to obtain the tin sulfide/sulfur/few-layer graphene composite material; in the mixture of tin powder, sulfur powder and expanded graphite, the mass fraction of the expanded graphite is 20-80%, the molar ratio of the tin powder to the sulfur powder is 1: 1-1: 4, the ball-to-material ratio of ball milling is 30: 1-70: 1, and the ball milling time is 10-40 h.
The mass fraction of the expanded graphite is 30-50%.
The molar ratio of the tin powder to the sulfur powder is 1: 1-1: 3.
The ball-material ratio of the ball milling is 40: 1-60: 1.
The ball milling time is 15-30 h.
The dielectric barrier discharge plasma assisted high-energy ball milling method comprises the following specific steps:
(1) installing a front cover plate and an electrode rod of the ball milling tank, and respectively connecting iron cores in the front cover plate and the electrode rod with the positive electrode and the negative electrode of a plasma power supply, wherein the iron core in the electrode rod is connected with the positive electrode of the plasma power supply, and the front cover plate is connected with the negative electrode of the plasma power supply;
(2) filling a ball milling tank with milling balls and mixed powder of tin powder, sulfur powder and expanded graphite in a ratio;
(3) vacuumizing the ball milling tank through a vacuum valve, and then filling a discharge gas medium to enable the pressure value in the ball milling tank to reach 0.1 Mpa;
(4) and (3) switching on a plasma power supply, setting the voltage of the plasma power supply to be 15KV, the current to be 0.25A and the discharge frequency to be 60KHz, starting a driving motor to drive an excitation block, and simultaneously vibrating the rack and the ball milling tank fixed on the rack to perform dielectric barrier discharge plasma-assisted high-energy ball milling.
The excitation block adopts double amplitude of 7mm and motor speed of 960 r/min.
The discharge gas medium adopted by the dielectric barrier discharge plasma auxiliary high-energy ball milling method is inert gas or mixed gas of inert gas.
Tin sulfide/sulfur/few-layer graphene composite material (SnS) prepared by methodx/S/FLG composite material) made of nanocrystalline tin sulfide and amorphous tinThe composite material is formed by compounding crystalline sulfur and few-layer graphene, and the structure of the composite material is that nano-crystalline tin sulfide and amorphous sulfur are uniformly coated in a few-layer graphene carbon matrix.
The tin sulfide/sulfur/few-layer graphene composite material is applied to the preparation of a lithium/sodium ion battery cathode material.
According to the invention, tin sulfide is compounded with sulfur and a few-layer graphene carbon material, and a dielectric barrier discharge plasma auxiliary high-energy ball milling method is adopted to prepare the tin sulfide/sulfur/few-layer graphene composite material, the nanocrystalline tin sulfide in the composite material is also beneficial to the transmission of lithium/sodium ions, the few-layer graphene substrate is beneficial to the transmission of ions in the charging and discharging process, the electronic conductivity of the whole material is improved, and the huge volume change in the charging and discharging process of the tin sulfide is relieved. The obtained composite material has high capacity and excellent cycle performance and rate performance, and is particularly suitable for being used as a negative electrode material of a lithium/sodium ion battery.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention adopts the dielectric barrier discharge plasma auxiliary high-energy ball milling method to prepare the tin sulfide of the lithium/sodium ion battery cathode material for the first time, compared with the common chemical method for preparing the tin sulfide, the method has the advantages of wide raw material source, simple preparation method, low cost, easy large-scale production and no pollution to the environment.
(2) The tin sulfide/sulfur/few-layer graphene composite material is used as a lithium/sodium ion battery cathode material, and due to the compounding of few-layer graphene, the ionic migration and electronic conduction of the material can be improved, the huge volume change in the sodium intercalation process of tin sulfide is relieved, and the characteristics of high capacity, high cycle stability and the like are considered.
(3) The tin sulfide/sulfur/few-layer graphene composite material provided by the invention is used as a lithium/sodium ion battery cathode material, and shows high capacity and excellent cycle performance and rate performance.
Drawings
FIG. 1 is SnS prepared in example 3xXRD pattern of/S/FLG composite material;
FIG. 2 is a drawing showing a structure of example 3Prepared SnSxXPS sulfur spectra of/S/FLG composites;
FIG. 3 is SnS prepared in example 3xSEM image of/S/FLG composite material;
FIG. 4 is SnS prepared in example 3xHRTEM image of/S/FLG composite;
FIG. 5 is SnS prepared in example 3xA lithium intercalation charging and discharging curve diagram of the/S/FLG composite material;
FIG. 6 is SnS prepared in example 3xA lithium insertion cycle performance curve diagram of the/S/FLG composite material;
FIG. 7 is SnS prepared in example 3xA lithium insertion rate performance curve diagram of the/S/FLG composite material;
FIG. 8 is SnS prepared in example 3xA sodium-embedded charging and discharging curve diagram of the/S/FLG composite material;
FIG. 9 is SnS prepared in example 3xA sodium insertion cycle performance curve diagram of the/S/FLG composite material;
FIG. 10 is SnS prepared in example 3xAnd a sodium-insertion rate performance graph of the/S/FLG composite material.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The preparation of the composite material of each embodiment of the invention adopts a dielectric barrier discharge plasma auxiliary high-energy ball milling method.
The dielectric barrier discharge plasma assisted high-energy ball milling method comprises the following specific steps:
(1) installing a front cover plate and an electrode rod of the ball milling tank, and respectively connecting iron cores in the front cover plate and the electrode rod with the positive electrode and the negative electrode of a plasma power supply, wherein the iron core in the electrode rod is connected with the positive electrode of the plasma power supply, and the front cover plate is connected with the negative electrode of the plasma power supply;
(2) filling a ball milling tank with milling balls and mixed powder of tin powder, sulfur powder and expanded graphite in a ratio;
(3) vacuumizing the ball milling tank through a vacuum valve, and then filling inert gases such as discharge gas media argon, helium and the like or mixed gas of the inert gases to enable the pressure value in the ball milling tank to reach 0.1 Mpa;
(4) switching on a plasma power supply, setting the voltage of the plasma power supply to be 15KV, the current to be 0.25A and the discharge frequency to be 60KHz, starting a driving motor to drive an excitation block, and enabling a rack and a ball milling tank fixed on the rack to vibrate simultaneously to perform dielectric barrier discharge plasma-assisted high-energy ball milling; the excitation block adopts double amplitude of 7mm and motor speed of 960 r/min.
The prepared tin sulfide/sulfur/few-layer graphene composite material is used as a lithium ion battery cathode material to prepare a lithium ion battery:
SnSxMixing and pulping the/S/FLG composite material, the conductive agent Super P and the binder CMC according to the mass ratio of 8:1:1, and uniformly coating the mixture on a copper foil to prepare an electrode plate; in an argon atmosphere glove box, a lithium sheet is taken as a counter electrode, and the electrolyte is 1mol/LLIPF6The CR2016 button cell was assembled for testing with/EC/DEC (1: 1 by volume) with 5% by volume fluoroethylene carbonate (FEC) added and polypropylene as separator.
The prepared tin sulfide/sulfur/few-layer graphene composite material is used as a negative electrode material of a sodium ion battery to prepare the sodium ion battery:
SnSxMixing and pulping the/S/FLG composite material, the conductive agent Super P and the binder CMC according to the mass ratio of 8:1:1, and uniformly coating the mixture on a copper foil to prepare an electrode plate; in an argon atmosphere glove box, a sodium sheet is used as a counter electrode, and the electrolyte is 1mol/LNaClO4The CR2032 button cell is assembled by adding fluoroethylene carbonate (FEC) in a volume ratio of 5% into EC/PC (volume ratio of 1:1) and a glass fiber diaphragm to carry out testing.
Example 1
Adding tin powder, sulfur powder and expanded graphite raw material powder into a ball milling tank for mixing, wherein the mass fraction of the expanded graphite is 30%, the molar ratio of the tin powder to the sulfur powder is 1:1, the mass ratio of a grinding ball to the ball powder of the raw material is 50:1, and performing dielectric barrier discharge plasma assisted high-energy ball milling for 20 hours, wherein a discharge gas medium is argon.
And discharging and ball-milling to obtain the stannous sulfide/few-layer graphene composite material.
Preparing the prepared composite material into a lithium ion battery cathode electrode plate and assembling the battery with the cathode electrode plate 1A g-1The multiplying power of the SnS/FLG composite material is subjected to charge-discharge circulation between 0 and 3V, and the first reversible specific capacity of the SnS/FLG composite material is 746.5mAh g-1After circulating for 250 times, the reversible specific capacity is reduced to 588mAh g-1。
Preparing the prepared composite material into a negative electrode plate of a sodium-ion battery and assembling the battery to obtain a composite material with the weight ratio of 1A g-1The multiplying power of the SnS/FLG composite material is subjected to charge-discharge circulation between 0 and 3V, and the first reversible specific capacity of the SnS/FLG composite material is 443.9mAh g-1After 200 times of circulation, the reversible specific capacity is reduced to 373.4mAh g-1。
Example 2
The difference from example 1 is that the molar ratio of tin powder to sulfur powder is 1: 2.
After discharging and ball milling, tin reacts with sulfur to generate stannous sulfide and stannic sulfide, and the stannic sulfide/few-layer graphene composite material is obtained.
Preparing the prepared composite material into a lithium ion battery cathode electrode plate, assembling the lithium ion battery cathode electrode plate into a battery, and adding 1Ag-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/FLG composite material is 924.5mAh g-1After circulating for 250 times, the reversible specific capacity is reduced to 708mAh g-1。
Preparing the prepared composite material into a negative electrode plate of a sodium-ion battery and assembling the battery to obtain a composite material with the weight ratio of 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/FLG composite material is 560.9mAh g-1After 200 times of circulation, the reversible specific capacity is reduced to 508.6mAh g-1。
Example 3
The difference from example 1 is that the molar ratio of tin powder to sulfur powder is 1: 3.
After discharge ball milling, the prepared SnS is shown in FIG. 1xAn XRD (X-ray diffraction) spectrum of the/S/FLG composite material can be seen from figure 1, and the components of the composite material comprise stannous sulfide and stannic sulfide; FIG. 2 is SnS preparedxThe XPS sulfur spectrum of the/S/FLG composite material can see the existence of the elemental sulfur in the map, but the XPS sulfur spectrum is not shown in XRD, which shows that the elemental sulfur existsSulfur is present in amorphous form; prepared SnSxAs shown in fig. 3 and 4, the SEM and HRTEM of the/S/FLG composite material are respectively shown in fig. 3 and 4, and it is understood from fig. 3 and 4 that the nanocrystalline tin sulfide and the amorphous sulfur are uniformly coated in the few-layer graphene carbon matrix.
Preparing the prepared composite material into a negative electrode plate of a lithium ion battery, assembling the lithium ion battery with 0.1Ag-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first discharge specific capacity of the/S/FLG composite material is 1498mAh g-1The first charging specific capacity is 1271.5mAh g-1The first coulombic efficiency was 84.9% (fig. 5). With 1Ag-1The specific capacity of the composite material can reach 1080.2mAh g-1After circulating for 250 times, the reversible specific capacity still has 960.2mAh g-1(FIG. 6), high capacity and excellent cycle performance. As can be seen from the lithium insertion rate performance curve of FIG. 7, it is at 0.1A g-1The reversible specific capacity reaches 1241mAh g-1That is, the charge/discharge rate is increased to 2, 5, 10A g-1The capacity still remains 1014, 935 and 833mAh g-1And has excellent rate performance.
Preparing the prepared composite material into a negative electrode plate of a sodium-ion battery and assembling the battery, wherein the weight ratio of the negative electrode plate to the negative electrode plate is 0.1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first discharge specific capacity of the/S/FLG composite material is 936.6mAh g-1The first charging specific capacity is 786.1mAh g-1The first coulombic efficiency was 83.9% (fig. 8). At 1A g-1The specific capacity of the composite material can reach 652.3mAh g-1After 200 times of circulation, the reversible specific capacity still remains 597.6mAh g-1(FIG. 9), high capacity and excellent cycle performance. As can be seen from the sodium insertion rate performance curve of FIG. 10, it is 0.1A g-1The reversible specific capacity reaches 750mAh g-1That is, the charge/discharge rate is increased to 2, 5, 10A g-1595, 565 and 530mAh g are still available-1And has excellent rate performance.
Example 4
The difference from example 1 is that the molar ratio of tin powder to sulfur powder is 1: 4.
After discharging and ball milling, tin reacts with sulfur to generate stannous sulfide and stannic sulfide, and elemental sulfur remains at the same time, so that the stannic sulfide/sulfur/few-layer graphene composite material is obtained.
Preparing the prepared composite material into a lithium ion battery cathode electrode plate and assembling the battery with the cathode electrode plate 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/S/FLG composite material is 611mAh g-1After circulating for 250 times, the reversible specific capacity is reduced to 582.1mAh g-1。
Preparing the prepared composite material into a negative electrode plate of a sodium-ion battery and assembling the battery to obtain a composite material with the weight ratio of 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/S/FLG composite material is 357.9mAh g-1After 200 times of circulation, the reversible specific capacity is reduced to 353.6mAh g-1。
Example 5
The difference from example 3 was that the mass fraction of the expanded graphite in the raw material was 80%.
And (4) discharging and ball-milling to obtain the tin sulfide/sulfur/few-layer graphene composite material.
Preparing the prepared composite material into a lithium ion battery cathode electrode plate and assembling the battery with the cathode electrode plate 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/S/FLG composite material is 550.8mAh g-1After circulating for 250 times, the reversible specific capacity is reduced to 503.5mAh g-1。
Preparing the prepared composite material into a negative electrode plate of a sodium-ion battery and assembling the battery to obtain a composite material with the weight ratio of 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/S/FLG composite material is 345.6mAh g-1After 200 times of circulation, the reversible specific capacity is reduced to 303.6mAh g-1。
Example 6
The difference from example 3 was that the mass fraction of the expanded graphite in the raw material was 20%.
And (4) discharging and ball-milling to obtain the tin sulfide/sulfur/few-layer graphene composite material.
Preparing the prepared composite material into a lithium ion battery cathode electrode plate and assembling the battery with the cathode electrode plate 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/S/FLG composite material is 1050.8mAh g-1After circulating for 250 times, the reversible specific capacity is reduced to 663.5mAh g-1。
Preparing the prepared composite material into a negative electrode plate of a sodium-ion battery and assembling the battery to obtain a composite material with the weight ratio of 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/S/FLG composite material is 675.6mAh g-1After 200 times of circulation, the reversible specific capacity is reduced to 392.3mAh g-1。
Example 7
The difference from example 3 is that the ball powder mass ratio of the grinding balls to the raw material is 30: 1.
And (4) discharging and ball-milling to obtain the tin sulfide/sulfur/few-layer graphene composite material.
Preparing the prepared composite material into a lithium ion battery cathode electrode plate, assembling the lithium ion battery cathode electrode plate into a battery, and adding 1Ag-1The multiplying power of the SnS is subjected to charge-discharge circulation between 0 and 3V to prepare the SnSxThe first reversible specific capacity of the/S/FLG composite material is 880.5mAh g-1After circulating for 250 times, the reversible specific capacity is reduced to 545.5mAh g-1。
Preparing the prepared composite material into a negative electrode plate of a sodium-ion battery and assembling the battery to obtain a composite material with the weight ratio of 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/S/FLG composite material is 465.6mAh g-1After 200 times of circulation, the reversible specific capacity is reduced to 386.3mAh g-1。
Example 8
The difference from example 3 is that the ball powder mass ratio of the grinding balls to the raw material is 70: 1.
And (4) discharging and ball-milling to obtain the tin sulfide/sulfur/few-layer graphene composite material.
Preparing the prepared composite material into a lithium ion battery cathode electrode plate and assembling the battery with the cathode electrode plate 1A g-1The multiplying power of the SnS is subjected to charge-discharge circulation between 0 and 3V to prepare the SnSxThe first reversible specific capacity of the/S/FLG composite material is 960.5mAh g-1After circulating for 250 times, the reversible specific capacity is reduced to 655.4mAh g-1。
Preparing the prepared composite material into a negative electrode plate of a sodium-ion battery and assembling the battery to obtain a composite material with the weight ratio of 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/S/FLG composite material is 605.6mAh g-1After 200 times of circulation, the reversible specific capacity is reduced to 454.3mAh g-1。
Example 9
The difference from example 3 is that the ball milling time was 10 h.
And (4) discharging and ball-milling to obtain the tin sulfide/sulfur/few-layer graphene composite material.
Preparing the prepared composite material into a lithium ion battery cathode electrode plate and assembling the battery with the cathode electrode plate 1A g-1The multiplying power of the SnS is subjected to charge-discharge circulation between 0 and 3V to prepare the SnSxThe first reversible specific capacity of the/S/FLG composite material is 763.5mAh g-1After circulating for 250 times, the reversible specific capacity is reduced to 455.6mAh g-1。
Preparing the prepared composite material into a negative electrode plate of a sodium-ion battery and assembling the battery to obtain a composite material with the weight ratio of 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/S/FLG composite material is 415.6mAh g-1After 200 times of circulation, the reversible specific capacity is reduced to 284.3mAh g-1。
Example 10
The difference from example 3 is that the ball milling time was 40 h.
And (4) discharging and ball-milling to obtain the tin sulfide/sulfur/few-layer graphene composite material.
Preparing the prepared composite material into a lithium ion battery cathode electrode plate and assembling the battery with the cathode electrode plate 1A g-1The multiplying power of the SnS is subjected to charge-discharge circulation between 0 and 3V to prepare the SnSxThe first reversible specific capacity of the/S/FLG composite material is 983.6mAh g-1After circulating for 250 times, the reversible specific capacity is reduced to 635.6mAh g-1。
The prepared composite material is prepared into a sodium ion battery cathodeElectrode tab and assembled battery with 1A g-1The multiplying power of (A) is in a range of 0-3V for charge-discharge cycle, SnSxThe first reversible specific capacity of the/S/FLG composite material is 615.8mAh g-1After 200 times of circulation, the reversible specific capacity is reduced to 483.4mAh g-1。
As mentioned above, the present invention can be better realized, and the above embodiments are only some embodiments of the present invention, and are not intended to limit the scope of the present invention; all equivalent changes and modifications made according to the present disclosure are intended to be covered by the scope of the claims of the present invention.

Claims (8)

1. A preparation method of a tin sulfide/sulfur/few-layer graphene composite material is characterized by comprising the following steps: adding tin powder, sulfur powder and expanded graphite into a ball milling tank, mixing, and performing ball milling by adopting a dielectric barrier discharge plasma assisted high-energy ball milling method to obtain the tin sulfide/sulfur/few-layer graphene composite material; in the mixture of tin powder, sulfur powder and expanded graphite, the mass fraction of the expanded graphite is 20-30%, the molar ratio of the tin powder to the sulfur powder is 1: 2-1: 3, the ball-to-material ratio of ball milling is 30: 1-70: 1, and the ball milling time is 10-40 h.
2. The preparation method of claim 1, wherein the ball-milling has a ball-to-material ratio of 40:1 to 60: 1.
3. The preparation method of claim 2, wherein the ball milling time is 15-30 h.
4. The preparation method according to claim 3, wherein the specific steps of the dielectric barrier discharge plasma assisted high-energy ball milling method are as follows:
(1) installing a front cover plate and an electrode rod of the ball milling tank, and respectively connecting iron cores in the front cover plate and the electrode rod with the positive electrode and the negative electrode of a plasma power supply, wherein the iron core in the electrode rod is connected with the positive electrode of the plasma power supply, and the front cover plate is connected with the negative electrode of the plasma power supply;
(2) filling a ball milling tank with milling balls and mixed powder of tin powder, sulfur powder and expanded graphite in a ratio;
(3) vacuumizing the ball milling tank through a vacuum valve, and then filling a discharge gas medium to enable the pressure value in the ball milling tank to reach 0.1 Mpa;
(4) and (3) switching on a plasma power supply, setting the voltage of the plasma power supply to be 15KV, the current to be 0.25A and the discharge frequency to be 60KHz, starting a driving motor to drive an excitation block, and simultaneously vibrating the rack and the ball milling tank fixed on the rack to perform dielectric barrier discharge plasma-assisted high-energy ball milling.
5. The method as claimed in claim 4, wherein the block has a double amplitude of 7mm and a motor speed of 960 r/min.
6. The preparation method according to claim 5, wherein the discharge gas medium adopted by the dielectric barrier discharge plasma assisted high-energy ball milling method is an inert gas or a mixed gas of inert gases.
7. The tin sulfide/sulfur/few-layer graphene composite material prepared by the method of any one of claims 1 to 6 is characterized by being compounded by nanocrystalline tin sulfide, amorphous sulfur and few-layer graphene, and the structure of the composite material is that the nanocrystalline tin sulfide and the amorphous sulfur are uniformly coated in a few-layer graphene carbon matrix.
8. The use of the tin sulfide/sulfur/few layer graphene composite of claim 7 in the manufacture of a negative electrode material for a lithium/sodium ion battery.
CN201710348570.3A 2017-05-17 2017-05-17 Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof Active CN107316989B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201710348570.3A CN107316989B (en) 2017-05-17 2017-05-17 Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof
PCT/CN2017/111342 WO2018209912A1 (en) 2017-05-17 2017-11-16 Tin sulfide/sulfur/few-layer graphene composite material, preparation method therefor and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710348570.3A CN107316989B (en) 2017-05-17 2017-05-17 Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107316989A CN107316989A (en) 2017-11-03
CN107316989B true CN107316989B (en) 2020-05-22

Family

ID=60181963

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710348570.3A Active CN107316989B (en) 2017-05-17 2017-05-17 Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof

Country Status (2)

Country Link
CN (1) CN107316989B (en)
WO (1) WO2018209912A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107316989B (en) * 2017-05-17 2020-05-22 华南理工大学 Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof
CN108428880A (en) * 2018-03-30 2018-08-21 华南理工大学 A kind of stannic selenide/layer graphene composite material and preparation method and application less
CN109411737B (en) * 2018-12-06 2021-07-09 中国地质大学（北京） Polar sulfide-sulfur/porous carbon composite positive electrode material with three-dimensional structure and preparation method thereof
CN109841820A (en) * 2019-03-18 2019-06-04 华南理工大学 A kind of lithium ion battery amorphous Sn 4 P 3/phosphorus/few layer graphene negative electrode material and the preparation method and application thereof
CN111446439B (en) * 2020-05-20 2021-04-13 中南大学 S@MxSnSy@ C composite positive electrode active material, preparation method thereof and application of active material in lithium-sulfur battery
CN112234184A (en) * 2020-10-14 2021-01-15 桑顿新能源科技有限公司 SnS/CNTs/S composite material and preparation method and application thereof
CN112786858A (en) * 2021-01-19 2021-05-11 安徽光特新材料科技有限公司 SnS2Preparation method of nano-sheet loaded graphene-based nano composite material
CN113823787B (en) * 2021-08-17 2023-03-21 华南理工大学 Porous sulfur composite cathode material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101447338A (en) * 2008-10-21 2009-06-03 上海第二工业大学 SnS/MCNT nanometer combined electrode material for super capacitor and preparation method thereof
CN106410166A (en) * 2016-11-30 2017-02-15 华南理工大学 Tin oxide/tin/few-layer graphene composite material as well as preparation method and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8142933B2 (en) * 2009-09-30 2012-03-27 Conocophillips Company Anode material for high power lithium ion batteries
CN102280630B (en) * 2011-07-04 2014-09-24 中国科学院过程工程研究所 Sulphur-graphene composite cathode material and manufacturing method thereof
CN102427127A (en) * 2011-12-02 2012-04-25 华南理工大学 Stannum oxide/stannum-carbon composite material, and preparation method and application thereof
CN103247803B (en) * 2013-04-16 2017-02-22 华南理工大学 Graphene-cladding nano germanium composite material as well as preparation method and application thereof
CN106654192B (en) * 2016-08-13 2020-02-18 华南理工大学 Tin sulfide/graphene sodium-ion battery composite negative electrode material and preparation method thereof
CN107316989B (en) * 2017-05-17 2020-05-22 华南理工大学 Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101447338A (en) * 2008-10-21 2009-06-03 上海第二工业大学 SnS/MCNT nanometer combined electrode material for super capacitor and preparation method thereof
CN106410166A (en) * 2016-11-30 2017-02-15 华南理工大学 Tin oxide/tin/few-layer graphene composite material as well as preparation method and application thereof

Also Published As

Publication number Publication date
WO2018209912A1 (en) 2018-11-22
CN107316989A (en) 2017-11-03

Similar Documents

Publication Publication Date Title
CN107316989B (en) Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof
CN103700820B (en) A kind of lithium ion selenium battery with long service life
CN103219491B (en) Copper sulfide anode and preparation method thereof
CN109742489B (en) Lithium-oxygen/air battery and preparation method thereof
CN107331853B (en) Graphene composite multilayer porous spherical lithium manganate electrode material and lithium ion battery prepared from same
CN102231434A (en) Modified natural graphite material used in lithium ion battery negative electrodes, and preparation method thereof
CN109904408B (en) MoS2Preparation method and application of composite material with nanosheet embedded in carbon substrate
CN108550789B (en) Sodium ion battery cathode, preparation method thereof and sodium ion battery
WO2016176928A1 (en) Negative electrode material, preparation method therefor, and lithium-ion secondary battery using the negative electrode material
CN101304084A (en) Method for preparing Li3V2(PO4)3/C composite anode material and anode material made by the same
CN108428880A (en) A kind of stannic selenide/layer graphene composite material and preparation method and application less
CN105742695B (en) A kind of lithium ion battery and preparation method thereof
CN105185963A (en) High-performance nitrogen-rich carbon composite electrode material and preparation method thereof
CN104852020A (en) Lithium ion battery silicon oxide composite negative electrode material and preparation method thereof
Huang et al. Al3+-doped FeNb11O29 anode materials with enhanced lithium-storage performance
WO2020125560A1 (en) Pre-embedded potassium negative electrode, preparation method and use, and potassium-based double ion battery, preparation method therefor and electric device
CN106410166A (en) Tin oxide/tin/few-layer graphene composite material as well as preparation method and application thereof
CN111129491A (en) Lithium ion battery negative electrode active material, preparation method thereof and lithium ion battery
CN107240693A (en) Phosphorous doped silicon graphite composite material and negative material and lithium ion battery containing it
WO2020124328A1 (en) Pre-lithiated negative electrode fabrication method, fabricated pre-lithiated negative electrode, energy storage device, energy storage system, and electrical device
CN112803018B (en) Silicon-doped graphene composite material and preparation method and application thereof
CN105513827A (en) (LMO-NCM-AC)/(LTO-AC) hybrid battery capacitor electrode material and electrode sheets
CN103378355A (en) Alkali metal secondary battery as well as negative active substance, negative material and negative electrode thereof, and preparation method of negative active substance
Peng et al. Hierarchical porous biomass activated carbon for hybrid battery capacitors derived from persimmon branches
CN110867607A (en) Method for reducing preparation cost of solid-state battery of lithium battery by doping modification

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
GR01 Patent grant
GR01 Patent grant