CN105621355A - Composite material with hollow graphene spheres loaded with nanometer tin disulfide and method for preparing composite material - Google Patents
Composite material with hollow graphene spheres loaded with nanometer tin disulfide and method for preparing composite material Download PDFInfo
- Publication number
- CN105621355A CN105621355A CN201610130529.4A CN201610130529A CN105621355A CN 105621355 A CN105621355 A CN 105621355A CN 201610130529 A CN201610130529 A CN 201610130529A CN 105621355 A CN105621355 A CN 105621355A
- Authority
- CN
- China
- Prior art keywords
- tin disulfide
- ball
- composite material
- plumbago alkene
- loaded
- 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.)
- Granted
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/58—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
- H01M4/36—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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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 composite material with hollow graphene spheres loaded with nanometer tin disulfide. The composite material is characterized in that the hollow graphene spheres with sub-micron sizes are used as carriers, tin disulfide nanometer particles are loaded on the inner walls and the outer walls of the hollow graphene spheres, and the sizes of the tin disulfide nanometer particles grown on the surfaces of the hollow graphene spheres range from 10 nm to 40 nm. A method for preparing the composite material includes steps of a, synthesizing cationic polystyrene spheres; b, synthesizing the hollow graphene spheres; c, loading the tin disulfide to obtain the composite material with the hollow graphene spheres loaded with the nanometer tin disulfide. The composite material and the method have the advantages that the composite material is a carbon material with a two-dimensional structure, the tin disulfide with an expanded volume can be accommodated in charging and discharging procedures, and the electric conductivity and the structural stability of electrode materials can be improved; the electric conductivity and the ion transport performance of the materials can be improved by porous graphene structures, and the composite material is favorable for embedding lithium ions in the materials and releasing the lithium ions from the materials.
Description
Technical field
The present invention relates to a kind of hollow plumbago alkene ball loaded with nano tin disulfide matrix material as lithium cell cathode material and its preparation method, belong to electrochemistry and field of material synthesis technology.
Background technology
Lithium ion battery because having energy density height, have extended cycle life, the plurality of advantages such as memory-less effect, become the secondary cell that the world today is most widely used. Along with going deep into further of Study on Li-ion batteries, exploitation heavy body, high rate capability, the battery material having extended cycle life becomes the emphasis in this field. At present, the negative material being actually used in lithium ion battery is generally all carbon materials, such as graphite, and soft carbon, hard carbon etc. Carbon negative pole material (theoretical capacity 372mAh/g) can not meet the needs of following heavy body, and various metal composite, metal oxide and metallic sulfide are studied to replace Carbon anode widely. Tin disulfide is owing to having lower embedding lithium voltage and higher theoretical capacity (645mAh/g), it is subject to the extensive concern of research worker in recent years always, when but tin disulfide is as lithium ion battery negative material, the same with other tin-based materials, the problem of this lithium ion battery negative material is in embedding, de-lithium process, volumetric expansion, causes electrode powder, causes storage volume and cycle life rapid decrease.
Graphene is a kind of carbon material with special two-dirnentional structure, has excellent electroconductibility and chemical property, has great application prospect in lithium ion battery electrode material. Graphene and tin disulfide compound can improve the specific conductivity of material entirety, and the volume change in buffering tin disulfide charge and discharge process, suppresses the effect that tin disulfide is reunited, and then meets the needs of following lithium ion cell high-capacity.
Summary of the invention
For the defect that prior art exists, it is an object of the invention to, a kind of hollow plumbago alkene ball loaded with nano tin disulfide matrix material and its preparation method are provided, hollow plumbago alkene ball loaded with nano tin disulfide matrix material is the carbon material of a kind of two-dirnentional structure, this matrix material can hold the volumetric expansion of tin disulfide in charge and discharge process, improve electroconductibility and the structural stability of electrode materials, and porous graphene structure can improve conductivity and the ion transmission performance of material, lithium ion is conducive to embed in the material and deviate from.
For achieving the above object, the present invention adopts following technical scheme.
A kind of hollow plumbago alkene ball loaded with nano tin disulfide matrix material, it is characterized in that, taking the hollow plumbago alkene ball of submicron-scale as carrier, tin disulfide nano particle load is at the inner and outer wall of Graphene hollow ball, and the tin disulfide particle size of growth on hollow plumbago alkene ball surface is between 10-40nm.
A preparation method for hollow plumbago alkene ball loaded with nano tin disulfide matrix material, comprises the following steps:
A. synthesizing cationic type polystyrene spheres: get initiator potassium persulfate 0.1-1g and add in round bottom there-necked flask, add 50mL deionized water again, obtain potassium persulfate solution, at the stirred potassium sulfate solution of nitrogen atmosphere, it is heated to 50-80 DEG C, add styrene monomer 2-10mL again, condensing reflux reaction 24h, condensing reflux reaction adds 100-500 �� L methylacryoyloxyethyl trimethyl ammonium chloride after carrying out 2-10h, reaction uses deionized water centrifuge washing, through vacuum-drying 6-12h after terminating, the solid obtained after dry, obtains cationic polystyrene ball;
B. hollow plumbago alkene ball is synthesized: above-mentioned steps a is obtained cationic polystyrene ball and is dispersed in water, ultrasonic 1h, get the ultrasonic 1h of a certain amount of graphene oxide solution, after ultrasonic, by graphene oxide water solution and the cationic polystyrene ball after dispersion in mass ratio 1:4 mix, ultrasonic 30min again, obtain mixed solution, then above-mentioned mixed solution is poured into round-bottomed flask, adding with graphene oxide mass ratio is (0.1-2): the hydrazine hydrate of 1, at 95 DEG C of back flow reaction 1-6h, building-up reactions terminates final vacuum and takes out filter, with deionized water wash, vacuum-drying 6-12h, then dried solid is immersed in toluene to remove A Polystyrene Spheres Template, again with absolute ethanol washing, obtain hollow plumbago alkene ball,
C. tin disulfide is loaded: the tin tetrachloride getting 1-10mmol is dissolved in ethanol in proper amount, the hollow plumbago alkene ball obtained by above-mentioned steps b is immersed in tin tetrachloride solution, soak 12h, getting 1-10mmol sulphur source is dissolved in 30mL ethanol, then join above-mentioned mixing solutions and proceed in reactor, at 160-180 DEG C, hydro-thermal reaction 4-12h, after reaction terminates, reactor naturally cools to room temperature, by product centrifugation, with absolute ethanol washing 1-3 time, vacuum is drained, and namely obtains the matrix material of hollow plumbago alkene ball loaded with nano tin disulfide.
Graphene oxide described in above-mentioned steps b add the 20-100% that quality is the quality of the cationic polystyrene ball described in step a.
Sulphur source described in above-mentioned steps c is the one in thiocarbamide, thioacetamide, Cys, dithiocarbonic anhydride.
The present invention possesses following outstanding feature compared with other tin disulfide/graphene composite material and its preparation method:
(1) preparation technology is simple, and raw materials cost is low.
(2) the hollow plumbago alkene ball prepared is the macroporous structure of a kind of three-dimensional communication, not only remains the advantage that Graphene specific surface area is big, can suppress the reunion between graphene sheet layer, it is to increase the contact area of electrode and electrolytic solution, add electrochemical reaction efficiency. And, the hollow plumbago alkene spherical structure owing to preparing is the pore passage structure of a kind of three-dimensional communication, increases the contact area of material with ion phase, increases the avtive spot of ion transmission, reduces the diffusion length of ion, it is to increase ion transportcapacity in the electrolytic solution.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of hollow plumbago alkene ball loaded with nano tin disulfide matrix material prepared by embodiment 1.
Fig. 2 is the SEM picture of hollow plumbago alkene ball loaded with nano tin disulfide matrix material prepared by embodiment 1.
Fig. 3 is the TEM picture of hollow plumbago alkene ball loaded with nano tin disulfide matrix material prepared by embodiment 1.
Fig. 4 is the charge-discharge performance figure of hollow plumbago alkene ball loaded with nano tin disulfide matrix material prepared by embodiment 1.
Embodiment
Below by embodiment, method provided by the present invention is described further.
Embodiment 1
A Preparation Method for hollow plumbago alkene ball loaded with nano tin disulfide matrix material, the step of the method is as follows:
Get initiator potassium persulfate 0.3g to add in round bottom there-necked flask, then add 50mL deionized water, add the stirred potassium sulfate solution of rotor, lead to into nitrogen protection, it is heated to 60 DEG C, then adds styrene monomer 2mL, condensing reflux reaction 24h, condensing reflux reaction adds 500 �� L methylacryoyloxyethyl trimethyl ammonium chlorides after carrying out 7h, reaction uses deionized water centrifuge washing, through vacuum-drying 12h after terminating, the solid obtained after dry, obtains cationic polystyrene ball;
Cation polystyrene ball will be obtained be dispersed in water, ultrasonic 1h, get the ultrasonic 1h of a certain amount of graphene oxide solution, after ultrasonic, by graphene oxide water solution and the cation polystyrene ball after dispersion in mass ratio 1:4 mix, ultrasonic 30min again, obtain mixed solution, then above-mentioned mixed solution is poured into round-bottomed flask, adding with Graphene mass ratio is the hydrazine hydrate of 0.5:1, at 95 DEG C of back flow reaction 2h, building-up reactions terminates final vacuum and takes out filter, with deionized water wash, vacuum-drying 12h, then dried solid is immersed in toluene to remove A Polystyrene Spheres Template, again with absolute ethanol washing, obtain hollow plumbago alkene ball,
The tin tetrachloride getting 5mmol is dissolved in 40mL ethanol, the hollow plumbago alkene ball obtained by above-mentioned steps b is immersed in 12h in tin tetrachloride solution, gets 5mmol thiocarbamide and is dissolved in 30mL ethanol, then joins above-mentioned solution and proceed in reactor, at 180 DEG C, hydro-thermal reaction 4h, after reaction terminates, reactor naturally cools to room temperature, by product centrifugation, with absolute ethanol washing 2 times, vacuum is drained, and namely obtains the matrix material of hollow plumbago alkene ball loaded with nano tin disulfide.
The electric performance test of the matrix material of obtained hollow plumbago alkene ball loaded with nano tin disulfide:
Using the product of preparation as working electrode; Take metal lithium sheet as negative pole; Take microporous polypropylene membrane as barrier film; Electrolytic solution is by l.0mol/LLiPF6Solution (is dissolved in the solution that the mass ratioes such as EC/DMC are made into); The glove box of full argon gas is assembled CR2032 type button cell, carries out constant current charge-discharge test, through can be calculated the specific capacitance of single electrode of material. The XRD of product as shown in Figure 1, as seen from the figure, contains the tin disulfide of pure phase, without obvious impurity peaks in this product in the matrix material of preparation. Fig. 2 and Fig. 3 is the scanning electron microscope (SEM) of matrix material and transmission electron microscope (TEM) photo of preparation, can find out that hollow plumbago alkene ball is curling and become by the Graphene of thin layer from Fig. 2 with Fig. 3, and the size of its hollow ball is about 1 ��m; Nanometer tin disulfide particle that uniform loading is a large amount of on the porous hollow inside and outside wall of spherical Graphene, tin disulfide is of a size of 10-40nm. Fig. 4 is the charging and discharging curve of hollow plumbago alkene ball loaded with nano tin disulfide matrix material at 0.005-3.00V voltage range of preparation. As shown in Figure 4, under 100mA/g current density, the first discharge specific capacity of this matrix material can reach 1133mAh/g, and the 2nd time specific discharge capacity can reach 660mAh/g, 3rd time specific discharge capacity is obviously decayed compared with the 2nd nothing, it is shown that the matrix material of the present invention has good cycle performance.
Embodiment 2
A Preparation Method for hollow plumbago alkene ball loaded with nano tin disulfide matrix material, the step of the method is as follows
Get initiator potassium persulfate 0.25g to add in round bottom there-necked flask, then add 50mL deionized water, add the stirred potassium sulfate solution of rotor, lead to into nitrogen protection, it is heated to 75 DEG C, then adds styrene monomer 5mL, condensing reflux reaction 24h, condensing reflux reaction adds 500 �� L methylacryoyloxyethyl trimethyl ammonium chlorides after carrying out 5h, reaction uses deionized water centrifuge washing, through vacuum-drying 6h after terminating, the solid obtained after dry, obtains cationic polystyrene ball;
Cation polystyrene ball will be obtained be dispersed in water, ultrasonic 1h, get the ultrasonic 1h of a certain amount of graphene oxide solution, after ultrasonic, by graphene oxide water solution and the cation polystyrene ball after dispersion in mass ratio 1:3 mix, ultrasonic 30min again, obtain mixed solution, then above-mentioned mixed solution is poured into round-bottomed flask, adding with Graphene mass ratio is the hydrazine hydrate of 0.7:1, at 95 DEG C of back flow reaction 4h, building-up reactions terminates final vacuum and takes out filter, with deionized water wash, vacuum-drying 6h, then dried solid is immersed in toluene to remove A Polystyrene Spheres Template, again with absolute ethanol washing, obtain hollow plumbago alkene ball,
The tin tetrachloride getting 3mmol is dissolved in 40mL ethanol, the hollow plumbago alkene ball obtained by above-mentioned steps b is immersed in 12h in tin tetrachloride solution, gets 3mmol thioacetamide and is dissolved in 30mL ethanol, then joins above-mentioned solution and proceed in reactor, at 160 DEG C, hydro-thermal reaction 12h, after reaction terminates, reactor naturally cools to room temperature, by product centrifugation, with absolute ethanol washing 2 times, vacuum is drained, and namely obtains the matrix material of hollow plumbago alkene ball loaded with nano tin disulfide.
Embodiment 3
A Preparation Method for hollow plumbago alkene ball loaded with nano tin disulfide matrix material, the step of the method is as follows
Get initiator potassium persulfate 0.5g to add in round bottom there-necked flask, then add 50mL deionized water, add the stirred potassium sulfate solution of rotor, lead to into nitrogen protection, it is heated to 85 DEG C, then adds styrene monomer 8mL, condensing reflux reaction 24h, condensing reflux reaction adds 400 �� L methylacryoyloxyethyl trimethyl ammonium chlorides after carrying out 10h, reaction uses deionized water centrifuge washing, through vacuum-drying 12h after terminating, the solid obtained after dry, obtains cationic polystyrene ball;
Cation polystyrene ball will be obtained be dispersed in water, ultrasonic 1h, get the ultrasonic 1h of a certain amount of graphene oxide solution, after ultrasonic, by graphene oxide water solution and the cation polystyrene ball after dispersion in mass ratio 1:1 mix, ultrasonic 30min again, obtain mixed solution, then above-mentioned mixed solution is poured into round-bottomed flask, adding with Graphene mass ratio is the hydrazine hydrate of 0.3:1, at 95 DEG C of back flow reaction 5h, building-up reactions terminates final vacuum and takes out filter, with deionized water wash, vacuum-drying 8h, then dried solid is immersed in toluene to remove A Polystyrene Spheres Template, again with absolute ethanol washing, obtain hollow plumbago alkene ball,
The tin tetrachloride getting 10mmol is dissolved in 40mL ethanol, the hollow plumbago alkene ball obtained by above-mentioned steps b is immersed in 12h in tin tetrachloride solution, getting 8mmolL-halfcystine is dissolved in 30mL ethanol, then joins above-mentioned solution and proceeds in reactor, reacts 8h at 180 DEG C, after reaction terminates, reactor naturally cools to room temperature, by product centrifugation, with absolute ethanol washing 2 times, vacuum is drained, and namely obtains the matrix material of hollow plumbago alkene ball loaded with nano tin disulfide.
Embodiment 4
A Preparation Method for hollow plumbago alkene ball loaded with nano tin disulfide matrix material, the step of the method is as follows
Get initiator potassium persulfate 1.0g to add in round bottom there-necked flask, then add 50mL deionized water, add the stirred potassium sulfate solution of rotor, lead to into nitrogen protection, it is heated to 90 DEG C, then adds styrene monomer 10mL, condensing reflux reaction 24h, condensing reflux reaction adds 100 �� L methylacryoyloxyethyl trimethyl ammonium chlorides after carrying out 5h, reaction uses deionized water centrifuge washing, through vacuum-drying 12h after terminating, the solid that will obtain after dry, obtains cationic polystyrene ball;
Cation polystyrene ball will be obtained be dispersed in water, ultrasonic 1h, get the ultrasonic 1h of a certain amount of graphene oxide solution, by graphene oxide water solution and the cation polystyrene ball after dispersion in mass ratio 1:5 mix, ultrasonic 30min again, obtain mixed solution, then above-mentioned mixed solution is poured into round-bottomed flask, adding with Graphene mass ratio is the hydrazine hydrate of 1:1, at 95 DEG C of back flow reaction 1h, building-up reactions terminates final vacuum and takes out filter, and wash with ionized water, vacuum-drying 9h, then dried solid is immersed in toluene to remove A Polystyrene Spheres Template, again with absolute ethanol washing, obtain hollow plumbago alkene ball,
The tin tetrachloride getting 3mmol is dissolved in 40mL ethanol, the hollow plumbago alkene ball obtained by above-mentioned steps b is immersed in 12h in tin tetrachloride solution, getting 3mmol dithiocarbonic anhydride is dissolved in 30mL ethanol, then joins above-mentioned solution and proceeds in reactor, at 180 DEG C of hydro-thermal reaction 12h, after reaction terminates, reactor naturally cools to room temperature, by product centrifugation, with absolute ethanol washing 3 times, vacuum is drained, and namely obtains the matrix material of hollow plumbago alkene ball loaded with nano tin disulfide.
Claims (4)
1. a hollow plumbago alkene ball loaded with nano tin disulfide matrix material, it is characterized in that, taking the hollow plumbago alkene ball of submicron-scale as carrier, tin disulfide nano particle load is at the inner and outer wall of Graphene hollow ball, and the tin disulfide particle size of growth on hollow plumbago alkene ball surface is between 10-40nm.
2. the preparation method of a kind of hollow plumbago alkene ball loaded with nano tin disulfide matrix material described in a claim 1, it is characterised in that, comprise the steps:
A. synthesizing cationic type polystyrene spheres: get initiator potassium persulfate 0.1-1g and add in round bottom there-necked flask, add 50mL deionized water again, obtain potassium persulfate solution, at the stirred potassium sulfate solution of nitrogen atmosphere, it is heated to 50-80 DEG C, add styrene monomer 2-10mL again, condensing reflux reaction 24h, condensing reflux reaction adds 100-500 �� L methylacryoyloxyethyl trimethyl ammonium chloride after carrying out 2-10h, reaction uses deionized water centrifuge washing, through vacuum-drying 6-12h after terminating, the solid obtained after dry, obtains cationic polystyrene ball;
B. hollow plumbago alkene ball is synthesized: above-mentioned steps a is obtained cationic polystyrene ball and is dispersed in water, ultrasonic 1h, get the ultrasonic 1h of a certain amount of graphene oxide solution, after ultrasonic, by graphene oxide water solution and the cationic polystyrene ball after dispersion in mass ratio 1:4 mix, ultrasonic 30min again, obtain mixed solution, then above-mentioned mixed solution is poured into round-bottomed flask, adding with graphene oxide mass ratio is (0.1-2): the hydrazine hydrate of 1, at 95 DEG C of back flow reaction 1-6h, building-up reactions terminates final vacuum and takes out filter, with deionized water wash, vacuum-drying 6-12h, then dried solid is immersed in toluene to remove A Polystyrene Spheres Template, again with absolute ethanol washing, obtain hollow plumbago alkene ball,
C. tin disulfide is loaded: the tin tetrachloride getting 1-10mmol is dissolved in ethanol in proper amount, the hollow plumbago alkene ball obtained by above-mentioned steps b is immersed in tin tetrachloride solution, soak 12h, getting 1-10mmol sulphur source is dissolved in 30mL ethanol, then join above-mentioned mixing solutions and proceed in reactor, at 160-180 DEG C, hydro-thermal reaction 4-12h, after reaction terminates, reactor naturally cools to room temperature, by product centrifugation, with absolute ethanol washing 1-3 time, vacuum is drained, and namely obtains the matrix material of hollow plumbago alkene ball loaded with nano tin disulfide.
3. the preparation method of a kind of hollow plumbago alkene ball loaded with nano tin disulfide matrix material according to claim 2, it is characterized in that, the graphene oxide described in above-mentioned steps b add the 20-100% that quality is the quality of the cationic polystyrene ball described in step a.
4. the preparation method of a kind of hollow plumbago alkene ball loaded with nano tin disulfide matrix material according to claim 3, it is characterised in that, the sulphur source described in above-mentioned steps c is the one in thiocarbamide, thioacetamide, Cys, dithiocarbonic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610130529.4A CN105621355B (en) | 2016-03-08 | 2016-03-08 | A kind of hollow plumbago alkene ball load nanometer stannic disulfide composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610130529.4A CN105621355B (en) | 2016-03-08 | 2016-03-08 | A kind of hollow plumbago alkene ball load nanometer stannic disulfide composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105621355A true CN105621355A (en) | 2016-06-01 |
| CN105621355B CN105621355B (en) | 2018-01-02 |
Family
ID=56036764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610130529.4A Active CN105621355B (en) | 2016-03-08 | 2016-03-08 | A kind of hollow plumbago alkene ball load nanometer stannic disulfide composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105621355B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106129376A (en) * | 2016-08-30 | 2016-11-16 | 上海大学 | The lithium ion battery cathode pole piece of Graphene hollow ball load stannic disulfide composite |
| CN107689271A (en) * | 2017-08-22 | 2018-02-13 | 京东方科技集团股份有限公司 | Preparation method, porous graphene film and the electronic product of porous graphene film |
| CN107887586A (en) * | 2017-11-06 | 2018-04-06 | 陈少华 | A kind of preparation method of ion cathode material lithium |
| CN108155369A (en) * | 2018-01-23 | 2018-06-12 | 福州大学 | The preparation method of one type graphene/metal sulfide/carbon composite electrode material |
| CN108281625A (en) * | 2018-01-03 | 2018-07-13 | 兰州理工大学 | A kind of nanometer of compound nucleocapsid of stannic disulfide/carbosphere and preparation method thereof |
| CN108390042A (en) * | 2018-03-01 | 2018-08-10 | 中国科学院福建物质结构研究所 | A kind of carbon packet SnS2Composite material and preparation method and application |
| CN109148942A (en) * | 2017-06-28 | 2019-01-04 | 福建省辉锐材料科技有限公司 | A kind of preparation method of novel aluminum Dual-ion cell |
| CN109286011A (en) * | 2018-09-28 | 2019-01-29 | 哈尔滨理工大学 | A kind of preparation method of stannic disulfide/vertical graphene nanometer sheet array electrode |
| CN109301229A (en) * | 2018-11-12 | 2019-02-01 | 陕西科技大学 | A kind of preparation method and application of kalium ion battery negative electrode material graphene coated tin oxide/stannic disulfide nano flower |
| CN109422262A (en) * | 2017-08-28 | 2019-03-05 | 深圳先进技术研究院 | A kind of super-dispersed nano diamond dispersion liquid and its preparation method and application |
| CN110707286A (en) * | 2019-10-30 | 2020-01-17 | 上海理工大学 | High-energy-density lithium ion battery integrated electrode and preparation method thereof |
| CN111106346A (en) * | 2019-12-17 | 2020-05-05 | 合肥国轩高科动力能源有限公司 | SnS2rGO modified sulfur cathode material and preparation method and application thereof |
| CN111252806A (en) * | 2020-02-14 | 2020-06-09 | 西安交通大学 | Tin disulfide-black phosphorus composite material, preparation method and application thereof |
| CN114242982A (en) * | 2021-12-20 | 2022-03-25 | 北京理工大学重庆创新中心 | Graphene-coated two-dimensional metal compound electrode material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522543A (en) * | 2011-12-15 | 2012-06-27 | 清华大学 | Method for preparing nanometer compound of tin disulfide-graphene |
| CN103346299A (en) * | 2013-06-08 | 2013-10-09 | 上海大学 | In-situ etching method for preparing hollow tin-based oxide/carbon composite nano-material |
| CN105098151A (en) * | 2015-06-19 | 2015-11-25 | 上海交通大学 | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof |
-
2016
- 2016-03-08 CN CN201610130529.4A patent/CN105621355B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522543A (en) * | 2011-12-15 | 2012-06-27 | 清华大学 | Method for preparing nanometer compound of tin disulfide-graphene |
| CN103346299A (en) * | 2013-06-08 | 2013-10-09 | 上海大学 | In-situ etching method for preparing hollow tin-based oxide/carbon composite nano-material |
| CN105098151A (en) * | 2015-06-19 | 2015-11-25 | 上海交通大学 | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106129376A (en) * | 2016-08-30 | 2016-11-16 | 上海大学 | The lithium ion battery cathode pole piece of Graphene hollow ball load stannic disulfide composite |
| CN109148942A (en) * | 2017-06-28 | 2019-01-04 | 福建省辉锐材料科技有限公司 | A kind of preparation method of novel aluminum Dual-ion cell |
| CN107689271A (en) * | 2017-08-22 | 2018-02-13 | 京东方科技集团股份有限公司 | Preparation method, porous graphene film and the electronic product of porous graphene film |
| US11512000B2 (en) | 2017-08-22 | 2022-11-29 | Fuzhou Boe Optoelectronics Technology Co., Ltd. | Porous graphene film, its manufacturing method and electronic product |
| CN109422262A (en) * | 2017-08-28 | 2019-03-05 | 深圳先进技术研究院 | A kind of super-dispersed nano diamond dispersion liquid and its preparation method and application |
| CN109422262B (en) * | 2017-08-28 | 2023-04-21 | 深圳先进技术研究院 | Super-dispersed nano-diamond dispersion liquid and preparation method and application thereof |
| CN107887586A (en) * | 2017-11-06 | 2018-04-06 | 陈少华 | A kind of preparation method of ion cathode material lithium |
| CN108281625A (en) * | 2018-01-03 | 2018-07-13 | 兰州理工大学 | A kind of nanometer of compound nucleocapsid of stannic disulfide/carbosphere and preparation method thereof |
| CN108155369A (en) * | 2018-01-23 | 2018-06-12 | 福州大学 | The preparation method of one type graphene/metal sulfide/carbon composite electrode material |
| CN108155369B (en) * | 2018-01-23 | 2020-10-09 | 福州大学 | Preparation method of graphene-like/metal sulfide/carbon composite electrode material |
| CN108390042A (en) * | 2018-03-01 | 2018-08-10 | 中国科学院福建物质结构研究所 | A kind of carbon packet SnS2Composite material and preparation method and application |
| CN109286011A (en) * | 2018-09-28 | 2019-01-29 | 哈尔滨理工大学 | A kind of preparation method of stannic disulfide/vertical graphene nanometer sheet array electrode |
| CN109301229A (en) * | 2018-11-12 | 2019-02-01 | 陕西科技大学 | A kind of preparation method and application of kalium ion battery negative electrode material graphene coated tin oxide/stannic disulfide nano flower |
| CN109301229B (en) * | 2018-11-12 | 2021-02-05 | 陕西科技大学 | Preparation method and application of graphene-coated tin oxide/tin disulfide nanoflower serving as negative electrode material of potassium ion battery |
| CN110707286A (en) * | 2019-10-30 | 2020-01-17 | 上海理工大学 | High-energy-density lithium ion battery integrated electrode and preparation method thereof |
| CN111106346B (en) * | 2019-12-17 | 2022-03-11 | 合肥国轩高科动力能源有限公司 | SnS2rGO modified sulfur cathode material and preparation method and application thereof |
| CN111106346A (en) * | 2019-12-17 | 2020-05-05 | 合肥国轩高科动力能源有限公司 | SnS2rGO modified sulfur cathode material and preparation method and application thereof |
| CN111252806A (en) * | 2020-02-14 | 2020-06-09 | 西安交通大学 | Tin disulfide-black phosphorus composite material, preparation method and application thereof |
| CN114242982A (en) * | 2021-12-20 | 2022-03-25 | 北京理工大学重庆创新中心 | Graphene-coated two-dimensional metal compound electrode material and preparation method and application thereof |
| CN114242982B (en) * | 2021-12-20 | 2023-11-07 | 北京理工大学重庆创新中心 | Graphene-coated two-dimensional metal compound electrode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105621355B (en) | 2018-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105621355A (en) | Composite material with hollow graphene spheres loaded with nanometer tin disulfide and method for preparing composite material | |
| Wang et al. | Polar and conductive iron carbide@ N-doped porous carbon nanosheets as a sulfur host for high performance lithium sulfur batteries | |
| Du et al. | Constructing sheet-assembled hollow CuSe nanocubes to boost the rate capability of rechargeable magnesium batteries | |
| Jin et al. | Facile synthesis of Fe-MOF/RGO and its application as a high performance anode in lithium-ion batteries | |
| Zhang et al. | A facile synthesis of 3D flower-like NiCo2O4@ MnO2 composites as an anode material for Li-ion batteries | |
| Sun et al. | Catalytic Co 9 S 8 decorated carbon nanoboxes as efficient cathode host for long-life lithium-sulfur batteries | |
| Bai et al. | Facile synthesis of mesoporous Mn 3 O 4 nanorods as a promising anode material for high performance lithium-ion batteries | |
| Zeng et al. | Highly crosslinked organosulfur copolymer nanosheets with abundant mesopores as cathode materials for efficient lithium-sulfur batteries | |
| CN103346304B (en) | Tin-carbon composite material for lithium secondary battery negative electrode and preparation method thereof | |
| CN103165874A (en) | Porous silicon negative material of lithium ion battery and preparation method and application of material | |
| CN104916828B (en) | Three-dimensional grapheme hollow carbon sphere/sulphur composite and preparation method thereof and the application in lithium-sulfur cell | |
| CN106654221A (en) | Three-dimensional porous carbon-coated zinc selenide material for lithium ion battery anodes and preparation method of material | |
| CN105742602A (en) | Sn/MoS<2>/C composite material for sodium ion battery negative electrode and preparation method therefor | |
| CN105428618B (en) | A kind of preparation method and applications of core-shell type carbon-clad metal sulfide nano-complex particle | |
| Kim et al. | Formation of ordered macroporous ZnFe2O4 anode materials for highly reversible lithium storage | |
| Liu et al. | Electrochemical reaction of sulfur cathodes with Ni foam current collector in Li-S batteries | |
| CN107768617B (en) | Lithium-sulfur battery composite cathode material and preparation method thereof | |
| CN105914369A (en) | Nanoscale carbon coated lithium sulfide composite material, preparation method and application thereof | |
| Cai et al. | Template-free fabrication of porous CuCo 2 O 4 hollow spheres and their application in lithium ion batteries | |
| CN108987729A (en) | A kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell | |
| CN108767203B (en) | Titanium dioxide nanotube-graphene-sulfur composite material and preparation method and application thereof | |
| CN109360989A (en) | A kind of high-performance lithium-sulfur cell and preparation method thereof of sulfide quantum dots doping | |
| CN104577126A (en) | Method for preparing MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and application of material in lithium electrode | |
| Gu et al. | A Typha Angustifolia-like MoS2/carbon nanofiber composite for high performance Li-S batteries | |
| Zhang et al. | Ultrafine ZnSe/CoSe nanodots encapsulated in core–shell MOF-derived hierarchically porous N-doped carbon nanotubes for superior lithium/sodium storage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |