CN107611388A - A kind of shell has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure - Google Patents
A kind of shell has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure Download PDFInfo
- Publication number
- CN107611388A CN107611388A CN201710772753.8A CN201710772753A CN107611388A CN 107611388 A CN107611388 A CN 107611388A CN 201710772753 A CN201710772753 A CN 201710772753A CN 107611388 A CN107611388 A CN 107611388A
- Authority
- CN
- China
- Prior art keywords
- carbon
- nano
- shell
- sphere
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
A kind of shell has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure, belong to nano material production technical field, by ethanol, deionized water, ammoniacal liquor, tetraethyl orthosilicate, resorcinol and formaldehyde hybrid reaction, solid phase is obtained to dry, etched after being calcined in argon gas through sodium hydrate aqueous solution, obtain hollow mesoporous carbon nanosphere；Tungsten chloride and thiocarbamide solid are dissolved in after deionized water and add hollow mesoporous Nano carbon balls, through the laggard water-filling thermal response of ultrasonic disperse, obtains after solid phase is dried and is calcined in argon gas, obtaining shell has the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure.The characteristics of present invention process raw material is cheap, technique is simple and environmentally-friendly, yield is big, excellent performance, obtained shell have the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure can be as the application of lithium ion battery electrode material, catalysis material or electrocatalysis material.
Description
Technical field
The invention belongs to nano material production technical field, and in particular to a kind of shell has the carbon coating of sandwich structure
Tungsten sulfide（WS2@C）The preparation method of hollow nano-sphere.
Background technology
Since graphene is found, other class graphene-structureds are studied in succession, especially the transition metal vulcanization of stratiform
Thing（MoS2, WS2）.It is a kind of important storage lithium compound because it has electrochemical conversion and ionic conduction, in Transition Metal Sulfur
In compound, stratiform tungsten disulfide（WS2）It is a kind of layered semiconductor material, there is unique sandwich type layer structure（S-W-
S）, the covalent atom of interlayer is combined with weak Van der Waals force, and the space of atom interlayer can allow external reactant to carry out
Insertion reaction, and have and be better than MoS2Ionic conductivity, WS2（433mA h g-1）Negative electrode of lithium ion battery theoretical capacity is higher than
Graphene（372 mA h g-1）.It is widely used in the side such as solid lubricant, catalysis, hydrogen storage material, li-ion electrode materials
Face.In addition, two-dimensional structure meets the stability that the storage of quick lithium needs, effective surface area and lithium ion deintercalation need compared with
Short open approach.
Carbon material species is more（CNT, graphene, hollow carbon sphere etc.）, source is wide, cheap, good conductivity, be suitable as
Electrode material.In conductive Carbon Materials compound, because the introducing of carbon material causes composite to have special physics and change
Performance is learned, conductive carbon material compound is used widely in lubrication, catalysis, energy storage and conversion equipment.Relative to it
His carbon material, mesoporous carbon can improve the electric conductivity of material, and porous carbon skeleton has high specific surface area and abundant duct
Be advantageous to permeate electrolyte, can fully infiltrate active electrode material so that active material and electrolyte contacts are good, and can
To provide huge reaction interface, the activation point increase that stores lithium ion, improve material it is reversible it is embedding it is de- during Li+
Exchange and transmission.In addition, the cavity inside mesoporous carbon can also buffer WS2Embedding/de- Li of nanometer sheet+The bulk effect of process, prevent
Coming off and assembling for limited step layer, ensures that the stability of composite construction, make the structural stability that its composite has had with
Chemical property.
Because tungsten disulfide is the structure of multiple-level stack, the insertion of lithium ion can cause the change of volume or structure, simultaneously
Tungsten disulfide is that semiconducting electrical conductivity is poor.
At present, this is turned into by synthesizing the Wolfram disulfide nano material with special appearance to improve its chemical property
The hot issue in field.
The content of the invention
The defects of for above-mentioned prior art, the present invention propose that one kind can be used as lithium ion battery electrode material, photocatalysis
The shell of material or electrocatalysis material has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure.
The present invention comprises the following steps：
1）Under magnetic agitation, after first mixing ethanol, deionized water and ammoniacal liquor, tetraethyl orthosilicate is added, after remixing, then is added
Enter resorcinol and formaldehyde is reacted；
Reaction terminates rear centrifuge washing, obtains solid phase and dries, then the high-temperature calcination under argon gas atmosphere protection, then by high-temperature calcination
Product afterwards etches through sodium hydrate aqueous solution, finally by the product centrifuge washing after etching, and obtained solid phase is dried, i.e.,
Obtain hollow mesoporous carbon nanosphere.
The present invention is using resorcinol and formaldehyde as carbon source, using tetraethyl orthosilicate as silicon source so as to forming silica@dioxies
SiClx/resorcinol-formaldehyde oligomer nanoparticle, etching obtains uniform particle diameter, constitutionally stable hollow Jie after high-temperature calcination
Hole Nano carbon balls, good template and reactor are provided for subsequent technique.
2）Tungsten chloride and thiocarbamide solid are dissolved in deionized water under ultrasound condition, then add hollow mesoporous carbon nanometer
Ball, through the laggard water-filling thermal response of ultrasonic disperse；
Hydro-thermal reaction terminates rear centrifuge washing, obtains the high-temperature calcination under argon gas atmosphere protection after solid phase is dried, produces shell tool
There is the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure.
The present invention has synthesized a kind of inside/outside wall growth sheet tungsten disulfide in hollow carbon sphere carbon shell with the method for hydro-thermal and received
The novel structure of rice piece, its shell form a kind of sandwich structure.The carbon coating that this shell has sandwich structure vulcanizes
Tungsten（WS2@C）Hollow nano-sphere has larger reference area.Tungsten disulfide nano slices are given birth in the inside and outside wall of hollow mesoporous carbon shell
It is long, the avtive spot of tungsten disulfide can be increased, obtain the tungsten disulfide nano slices of few layer, reduce the heap of tungsten disulfide nano slices
Product, the diffusion path of lithium ion is shortened, so as to improve its capacity and high rate performance.Porous carbon shell not only increases composite wood
The electric conductivity of material, the loose structure on carbon shell also provide passage for the diffusion of lithium ion.In addition, tungsten disulfide nano slices are in carbon
Shell inside and outside wall, this heterojunction structure also promote the electrochemical properties of composite, can also prevent from tying in its charge and discharge process
Structure comes off, and the space of the inside of hollow-core construction can buffer the bulk effect during Li insertion extraction, beneficial to being tied in cyclic process
The stabilization of structure, so that high rate performance and stable circulation performance that material has possessed so that active material is in high current, long circulating
In be effectively protected.Therefore, the shell of above method synthesis of the present invention has the carbon coating tungsten sulfide of sandwich structure hollow
Nanosphere is ion cathode material lithium a kind of and with application prospect.
In a word, the characteristics of present invention process raw material is cheap, technique is simple and environmentally-friendly, yield is big, excellent performance, obtained shell
Carbon coating tungsten sulfide hollow nano-sphere with sandwich structure can be used as lithium ion battery electrode material, catalysis material or electricity
The application of catalysis material.
Further, step 1 of the present invention）In, the mass ratio that feeds intake of resorcinol and formaldehyde is 1: 1~6.
The step 1）In, the reaction time is 12 h.
The present invention with control the amount ratio of formalin and resorcinol and reaction time adjust the thickness of carbon wall and
The surface mesoporous size of carbon-coating.So that etching removing silica therein obtains uniform porous hollow after high-temperature calcination
Carbon ball, the thickness of carbon-coating is about 10~25 nm, and particle diameter is in 200~500 nm or so, with the end-product particle diameter obtained thereafter
It is basically identical.2~7 layers of tungsten disulfide nano slices of the inside/outside surface homoepitaxial of carbon shell, and the WS of inwall growth2Nanometer sheet
Far more than outer wall.This sandwich structure is not only with big specific surface area also with good interface performance and high electric conductivity.
In addition, internal cavity can also buffer WS2The bulk effect of nanometer sheet.
The step 1）In, the concentration of the sodium hydrate aqueous solution is 1~2 M, and the temperature of sodium hydrate aqueous solution is
50~90 DEG C.Etching on this condition, which not only makes silica remove completely, can also make the presentation of carbon ball surface porous, also simultaneously
The integrality that carbon ball keeps carbon ball can not be destroyed.
In addition, the step 2）In, the mass ratio that feeds intake of tungsten chloride, thiocarbamide and hollow mesoporous Nano carbon balls is 1: 1~5:
0.05~0.5.Hydrothermal temperature is 150~250 DEG C in reaction, the h of reaction time 6~24.It can obtain on this condition hollow mesoporous
The dispersed tungsten disulfide laminated structure of the inside/outside shells of Nano carbon balls, the piece number of plies of tungsten disulfide is 2~7, hollow carbon sphere according to
Original pattern so can be kept, the porous carbon ball containing tungsten disulfide sheet is disperseed homogeneous without obvious agglomeration.
The step 2）In, with 1~5 DEG C/min heating rate during high-temperature calcination, temperature is risen to 500~800 DEG C and forged
Burn 1~12 h.The crystal formation of tungsten disulfide nano slices can be improved on this condition, while also can obtain the degree of graphitization of shell carbon
To raising, so as to improve the chemical property of composite.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the silica@silica/resorcinol-formaldehyde oligomer nanosphere prepared.
Fig. 2 is the transmission electron microscope picture of the silica@silicon/carbon dioxide nanospheres prepared.
Fig. 3 is the transmission electron microscope picture of the hollow mesoporous Nano carbon balls prepared.
Fig. 4 is the carbon coating tungsten sulfide that the shell prepared has sandwich structure（WS2@C）The transmission electricity of hollow nano-sphere
Mirror figure.
Fig. 5 is the carbon coating tungsten sulfide that the shell prepared has sandwich structure（WS2@C）The high power of hollow nano-sphere is put
Big figure.
Fig. 6 is the carbon coating tungsten sulfide that the shell prepared has sandwich structure（WS2@C）The discharge and recharge of hollow nano-sphere
Cycle performance figure（Current density is 1 A g-1）.
Fig. 7 is the carbon coating tungsten sulfide that the shell prepared has sandwich structure（WS2@C）Hollow nano-sphere different multiplying
Charge-discharge performance figure.
Embodiment
First, shell has the preparation embodiment of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure.
Embodiment 1：
1st, hollow mesoporous Nano carbon balls are prepared：
25 mL absolute ethyl alcohols, 5 mL deionized waters, 0.5 mL ammoniacal liquor are added in beaker and carry out magnetic agitation, while upwards
State and 0.5 mL tetraethyl orthosilicates are added in mixed liquor, by mixed liquor magnetic agitation for a period of time, weigh 0.1 g resorcinols and amount
0.1 g formaldehyde is taken to be added sequentially in above-mentioned mixed solution, magnetic agitation reacts 12 h.Question response terminates rear centrifuge washing, takes
Dried after obtaining solid phase, by dried product under argon gas protection, heating rate 1 DEG C/min, 500 DEG C of h of high-temperature calcination 24.With
The product after high-temperature calcination is etched into 12 h under 50 DEG C of water bath conditions with 2 M sodium hydroxide solutions afterwards.Finally, by after etching
Product centrifuge washing, and by obtained solid phase dry, produce hollow mesoporous Nano carbon balls.
The hollow mesoporous nm of Nano carbon balls diameter 200, carbon wall thickness are 10 nm, the nm of surface apertures size 2.0.
2nd, preparing shell has the carbon coating tungsten sulfide of sandwich structure（WS2@C）Hollow nano-sphere：
0.4 g tungsten chlorides and 0.4 g thiocarbamide solids are dissolved in 50 mL deionized waters, ultrasonic mixing is uniform, and adds 20 mg
For hollow mesoporous Nano carbon balls ultrasonic disperse in above-mentioned solution, 150 DEG C of h of hydro-thermal reaction 24, question response terminates rear centrifuge washing,
Dried after obtaining solid phase, by dried product under argon gas protection, heating rate 1 DEG C/min, 500 DEG C of h of high-temperature calcination 12,
Producing shell has the carbon coating tungsten sulfide of sandwich structure（WS2@C）Hollow nano-sphere.
Embodiment 2：
1st, hollow mesoporous Nano carbon balls are prepared：
50 mL absolute ethyl alcohols, 15 mL deionized waters, 3 mL ammoniacal liquor are added in beaker and carry out magnetic agitation, while to above-mentioned
0.7 mL tetraethyl orthosilicates are added in mixed liquor, by mixed liquor magnetic agitation for a period of time, 0.1 g resorcinols is weighed and measures
0.5 g formaldehyde is added sequentially in above-mentioned mixed solution, and magnetic agitation reacts 12 h.Question response terminates rear centrifuge washing, obtains
Dried after solid phase, by dried product under argon gas protection, heating rate 2 DEG C/min, 700 DEG C of h of high-temperature calcination 5.Then will
Product after high-temperature calcination etches 20 h under 60 DEG C of water bath conditions with 1.5 M sodium hydroxide solutions.Finally, by the production after etching
Thing centrifuge washing, and obtained solid phase is dried, produce hollow mesoporous Nano carbon balls.
The hollow mesoporous nm of Nano carbon balls diameter 360, carbon wall thickness are 22 nm, the nm of surface apertures size 2.2.
2nd, preparing shell has the carbon coating tungsten sulfide of sandwich structure（WS2@C）Hollow nano-sphere：
0.4 g tungsten chlorides and 1.0 g thiocarbamide solids are dissolved in 50 mL deionized waters, ultrasonic mixing is uniform, and adds 0.1 g
For hollow mesoporous Nano carbon balls ultrasonic disperse in above-mentioned solution, 200 DEG C of h of hydro-thermal reaction 12, question response terminates rear centrifuge washing,
Dried after obtaining solid phase, by dried product under argon gas protection, heating rate 2 DEG C/min, 700 DEG C of h of high-temperature calcination 6, i.e.,
Obtain the hollow mesoporous Nano carbon balls covering piece shape tungsten disulfide of sandwich structure（WS2@C）Nanoparticle.
Embodiment 3：
1st, hollow mesoporous Nano carbon balls are prepared：
160 mL absolute ethyl alcohols, 40 mL deionized waters, 8 mL ammoniacal liquor are added in beaker and carry out magnetic agitation, while upwards
State and 0.8 mL tetraethyl orthosilicates are added in mixed liquor, by mixed liquor magnetic agitation for a period of time, weigh 0.1 g resorcinols and amount
0.6 g formaldehyde is taken to be added sequentially in above-mentioned mixed solution, magnetic agitation reaction 24h.Question response terminates rear centrifuge washing, obtains
Dried after solid phase, by dried product under argon gas protection, heating rate 5 DEG C/min, 800 DEG C of h of high-temperature calcination 2.Then
Product after high-temperature calcination is etched into 12h under 90 DEG C of water bath conditions with 2 M sodium hydroxide solutions.Finally, by the production after etching
Thing centrifuge washing, and obtained solid phase is dried, produce hollow mesoporous Nano carbon balls.
The hollow mesoporous nm of Nano carbon balls diameter 500, carbon wall thickness are 25 nm, the nm of surface apertures size 5.4.
2nd, preparing shell has the carbon coating tungsten sulfide of sandwich structure（WS2@C）Hollow nano-sphere：
0.4 g tungsten chlorides and 2.0 g thiocarbamide solids are dissolved in 50 mL deionized waters, ultrasonic mixing is uniform, and adds 0.2 g
In above-mentioned solution, 250 DEG C of h of hydro-thermal reaction 6, question response terminates rear centrifuge washing, taken hollow mesoporous Nano carbon balls ultrasonic disperse
Dry after obtaining solid phase, by dried product under argon gas protection, 5 DEG C/min of heating rate, 800 DEG C of h of high-temperature calcination 1, produce
The hollow mesoporous Nano carbon balls covering piece shape tungsten disulfide of sandwich structure（WS2@C）Nanoparticle.
2nd, product is verified：
Fig. 1 is the transmission electron microscope picture of the silica@silica/resorcinol-formaldehyde oligomer nanosphere prepared.Can from figure
See：Prepared product is that particle diameter is about 360 nm, scattered homogeneous, and surface is smooth, and core shell structure is presented（Titanium dioxide
Silicon@silica/resorcinol-formaldehyde oligomer nanosphere）.
Fig. 2 is the transmission electron microscope picture of the silica@silicon/carbon dioxide nanospheres prepared.From figure：Prepared receives
The particle diameter of rice ball is about 360 nm, and surface is slightly coarse, and outside shell is carbon, and internal core is that silica is titanium dioxide
Silicon@silicon/carbon dioxide nanospheres.
Fig. 3 is the transmission electron microscope picture of the hollow mesoporous Nano carbon balls prepared.From figure：Prepared interiors of products is sky
Core structure is that internal silica is etched completely, and the rough surface of shell is presented cellular, and hollow ball shell is intact and grain
Footpath is homogeneous, is uniformly dispersed.Hollow mesoporous Nano carbon balls diameter is about 360 nm, and carbon wall thickness is about 22nm.
Fig. 4 is the carbon coating tungsten sulfide that the shell prepared has sandwich structure（WS2@C）The transmission electricity of hollow nano-sphere
Mirror figure.From figure：Prepared product is that grown few layer of sheet in the carbon shell inside/outside walls of hollow mesoporous Nano carbon balls
Tungsten disulfide nano slices, tungsten disulfide nano slices are predominantly located at the inwall of carbon shell and outer wall tungsten disulfide nano slices skewness
It is even, and tungsten disulfide nano slices are without obvious agglomeration, while the pattern of carbon ball is not destroyed, outside carbon ball is reunited without obvious
Phenomenon, it is uniformly dispersed.
Fig. 5 is the carbon coating tungsten sulfide that the shell prepared has sandwich structure（WS2@C）The high-resolution of hollow nano-sphere
Transmission electron microscope picture.From figure：Few layer of WS has been loaded on the inside and outside wall of carbon shell2Nanometer sheet, form the three of a kind of shell
Mingzhi's structure WS2@C@WS2。
3rd, application effect：
The tungsten disulfide of the sheet of the hollow mesoporous Nano carbon balls cladding of sandwich structure prepared by the inventive method（WS2@C）Receive
Rice ball is assembled into button cell.
Fig. 6 and Fig. 7 is respectively the tungsten disulfide of the sheet of the hollow mesoporous Nano carbon balls cladding of the sandwich structure prepared
（WS2@C）The charge-discharge performance figure of nanosphere, the A g of current density 0.1-1With high rate performance figure.
Fig. 6 is electrode material in 0.1 A g-1Constant current density under charge-discharge performance figure, by 400 circle circulate
Afterwards, the tungsten disulfide of the sheet of the hollow mesoporous Nano carbon balls cladding of sandwich structure（WS2@C）The reversible specific capacity of nanosphere
For 892 mA h g-1。
Fig. 7 is the charge-discharge performance figure under different multiplying, by material in 0.1 A g-1、0.2 A g-1、0.5 A g-1、1 A g-1、2 A g-1、5 A g-1、8A g-1、10 A g-1Discharged under current density, be then returned to 0.1 A g-1Electric current is close
Degree is lower to discharge, and cycle charge-discharge 9 encloses respectively, when current density reaches 10 A g-1, its specific discharge capacity can still reach 336 mA
h g-1.Finally, when current density is returned to 0.1 A g-1Its specific discharge capacity and can returns to initial 848 mA h g-1, table
It is bright that there is fabulous high rate performance.
Claims (7)
1. a kind of shell has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure, it is characterised in that including
Following steps：
1）Under magnetic agitation, after first mixing ethanol, deionized water and ammoniacal liquor, tetraethyl orthosilicate is added, after remixing, then is added
Enter resorcinol and formaldehyde is reacted；
Reaction terminates rear centrifuge washing, obtains solid phase and dries, then the high-temperature calcination under argon gas atmosphere protection, then by high-temperature calcination
Product afterwards etches through sodium hydrate aqueous solution, finally by the product centrifuge washing after etching, and obtained solid phase is dried, i.e.,
Obtain hollow mesoporous carbon nanosphere；
2）Tungsten chloride and thiocarbamide solid are dissolved in deionized water under ultrasound condition, then add hollow mesoporous Nano carbon balls, is passed through
The laggard water-filling thermal response of ultrasonic disperse；
Hydro-thermal reaction terminates rear centrifuge washing, obtains the high-temperature calcination under argon gas atmosphere protection after solid phase is dried, produces shell tool
There is the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure.
2. preparation method according to claim 1, it is characterised in that the step 1）In, resorcinol and formaldehyde feed intake
Mass ratio is 1: 1~6.
3. preparation method according to claim 1 or 2, it is characterised in that the step 1）In, the reaction time is 12 h.
4. preparation method according to claim 1, it is characterised in that the step 1）In, the sodium hydrate aqueous solution
Concentration is 1~2 M, and the temperature of sodium hydrate aqueous solution is 50~90 DEG C.
5. preparation method according to claim 1, it is characterised in that the step 2）In, tungsten chloride, thiocarbamide and hollow Jie
The mass ratio that feeds intake of hole Nano carbon balls is 1: 1~5: 0.05~0.5.
6. preparation method according to claim 1 or 5, it is characterised in that the step 2）In, hydrothermal temperature is in reaction
150~250 DEG C, the h of reaction time 6~24.
7. preparation method according to claim 1, it is characterised in that the step 2）In, during high-temperature calcination with 1~5 DEG C/
Min heating rate, temperature is risen into 500~800 DEG C of 1~12 h of calcining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710772753.8A CN107611388A (en) | 2017-08-31 | 2017-08-31 | A kind of shell has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710772753.8A CN107611388A (en) | 2017-08-31 | 2017-08-31 | A kind of shell has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107611388A true CN107611388A (en) | 2018-01-19 |
Family
ID=61056789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710772753.8A Pending CN107611388A (en) | 2017-08-31 | 2017-08-31 | A kind of shell has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107611388A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109309224A (en) * | 2018-10-30 | 2019-02-05 | 陕西科技大学 | A kind of preparation method of tungsten disulfide/CFC@C multiphase composite electrode material |
| CN109545573A (en) * | 2018-03-21 | 2019-03-29 | 信阳学院 | The preparation method of metal 1T phase sulfuration rhenium hollow nanospheres electrode material for super capacitor |
| CN110600682A (en) * | 2018-06-12 | 2019-12-20 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
| CN111477847A (en) * | 2020-04-08 | 2020-07-31 | 扬州大学 | Box-shaped necklace multilevel structure Fe7S8/WS2@ C-CNFs lithium ion battery negative electrode material and preparation method thereof |
| CN112062919A (en) * | 2020-09-11 | 2020-12-11 | 华东理工大学 | Preparation method and application method of phenolic resin with hollow shell structure |
| CN113697856A (en) * | 2021-08-30 | 2021-11-26 | 齐齐哈尔大学 | NbS2Solvothermal preparation method of nanosheet self-assembled hollow microsphere |
| CN114512729A (en) * | 2020-11-16 | 2022-05-17 | 比亚迪股份有限公司 | Nanomaterial for negative electrode protection layer, negative electrode protection slurry, lithium negative electrode and lithium battery |
| CN114908372A (en) * | 2022-03-31 | 2022-08-16 | 福州大学 | Preparation method and application of mesoporous carbon sphere-coated zirconium supported catalyst |
| CN115064391A (en) * | 2022-05-25 | 2022-09-16 | 电子科技大学长三角研究院(湖州) | Preparation method of electrode material applied to asymmetric supercapacitor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816602A (en) * | 2017-03-28 | 2017-06-09 | 中南大学 | A kind of two selenium（Sulphur）Change molybdenum（Tungsten）/ carbon composite and its preparation method and application |
-
2017
- 2017-08-31 CN CN201710772753.8A patent/CN107611388A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816602A (en) * | 2017-03-28 | 2017-06-09 | 中南大学 | A kind of two selenium（Sulphur）Change molybdenum（Tungsten）/ carbon composite and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| XIAOHUI ZENG ET AL.: ""Hierarchical Nanocomposite of Hollow N‑Doped Carbon Spheres Decorated with Ultrathin WS2 Nanosheets for High-Performance Lithium-Ion Battery Anode"", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| XIUE ZHANG ET AL.: ""Petal-like MoS2 Nanosheets Space-Confined in Hollow Mesoporous Carbon Spheres for Enhanced Lithium Storage Performance"", 《ACS NANO》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109545573B (en) * | 2018-03-21 | 2020-08-28 | 信阳学院 | Preparation method of metal 1T-phase rhenium sulfide hollow nanosphere supercapacitor electrode material |
| CN109545573A (en) * | 2018-03-21 | 2019-03-29 | 信阳学院 | The preparation method of metal 1T phase sulfuration rhenium hollow nanospheres electrode material for super capacitor |
| CN110600682B (en) * | 2018-06-12 | 2022-03-01 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
| CN110600682A (en) * | 2018-06-12 | 2019-12-20 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
| CN109309224B (en) * | 2018-10-30 | 2021-07-27 | 陕西科技大学 | Preparation method of tungsten disulfide/CFC @ C multiphase composite electrode material |
| CN109309224A (en) * | 2018-10-30 | 2019-02-05 | 陕西科技大学 | A kind of preparation method of tungsten disulfide/CFC@C multiphase composite electrode material |
| CN111477847A (en) * | 2020-04-08 | 2020-07-31 | 扬州大学 | Box-shaped necklace multilevel structure Fe7S8/WS2@ C-CNFs lithium ion battery negative electrode material and preparation method thereof |
| CN111477847B (en) * | 2020-04-08 | 2022-07-19 | 扬州大学 | Box-shaped necklace multilevel structure Fe7S8/WS2@ C-CNFs lithium ion battery negative electrode material and preparation method thereof |
| CN112062919A (en) * | 2020-09-11 | 2020-12-11 | 华东理工大学 | Preparation method and application method of phenolic resin with hollow shell structure |
| CN114512729A (en) * | 2020-11-16 | 2022-05-17 | 比亚迪股份有限公司 | Nanomaterial for negative electrode protection layer, negative electrode protection slurry, lithium negative electrode and lithium battery |
| CN114512729B (en) * | 2020-11-16 | 2023-07-14 | 比亚迪股份有限公司 | Nanomaterial, negative electrode protection slurry, lithium negative electrode and lithium battery |
| CN113697856A (en) * | 2021-08-30 | 2021-11-26 | 齐齐哈尔大学 | NbS2Solvothermal preparation method of nanosheet self-assembled hollow microsphere |
| CN114908372A (en) * | 2022-03-31 | 2022-08-16 | 福州大学 | Preparation method and application of mesoporous carbon sphere-coated zirconium supported catalyst |
| CN114908372B (en) * | 2022-03-31 | 2023-11-17 | 福州大学 | Preparation method and application of mesoporous carbon sphere coated zirconium supported catalyst |
| CN115064391A (en) * | 2022-05-25 | 2022-09-16 | 电子科技大学长三角研究院(湖州) | Preparation method of electrode material applied to asymmetric supercapacitor |
| CN115064391B (en) * | 2022-05-25 | 2023-08-29 | 电子科技大学长三角研究院(湖州) | Preparation method of electrode material applied to asymmetric supercapacitor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107611388A (en) | A kind of shell has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure | |
| CN107591527A (en) | The preparation method of the hollow mesoporous carbon spheres of growth in situ petal-shaped molybdenum disulfide | |
| Li et al. | Ion-exchange strategy of CoS2/Sb2S3 hetero-structured nanocrystals encapsulated into 3D interpenetrating dual-carbon framework for high-performance Na+/K+ batteries | |
| CN102299326B (en) | Graphene modified lithium iron phosphate/carbon composite material and its application | |
| CN105355866B (en) | A kind of preparation method of cobaltosic oxide composite graphite alkene three-dimensional aeroge | |
| CN109286009B (en) | Preparation method of nano-sheet self-assembled three-dimensional nano-flower tin sulfide/graphitized carbon nitride lithium ion battery cathode material | |
| CN107522867A (en) | The preparation method of internal confinement growth MOFs hollow Nano carbon balls | |
| CN107481827A (en) | The preparation method of internal confinement growth MOFs hollow magnetic Nano carbon balls | |
| Tang et al. | Metal–organic frameworks-derived metal phosphides for electrochemistry application | |
| CN105047427B (en) | Ultracapacitor combination electrode material and preparation method thereof and ultracapacitor | |
| CN105826527A (en) | Porous silicon-carbon composite material and preparation method and application thereof | |
| Liu et al. | ZIF-67 derived carbon wrapped discontinuous CoxP nanotube as anode material in high-performance Li-ion battery | |
| CN108807957A (en) | Anode material of lithium-ion battery lacks layer rhenium disulfide nanometer sheet/hollow carbon sphere and preparation method thereof | |
| Yuan et al. | A facile room-temperature route to flower-like CuO microspheres with greatly enhanced lithium storage capability | |
| Zhu et al. | Three-dimensional hierarchical porous MnCo2O4@ MnO2 network towards highly reversible lithium storage by unique structure | |
| CN103682327A (en) | Lithium ion battery made of hollow porous nickel oxide composite material on basis of coating of N-doped carbon layer, and preparation method thereof | |
| Zhu et al. | Co-CoF2 heterojunctions encapsulated in N, F co-doped porous carbon as bifunctional oxygen electrocatalysts for Zn-air batteries | |
| Yu et al. | Porous MoO3 film as a high‐performance anode material for lithium‐ion batteries | |
| Wang et al. | Covalently binding ultrafine MoS2 particles to N, S co-doped carbon renders excellent Na storage performances | |
| Liu et al. | Uniform ReS2 porous nanospheres assembled from curly ReS2 few-layers with an expanded interlayer spacing for high-performance lithium-ion batteries | |
| CN108232158A (en) | A kind of preparation method of order mesoporous Co/CMK composite Nanos negative material | |
| Li et al. | Ethylene glycol combustion strategy towards 3D mesoporous ZnCo2O4 as anodes for Li-ion batteries | |
| CN102185155B (en) | Nanometer ferric phosphate hollow sphere/graphene lithium ion battery and preparation method thereof | |
| CN113506860A (en) | Carbon nanotube-in-tube @ selenium composite material and preparation method and application thereof | |
| Zhang et al. | Bimetallic dispersion zeolitic imidazolate framework derived spherical porous bifunctional catalysts for liquid/solid Zn-Air batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180119 |