CN103606642A - Preparation method and application of conjugated organic framework compound/sulfur composite material - Google Patents
Preparation method and application of conjugated organic framework compound/sulfur composite material Download PDFInfo
- Publication number
- CN103606642A CN103606642A CN201310639168.2A CN201310639168A CN103606642A CN 103606642 A CN103606642 A CN 103606642A CN 201310639168 A CN201310639168 A CN 201310639168A CN 103606642 A CN103606642 A CN 103606642A
- Authority
- CN
- China
- Prior art keywords
- organic frame
- composite material
- cyclic group
- frame compound
- conjugation organic
- 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
Images
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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method and an application of a conjugated organic framework compound/sulfur composite material. The composite material adopts a triazine ring group conjugated organic framework compound as a carrier, has a sulfur elementary substance loaded in pores of the triazine ring group conjugated organic framework compound, and can be used for preparing a positive electrode material of a lithium sulfur secondary battery. The preparation method comprises the steps: the liquid sulfur elementary substance flows into the pores of the triazine ring group conjugated organic framework compound, and thus the composite material of the triazine ring group conjugated organic framework compound and the sulfur elementary substance is obtained. The composite material is applied in the positive electrode material of the lithium sulfur secondary battery, and shows excellent charge/discharge performance and cycle stability performance.
Description
Technical field
The invention belongs to lithium-sulfur rechargeable battery anode material technology field, relate in particular to a kind of preparation method and application of conjugation organic frame compound/sulphur composite material.
Background technology
Have high-energy-density, long circulation life, high security, environmental protection and cheaply secondary cell at new energy field, there is huge application prospect.Lithium-sulfur rechargeable battery is that to take lithium metal be anodal secondary cell as negative pole, sulphur simple substance or sulfenyl composite material, and its theoretical energy density reaches 2600Wh/kg, is the representative of high-energy density secondary battery.With other secondary cells, compare, lithium-sulfur rechargeable battery has specific capacity, and high (theoretical specific capacity that the sulphur simple substance of take is anodal lithium-sulfur rechargeable battery reaches the advantages such as 1680mAh/g, sulphur aboundresources, environmental friendliness, low price.But lithium-sulfur rechargeable battery exists following not enough: sulphur simple substance can be reduced into the polysulfide of Yi Rong in discharge process, cause active material to run off, and polysulfide is dissolved in after electrolyte, increase concentration of electrolyte, thereby worsened the ionic conductivity of electrolyte.
Summary of the invention
The deficiency existing for prior art, the invention provides a kind of preparation method and application of triazine cyclic group conjugation organic frame compound/sulphur composite material, and this composite material can be used for the positive electrode of lithium-sulfur rechargeable battery.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
One, triazine cyclic group conjugation organic frame compound/sulphur composite material, the triazine cyclic group conjugation organic frame compound of take is carrier, its hole internal burden has sulphur simple substance.
Above-mentioned triazine cyclic group conjugation organic frame compound light weight, its component comprises C, N and H.
Above-mentioned triazine cyclic group conjugation organic frame compound structure is stable, chance water is difficult for decomposing.
The specific area of above-mentioned triazine cyclic group conjugation organic frame compound is preferably 700～900m
2/ g, can the more sulphur simple substance of load.
The pore volume of above-mentioned triazine cyclic group conjugation organic frame compound is preferably 0.3～1.0cm
3/ g.
The aperture of above-mentioned triazine cyclic group conjugation organic frame compound is preferably 1～2nm, this aperture is about 1～2 times of sulphur simple substance molecular diameter, can guarantee like this sulphur simple substance to be uniformly distributed in triazine cyclic group conjugation organic frame compound hole and not reunite, having improved the utilance of sulphur simple substance; And unnecessary space enough allows electrolyte and sulphur simple substance fully infiltrate.
Two, the preparation method of above-mentioned triazine cyclic group conjugation organic frame compound/sulphur composite material: liquid sulfur simple substance is flowed in triazine ring base conjugation organic frame compound hole, thereby obtain the composite material of triazine cyclic group conjugation organic frame compound and sulphur simple substance.
The above-mentioned intrapore concrete steps of liquid sulfur simple substance inflow triazine ring base conjugation organic frame compound that make are:
Mix triazine cyclic group conjugation organic frame compound and sulphur simple substance, be warming up to 140～155 ℃ and insulation, at this temperature, liquid sulfur has lower viscosity, can flow in triazine cyclic group conjugation organic frame compound hole, thereby can obtain triazine cyclic group conjugation organic frame compound/sulphur composite material.
In above-mentioned concrete steps, heating rate is preferably 3～5 ℃/min, and temperature retention time is preferably 9～15h, to guarantee that sulphur simple substance molecule fully enters in the hole of triazine cyclic group conjugation organic frame compound.
The mass ratio of above-mentioned triazine cyclic group conjugation organic frame compound and sulphur simple substance is 6:(3～5).
Three, above-mentioned triazine cyclic group conjugation organic frame compound/sulphur composite material can be applicable to the positive electrode of lithium-sulfur rechargeable battery.
Concrete application process is:
Mix triazine cyclic group conjugation organic frame compound/sulphur composite material and conductive agent, then add alite paste, after mixing, secondary rolls film forming, after dry by mould on collector, the mass ratio of triazine cyclic group conjugation organic frame compound/sulphur composite material, conductive agent and alite paste is (80～60): (30～10): 10.
Above-mentioned alite paste mass concentration is preferably 60%.
The present invention provides a kind of novel anode material for high-performance lithium sulfur rechargeable battery, absorption affinity due to triazine cyclic group conjugation organic frame compound hole, the loss by dissolution that can stop the polysulfide that sulphur simple substance produces in discharge process, thus the cycle performance of lithium-sulfur rechargeable battery improved.
In preferred version, the aperture of the triazine cyclic group conjugation organic frame compound hole adopting is 1～2 times of sulphur simple substance molecular diameter, there are so enough spaces to allow electrolyte and sulphur simple substance fully infiltrate, also guarantee that sulphur simple substance is uniformly distributed in triazine cyclic group conjugation organic frame compound hole and is difficult to reunion, thereby improve the utilance of sulphur simultaneously.
Compared with prior art, the present invention has following beneficial effect:
1, sulphur simple substance is dispersed in triazine cyclic group conjugation organic frame compound hole, realized the nanometer of sulphur simple substance, can effectively improve conductivity and the adsorption capacity of framework compound to solvable polysulfide of sulphur, thereby improve the utilance of sulphur, improve charge-discharge performance and the cyclical stability of lithium-sulfur rechargeable battery.
2, the load of sulphur simple substance is entered in framework compound hole, expanded the practical application of conjugation organic frame compound.
3, simple to operation, and in preparation process, sulphur simple substance can not produce any toxic gas, and environmental protection, has actual application prospect.
Accompanying drawing explanation
Fig. 1 is the head week charging and discharging curve of embodiment 2～4 prepared electrode materials;
Fig. 2 is first three week charging and discharging curve of embodiment 2 prepared electrode materials;
Fig. 3 is the specific discharge capacity of embodiment 2～4 prepared electrode materials and the curve of circulating cycle number;
Fig. 4 is the specific discharge capacity of embodiment 2 and 5 prepared electrode materials and the curve of circulating cycle number.
Embodiment
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, be only the present invention is described and never limit the present invention.
Embodiment 1
(1) preparation of triazine cyclic group conjugation organic frame Compound C TF-1:
Terephthalonitrile (1.0g, 7.8mmol) and zinc chloride (1.06g, 7.8mmol) are added to ampere pipe, vacuumize, and under vacuum condition tube sealing.The ampere pipe of sealing is put into Muffle furnace, keep 40 hours at 400 ℃, cooling rear taking-up, breaks ampere pipe into pieces and takes out product.Washed reaction product 4 hours is tentatively to remove zinc chloride; Product after washing is put into 1mol/L hydrochloric acid and soak 15 hours, to wash away zinc chloride, then, adopt respectively the product after water and oxolane cleaning and dipping, at 120 ℃, vacuumize obtains CTF-1.Gained CTF-1 specific area is 789m
2/ g, pore volume is 0.37cm
3/ g, aperture is 1.23nm.
(2) preparation of triazine cyclic group conjugation organic frame compound/sulphur composite material (CTF-1/S):
Get 0.3g CTF-1 and 0.2g sulphur simple substance and in mortar, grind and it is mixed obtain ground and mixed body, ground and mixed body is put into glassware in Muffle furnace, with 5 ℃/min heating rate, be warming up to 155 ℃, in 155 ℃ of insulations 15 hours; Then, naturally cool to room temperature, obtain CTF-1/S composite material.In the time of 155 ℃, sulphur simple substance has minimal viscosity, can make sulphur simple substance be adsorbed in micropore under the suction-operated of CTF-1 micropore.
Heating-up temperature of the present invention is not limited to 155 ℃, as long as guarantee that sulphur simple substance flows in triazine cyclic group conjugation organic frame compound hole for the liquid heating-up temperature simultaneously with less viscosity all can realize elemental sulfur.
Embodiment 2
Get CTF-1/S composite material, conductive agent acetylene black and the alite paste polytetrafluoroethylsolution solution of embodiment 1 preparation, the mass ratio of CTF-1/S composite material, conductive agent acetylene black and alite paste polytetrafluoroethylsolution solution is 60:30:10, and the mass fraction of polytetrafluoroethylsolution solution is 60%.CTF-1/S composite material and acetylene black ground and mixed are obtained to ground and mixed body, in ground and mixed body, add polytetrafluoroethylsolution solution, after mixing, roll into the film of thick approximately 100 microns, put into vacuum drying chamber and be dried 8 hours at 60 ℃, be pressed in collector aluminium online, obtained CTF-1/S electrode material.
Take CTF-1/S electrode material as anodal, and lithium sheet is negative pole, the LiTFSI/DOL:DME(1:1 volume ratio that electrolyte is 1mol/L, DOL: dioxolane, DME: glycol dimethyl ether), be assembled into button-shaped lithium-sulfur rechargeable battery.Employing discharges and recharges instrument this lithium-sulfur rechargeable battery is carried out to charge-discharge test, and current density is made as 0.1C, discharges and recharges cut-ff voltage and is made as between 1.1-3V.First all charging and discharging curves are shown in Fig. 1, within first three week, charging and discharging curve is shown in Fig. 2, the curve of specific discharge capacity and circulating cycle number is shown in Fig. 3, from Fig. 1～2, all specific discharge capacities of known head are that 1497mAh/g(calculates by the quality of sulphur), first all reversible capacities are that 1304mAh/g(calculates with the quality of sulphur), the discharge platform of battery remains two (2.3V and 2.1V), illustrates that in this material discharging process, electrode structure is stable, and discharge performance is excellent.As can be seen from Figure 3, after circulating 50 weeks, specific discharge capacity still maintains 762mAh/g(and calculates with the quality of sulphur).
Embodiment 3
Get CTF-1/S composite material, conductive agent acetylene black and the alite paste polytetrafluoroethylsolution solution of embodiment 1 preparation, the mass ratio of CTF-1/S composite material, conductive agent acetylene black and alite paste polytetrafluoroethylsolution solution is 70:20:10, and the mass fraction of polytetrafluoroethylsolution solution is 60%.CTF-1/S composite material and acetylene black ground and mixed are obtained to ground and mixed body, in ground and mixed body, add polytetrafluoroethylsolution solution, after mixing, roll into the film of thick approximately 100 microns, put into vacuum drying chamber and be dried 8 hours at 60 ℃, be pressed in collector aluminium online, obtained CTF-1/S electrode material.
Take CTF-1/S electrode material as anodal, and lithium sheet is negative pole, the LiTFSI/DOL:DME(1:1 volume ratio that electrolyte is 1mol/L, DOL: dioxolane, DME: glycol dimethyl ether), be assembled into button-shaped lithium-sulfur rechargeable battery.Employing discharges and recharges instrument this lithium-sulfur rechargeable battery is carried out to charge-discharge test, and current density is made as 0.1C, discharges and recharges cut-ff voltage and is made as between 1.1-3V.First all charging and discharging curves are shown in Fig. 1, and the curve of specific discharge capacity and circulating cycle number is shown in Fig. 3, and first all specific discharge capacities are that 1392mAh/g(calculates by the quality of sulphur as can be known from Fig. 1), first all reversible capacities are that 1230mAh/g(calculates with the quality of sulphur).As can be seen from Figure 3, after circulating 50 weeks, specific discharge capacity still maintains 635mAh/g(and calculates with the quality of sulphur).
Embodiment 4
Get CTF-1/S composite material, conductive agent acetylene black and the alite paste polytetrafluoroethylsolution solution of embodiment 1 preparation, the mass ratio of CTF-1/S composite material, conductive agent acetylene black and alite paste polytetrafluoroethylsolution solution is 80:10:10, and the mass fraction of polytetrafluoroethylsolution solution is 60%.CTF-1/S composite material and acetylene black ground and mixed are obtained to ground and mixed body, in ground and mixed body, add polytetrafluoroethylsolution solution, after mixing, roll into the film of thick approximately 100 microns, put into vacuum drying chamber and be dried 8 hours at 60 ℃, be pressed in collector aluminium online, obtained CTF-1/S electrode material.
Take CTF-1/S electrode material as anodal, and lithium sheet is negative pole, the LiTFSI/DOL:DME(1:1 volume ratio that electrolyte is 1mol/L, DOL: dioxolane, DME: glycol dimethyl ether), be assembled into button-shaped lithium-sulfur rechargeable battery.Employing discharges and recharges instrument this lithium-sulfur rechargeable battery is carried out to charge-discharge test, and current density is made as 0.1C, discharges and recharges cut-ff voltage and is made as between 1.1-3V.First all charging and discharging curves are shown in Fig. 1, and the curve of specific discharge capacity and circulating cycle number is shown in Fig. 3, and first all specific discharge capacities are that 1166mAh/g(calculates by the quality of sulphur as can be known from Fig. 1), first all reversible capacities are that 1035mAh/g(calculates with the quality of sulphur).As can be seen from Figure 3, after circulating 50 weeks, specific discharge capacity still maintains 565mAh/g(and calculates with the quality of sulphur).
Embodiment 5
Get the CTF-1 of 0.3g embodiment 1 preparation and 0.2g sulphur simple substance grinds and obtains ground and mixed body in mortar, by 60:30:10 mass ratio, get ground and mixed body, conductive agent acetylene black and alite paste polytetrafluoroethylsolution solution, the mass fraction of polytetrafluoroethylsolution solution is 60%.To after ground and mixed body and acetylene black ground and mixed, add polytetrafluoroethylsolution solution, after mixing, roll into the film of thick approximately 100 microns, put into vacuum drying chamber and be dried 8 hours at 60 ℃, be pressed in collector aluminium online, obtain CTF-1 electrode material.
Take CTF-1 electrode material as anodal, and lithium sheet is negative pole, the LiTFSI/DOL:DME(1:1 volume ratio that electrolyte is 1mol/L, DOL: dioxolane, DME: glycol dimethyl ether), be assembled into button-shaped lithium-sulfur rechargeable battery.Employing discharges and recharges instrument this lithium-sulfur rechargeable battery is carried out to charge-discharge test, and current density is made as 0.1C, discharges and recharges cut-ff voltage and is made as between 1.1-3V.Fig. 4 is the present embodiment battery and the specific discharge capacity of embodiment 2 batteries and the curve of circulating cycle number, known from this figure, embodiment 2 batteries its specific discharge capacity after circulation in 50 weeks is 762mAh/g, and the present embodiment battery its specific discharge capacity after circulation in 50 weeks is only 272mAh/g, illustrate that sulphur simple substance has really entered in CTF-1 micropore at 140～155 ℃ of temperature, and improved the cycle performance of battery.
Claims (8)
1. triazine cyclic group conjugation organic frame compound/sulphur composite material, is characterized in that: the triazine cyclic group conjugation organic frame compound of take is carrier, and its hole internal burden has sulphur simple substance.
2. triazine cyclic group conjugation organic frame compound/sulphur composite material as claimed in claim 1, is characterized in that: the specific area of described triazine cyclic group conjugation organic frame compound is 700～900m
2/ g, pore volume is 0.3～1.0cm
3/ g, hole aperture is 1～3nm.
3. the preparation method of triazine cyclic group conjugation organic frame compound/sulphur composite material claimed in claim 1, it is characterized in that: liquid sulfur simple substance is flowed in triazine ring base conjugation organic frame compound hole, thereby obtain the composite material of triazine cyclic group conjugation organic frame compound and sulphur simple substance.
4. the preparation method of triazine cyclic group conjugation organic frame compound/sulphur composite material as claimed in claim 3, is characterized in that: described make liquid sulfur simple substance flow into the intrapore concrete steps of triazine ring base conjugation organic frame compound to be:
Mix triazine cyclic group conjugation organic frame compound and sulphur simple substance, be warming up to 140 ~ 155 ℃ and insulation, thereby can obtain triazine cyclic group conjugation organic frame compound/sulphur composite material.
5. the preparation method of triazine cyclic group conjugation organic frame compound/sulphur composite material as claimed in claim 4, is characterized in that: described temperature retention time is 9～15h.
6. the preparation method of triazine cyclic group conjugation organic frame compound/sulphur composite material as claimed in claim 4, is characterized in that: described triazine cyclic group conjugation organic frame compound and the mass ratio of sulphur simple substance are 6:(3 ~ 5).
7. triazine cyclic group conjugation organic frame compound/sulphur composite material as claimed in claim 1 is applied to the positive electrode of lithium-sulfur rechargeable battery.
8. application as claimed in claim 7, it is characterized in that: mix triazine cyclic group conjugation organic frame compound/sulphur composite material and conductive agent, then add alite paste, after mixing, secondary rolls film forming, after dry by mould on collector, the mass ratio of triazine cyclic group conjugation organic frame compound/sulphur composite material, conductive agent and alite paste is (80 ~ 60): (30 ~ 10): 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310639168.2A CN103606642B (en) | 2013-12-02 | 2013-12-02 | A kind of preparation method of conjugation organic frame compound/sulphur composite material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310639168.2A CN103606642B (en) | 2013-12-02 | 2013-12-02 | A kind of preparation method of conjugation organic frame compound/sulphur composite material and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103606642A true CN103606642A (en) | 2014-02-26 |
| CN103606642B CN103606642B (en) | 2016-01-27 |
Family
ID=50124856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310639168.2A Expired - Fee Related CN103606642B (en) | 2013-12-02 | 2013-12-02 | A kind of preparation method of conjugation organic frame compound/sulphur composite material and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103606642B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126908A (en) * | 2015-08-24 | 2015-12-09 | 福州大学 | Sulfur-doped covalent triazine organic polymer visible photocatalyst, and preparation method and application thereof |
| KR101790877B1 (en) | 2016-05-17 | 2017-10-26 | 주식회사 엘지화학 | Polymer-sulfur complex, preparing method thereof, and lithium-sulfur battery comprising the same |
| CN108011094A (en) * | 2017-11-10 | 2018-05-08 | 上海交通大学 | A kind of preparation method of lithium-sulfur battery composite anode material |
| CN108807999A (en) * | 2018-05-07 | 2018-11-13 | 同济大学 | The method for synthesizing mixed crystal phase titanic oxide/covalent organic framework symbiosis interlocking structure |
| CN109244388A (en) * | 2018-08-20 | 2019-01-18 | 同济大学 | Covalent organic framework/titanium carbide nanosheet composite material preparation and application |
| CN110407165A (en) * | 2018-04-27 | 2019-11-05 | 宝山钢铁股份有限公司 | The covalent organic framework that lithium-sulfur cell is adulterated with selenium-sulphur anode composite material and its synthetic method |
| CN113845665A (en) * | 2021-09-28 | 2021-12-28 | 天津大学 | Full-conjugated organic triazine framework material and preparation method and application thereof |
| CN114171741A (en) * | 2020-09-11 | 2022-03-11 | 天津工业大学 | Positive active material carrier of lithium-sulfur battery and preparation method thereof |
| CN114873632A (en) * | 2022-04-24 | 2022-08-09 | 湖北大学 | Bis (trifluoromethanesulfonimide) lithium/zeolite imidazolate framework composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101587951A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | Novel carbon-sulfur compound for lithium-sulfur battery |
| CN102780001A (en) * | 2012-07-27 | 2012-11-14 | 中南大学 | Lithium-sulfur battery cathode material and preparation method thereof |
| US20130164615A1 (en) * | 2011-12-22 | 2013-06-27 | Arumugam Manthiram | Conductive polymer-coated, shaped sulfur-nanocomposite cathodes for rechargeable lithium-sulfur batteries and methods of making the same |
-
2013
- 2013-12-02 CN CN201310639168.2A patent/CN103606642B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101587951A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | Novel carbon-sulfur compound for lithium-sulfur battery |
| US20130164615A1 (en) * | 2011-12-22 | 2013-06-27 | Arumugam Manthiram | Conductive polymer-coated, shaped sulfur-nanocomposite cathodes for rechargeable lithium-sulfur batteries and methods of making the same |
| CN102780001A (en) * | 2012-07-27 | 2012-11-14 | 中南大学 | Lithium-sulfur battery cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| KEN SAKAUSHI等: ""Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device"", 《NATURE COMMUNICATIONS》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126908A (en) * | 2015-08-24 | 2015-12-09 | 福州大学 | Sulfur-doped covalent triazine organic polymer visible photocatalyst, and preparation method and application thereof |
| CN105126908B (en) * | 2015-08-24 | 2017-09-22 | 福州大学 | Sulfur doping covalent triazine organic polymer visible light catalyst and its preparation and application |
| KR101790877B1 (en) | 2016-05-17 | 2017-10-26 | 주식회사 엘지화학 | Polymer-sulfur complex, preparing method thereof, and lithium-sulfur battery comprising the same |
| CN108011094A (en) * | 2017-11-10 | 2018-05-08 | 上海交通大学 | A kind of preparation method of lithium-sulfur battery composite anode material |
| CN110407165A (en) * | 2018-04-27 | 2019-11-05 | 宝山钢铁股份有限公司 | The covalent organic framework that lithium-sulfur cell is adulterated with selenium-sulphur anode composite material and its synthetic method |
| CN108807999A (en) * | 2018-05-07 | 2018-11-13 | 同济大学 | The method for synthesizing mixed crystal phase titanic oxide/covalent organic framework symbiosis interlocking structure |
| CN108807999B (en) * | 2018-05-07 | 2021-03-26 | 同济大学 | Method for synthesizing mixed crystal phase titanium dioxide/covalent organic framework symbiotic interlocking structure |
| CN109244388A (en) * | 2018-08-20 | 2019-01-18 | 同济大学 | Covalent organic framework/titanium carbide nanosheet composite material preparation and application |
| CN109244388B (en) * | 2018-08-20 | 2021-05-11 | 同济大学 | Preparation and application of covalent organic framework/titanium carbide nanosheet composite material |
| CN114171741A (en) * | 2020-09-11 | 2022-03-11 | 天津工业大学 | Positive active material carrier of lithium-sulfur battery and preparation method thereof |
| CN113845665A (en) * | 2021-09-28 | 2021-12-28 | 天津大学 | Full-conjugated organic triazine framework material and preparation method and application thereof |
| CN113845665B (en) * | 2021-09-28 | 2022-11-08 | 天津大学 | Full-conjugated organic triazine framework material and preparation method and application thereof |
| CN114873632A (en) * | 2022-04-24 | 2022-08-09 | 湖北大学 | Bis (trifluoromethanesulfonimide) lithium/zeolite imidazolate framework composite material and preparation method and application thereof |
| CN114873632B (en) * | 2022-04-24 | 2023-09-22 | 湖北大学 | Double-trifluoro lithium methanesulfonimide/zeolite imidazole ester skeleton composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103606642B (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103606642B (en) | A kind of preparation method of conjugation organic frame compound/sulphur composite material and application | |
| CN106532012B (en) | A kind of sulphur-biomass carbon/transition metal combination electrode material and its preparation method and application | |
| CN102522530B (en) | Nano-sulfur composite cathode material for rare earth lithium-sulfur battery, and preparation method thereof | |
| CN103746098B (en) | A kind of preparation method of rich nitrogen multimode honeycomb carbon-sulphur composite positive pole | |
| CN106654215B (en) | Biological micromolecule and graphene composite material functional membrane and preparation method thereof | |
| CN102569759B (en) | Process for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries | |
| CN109768237B (en) | Lithium-sulfur battery positive electrode material, preparation method and application | |
| CN108269978B (en) | Quantum dot/carbon tube sulfur-carrying composite cathode material and preparation method and application thereof | |
| CN104966812A (en) | Three-dimensional porous quasi-graphene loaded molybdenum disulfide composite and preparation method thereof | |
| CN106920936B (en) | High-performance organic lithium ion battery positive electrode material and preparation method thereof | |
| CN102969481A (en) | Sulfur/carbon composite material for lithium-sulfur secondary battery and preparation method thereof | |
| CN103531759B (en) | Two step absorption preparation methods of high magnification sulphur/middle microporous carbon HAC anode composite material of lithium sulfur battery | |
| CN104600247A (en) | Sulfur-carbon composite positive electrode material for lithium-sulfur battery and preparation method of sulfur-carbon composite positive electrode material | |
| CN103515608A (en) | Graphene/sulfur composite material and preparation method thereof, battery positive electrode and preparation method thereof, and battery | |
| CN104362316A (en) | Lithium-sulfur battery composite cathode material, and preparation method and application thereof | |
| CN110148739A (en) | A kind of carbon@allyl sulfides itrile group polymer composite anode active material, anode and its preparation and the application in lithium-sulfur cell | |
| CN105609720A (en) | Preparation method and application of NiPC@CNTs/S composite material | |
| CN109346691B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
| CN107978736B (en) | Metal alloy/carbon tube/graphene sulfur-loaded composite cathode material and preparation method and application thereof | |
| CN107681130A (en) | A kind of preparation method of the lithium sulfur battery anode material of solid electrolyte | |
| CN106058229B (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN109411737B (en) | Polar sulfide-sulfur/porous carbon composite positive electrode material with three-dimensional structure and preparation method thereof | |
| CN109786690B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN105304866B (en) | A kind of lithium-sulphur cell positive electrode containing metal magnesium powder and preparation method thereof | |
| CN104716297B (en) | Oleophylic sulfur electrode preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160127 Termination date: 20171202 |