CN102315424A - Composite anode material for lithium sulfur battery, preparation method and application thereof - Google Patents
Composite anode material for lithium sulfur battery, preparation method and application thereof Download PDFInfo
- Publication number
- CN102315424A CN102315424A CN2010102202086A CN201010220208A CN102315424A CN 102315424 A CN102315424 A CN 102315424A CN 2010102202086 A CN2010102202086 A CN 2010102202086A CN 201010220208 A CN201010220208 A CN 201010220208A CN 102315424 A CN102315424 A CN 102315424A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- positive pole
- lithium
- sulphur
- composite positive
- 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
-
- 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 relates to a high-performance sulfur and set-appearance conductive polymer composite anode material for the anode of a lithium sulfur battery and a preparation technique thereof, belonging to the field of chemical power supplies. The composite anode material for the lithium sulfur battery provided by the invention is a sulfur and conductive polymer nanotube composite anode material. The sulfur is dispersed and absorbed on the surface of the conductive polymer nanotube and in the conductive polymer nanotube to form a hollow fibrous structure. The invention uses high-conductivity polymers with good adsorbability to the sulfur and the reduced product thereof as a conductive phase in a sulfur electrode, uses a co-heating method and a liquid sulfur infiltration method to enable the polymers to be evenly combined with the sulfur to obtain a composite electrode material, and solves the problems that the sulfur electrode and the reduced product thereof in the lithium sulfur battery are apt to be dissolved in organic electrolytes, the battery circulation performance is poor because of the non-conductivity of the sulfur and the like. The sixtieth cycling capacity of the composite material is larger than 650mAh/g and the electrochemical cycling stability is good.
Description
Technical field
The present invention relates to a kind of lithium-sulfur cell and use composite positive pole, especially relate to a kind of sulphur-polymer composites that is used as lithium-sulphur cell positive electrode and preparation method thereof and application, belong to field of chemical power source.
Background technology
At present; Along with various multifunctional portable electronic products and development such as electric motor car, energy storage field; Demand to the reversible secondary cell that uses is increasing; Therefore developing the reversible secondary cell with high-energy-density becomes the research focus, especially adopts the lithium metal to cause people's extensive concern especially as the high-energy-density lithium battery of electrode.One of limiting factor that it is main is the anodal application of height ratio capacity.Use sulphur is that the lithium-sulfur rechargeable battery of positive electrode has advantages such as high-energy-density, abundant raw materials; Wherein sulphur is that positive pole comprises: inorganic sulphide; Organic disulfide gathers organic disulfide, organic polysulfide, carbon-sulphur polymer, gathers thio-compounds and elemental sulfur.Wherein the specific discharge capacity of elemental sulfur is 1675mAh/g; Be that specific capacity is the highest in the positive electrode understood of present people, pollution-free, the low cost of elemental sulfur and nature reserves are abundant etc., and advantage makes it become one type of rising positive pole material of secondary lithium battery.But also there are two urgent problems in lithium-sulfur cell; The one, be insulator as the sulphur of electrode material; To cause problems such as the not good and utilance of the chemical property of sulphur in the electrode is low, so select the compound with it purpose that improves conductivity that reaches of one or more electronic conductors usually; Another many lithium sulfides that are discharge process produces are soluble in organic electrolyte; Cause the active material of electrode to reduce gradually, and because the principle of shuttling back and forth, many lithium sulfides of dissolving can pass on the negative pole lithium sheet that barrier film reaches battery; Product electric conductivity difference such as the lithium sulfide that generates and not dissolving; Cause the corrosion of GND and the increase of the internal resistance of cell, cause the cycle performance variation of battery, capacity is progressively decayed.Along with understanding to these problems; People have carried out a series of researchs: C.du.Liang in the control of the selection of conductive phase and pattern; Etal. (Chemistry ofMaterials 21 (2009) 4724-4730) use mesoporous carbon as conductive phase; Under heating condition, sulphur is infiltrated mesoporous carbon and form a kind of compound, 50 reversible capacities of this compound reach 700mAh/g; B.Zhang, the conductive phase that et al. (Electrochimica Acta 54 (2009) 3708-3713) uses is acetylene black, 50 reversible capacities of the compound that under heating condition, forms with sulphur are 500mAh/g; It is 650mAh/g that L.X.Yuan, et al. (Journal ofPower Sources 189 (2009) 1141-1146) adopt multi-walled carbon nano-tubes and sulphur to form 60 reversible specific capacities of electrically conductive composite.Can find out; Because the high conductivity of above-mentioned conductive phase and the diffusion that special pattern can limit many lithium sulfides; Make the cycle performance of lithium-sulfur cell therefore be greatly improved; But the synthesis technique of mesoporous carbon and multi-walled carbon nano-tubes is complicated, and cost is high, so be necessary to seek new alternative electric conducting material.
Summary of the invention
The objective of the invention is the problems such as battery cyclicity difference that cause to the non-conductive property of the sulphur utmost point in the lithium-sulfur cell and reduzate thereof easy dissolubility and the sulphur itself in organic bath, provide a kind of lithium-sulfur cell to use composite positive pole.
The present invention utilizes the conductivity of polymer, strong adsorption effect and specific nanotube-shaped pattern, prepares a kind of composite sulfur material that contains conducting polymer, solves the problems referred to above.
A kind of lithium-sulfur cell provided by the invention is used composite positive pole, is sulphur-conductive polymer nanometer pipe composite positive pole, and described sulphur content looses in the tube-surface be adsorbed in said conductive polymer nanometer pipe and the pipe, forms the filamentary structure of hollow.
The external diameter of said hollow fiber structure is 100～200nm, and the internal diameter of said hollow fiber structure is 50～80nm.Preferable, described sulphur accounts for 15～56% of said composite positive pole total weight, is preferably 40～56%.
Preferable, described conducting polymer is selected from polypyrrole, gathers propylamine, polythiophene, polyacetylene or their derivative.
Conductive polymer nanometer pipe described in the present invention can be synthetic through the selfdecomposition soft template method.The reaction mechanism of this method is: make a certain proportion of oxidant and methyl orange in the aqueous solution, form fibrous complex compound earlier; Under the oxidation of oxidant; The monomer that makes conducting polymer is at complex compound fiber surface polymerization reaction take place; Along with the carrying out of polymerization reaction, oxidant is reduced and causes the decomposition of complex compound fiber gradually, thereby stays nanotube-shaped conducting polymer fibres.This method preparation technology is simple, easy to operate, the employing cost of material is cheap, products therefrom is the nanotube of size homogeneous and controllable.
Preferable; The preparation method of the conductive polymer nanometer pipe described in the present invention may further comprise the steps: in the methyl orange solution of the 0.004-0.006mol/L of 100ml, drip the variable valency metal chloride of 0.004-0.006mol; And then the polymer monomer of adding 0.004-0.006mol; Room temperature reaction 8-24 hour, collect product, obtain the conductive polymer nanometer pipe.
Described oxidant is the chloride of variable valency metal, like FeCl
3, CrCl
3Deng.
Sulphur of the present invention-conductive polymer nanometer pipe composite positive pole can use hot altogether method or liquid phase sulphur infiltration method to synthesize.
Adopting altogether, hot legal system is equipped with sulphur-conductive polymer nanometer pipe composite positive pole; May further comprise the steps: mass ratio is (1～3): 1 sublimed sulfur and conductive polymer nanometer pipe mix; Under vacuum or protective atmosphere,, obtain sulphur-conductive polymer nanometer pipe composite positive pole after naturally cooling to room temperature in 150～250 ℃ of insulation 3～6h.
In the above-mentioned hot method altogether, described mixed method with conducting polymer and sublimed sulfur is mortar mill or planetary type ball-milling.Described protective gas can be argon gas or nitrogen.
In the above-mentioned hot method altogether; Described heat treatment temperature (150～250 ℃) sulphur down is a molten state; The sulphur of this moment has low viscosity and is easy to wetting conductive polymer nanometer pipe, and sulphur has bigger volatilization under higher temperature, and sulphur steam can get in the micropore of conductive polymer nanometer pipe substrate.Temperature retention time is 3-6 hour, can get in the pipe of conducting base with the sulphur that guarantees molten state.
Adopt liquid phase sulphur infiltration method to prepare sulphur-conductive polymer nanometer pipe composite positive pole, may further comprise the steps:
(1) with the complete fusion of sublimed sulfur, quench cooled in air or water is dissolved in the non-polar solven more then, obtains the solution of sulfur content 8～12wt% after the filtration;
(2) the conductive polymer nanometer pipe is immersed in the solution of step 1 gained, stir and leave standstill after 10～30 minutes, filter the back products therefrom, obtain sulphur-conductive polymer nanometer pipe composite positive pole in oven dry under vacuum or protective atmosphere under 50～100 ℃.
In the above-mentioned liquid phase sulphur infiltration method, also can with products therefrom again repeating step 2 obtain the sulphur-conductive polymer nanometer pipe composite positive pole of required sulfur content.
In the above-mentioned liquid phase sulphur infiltration method, said in air or water the purpose of quench cooled be in order to keep the high temperature phase of sulphur.
In the above-mentioned liquid phase sulphur infiltration method, described non-polar solven is mainly selected according to the similar principle that mixes, and is CS
2, CCl
4, toluene etc.
Related heat treatment process can adopt under vacuum or the protective atmosphere and carry out among the present invention, and protective gas can be argon gas or nitrogen.
In above-mentioned hot method altogether and the liquid phase sulphur infiltration method, described conductive polymer nanometer pipe and sublimed sulfur need under vacuum condition dry respectively before use.Described dry run can adopt under vacuum or the protective atmosphere carries out, and protective gas can be argon gas or nitrogen.
The present invention adopts the characteristic of sulphur-conducting polymer composite anode material that said method obtains following:
(1) the conducting polymer matrix is a nanotube, and its size is even, and the network that is intertwined to form is that the transmission of electric charge provides more path;
(2) sulphur all is evenly distributed in the surface or pipe of conductive polymer nanometer pipe through two kinds of diverse ways, and sulphur and conducting polymer matrix touch closely indirectly, improve the conductivity of composite material.
(3) content of sulphur in composite positive pole is controlled, i.e. the capacity controllable of composite positive pole
Conducting polymer is because its loose appearance structure; Sulphur there is certain suction-operated; Sulphur is attracted in the micropore of nanotube-shaped conducting polymer matrix; Effectively limited sulphur or many lithium sulfides diffuse out electrode matrix, and increased the sulphur of insulator and contacting of conductive phase, more reflecting points that combine with lithium are provided.And the electron channel that the formed network configuration of conductive polymer nanometer pipe is provided can help to improve the conductivity of electrode.
The present invention adopts has polymer that good adsorption property and have high conductivity itself as the conductive phase in the sulfur electrode to sulphur and reduzate thereof; Adopt altogether that hot method and sulphur infiltration method make it evenly to combine to obtain combination electrode material with sulphur, solved the non-conductive property of the sulphur utmost point in the lithium-sulfur cell and reduzate thereof easy dissolubility and the sulphur itself in organic bath and the problems such as battery cyclicity difference that cause.Material provided by the present invention can be used in the lithium-sulfur cell using as positive electrode, and the 60th circulation volume of this composite material be greater than 650mAh/g, and has good electrochemistry cyclical stability.
Description of drawings
Fig. 1 is the TEM shape appearance figure of sulphur-Pt/Polypyrrole composite material among the embodiment 2.
Fig. 2 is the situation of change of the discharge capacity of gained composite electrode among bright sulfur electrode and the embodiment with cycle-index.
Embodiment
For further setting forth content of the present invention, substantive features and marked improvement, enumerate following examples now and specify as follows, but be not limited only to embodiment.
The conducting polymer that the present invention relates to is example explanation with polypyrrole and polyaniline, and its preparation method is: the FeCl that in 100ml concentration is the methyl orange aqueous solution of 0.005mol/L, adds 0.005mol
3, evenly back formation is wadding fibrous for electromagnetic agitation, adds 0.005mol pyrroles or aniline monomer then, stirs 12 hours under the room temperature; Product alternately cleans the back with deionized water and alcohol and obtains the polypyrrole pipe at 80 ℃ of vacuum dryings.
Comparative Examples 1
With sublimed sulfur powder and acetylene black with gather oxireme (PEO) and in the acetonitrile medium, process slurry in 5: 3: 2 ratio, coat on the aluminium foil and carry out drying, process electrode film thus.With metallic lithium foil is to electrode, and U.S. Celgard company polypropylene screen is a barrier film, 1M LiCF
3SO
3/ TEGDME is an electrolyte, in the voltage range of 1-3V, and 0.1mA/cm
2Current density under discharge and recharge experiment.The experimental result of gained is as shown in table 1 below.From table, can find out that the capacity attenuation of bright sulfur electrode is very fast, after the 60th circulation, reversible capacity decays to 97.6mAh/g from initial value 698.1mAh/g, and the capacity attenuation rate reaches 86.1%.
Embodiment 1
At first respectively with sulphur and polypyrrole at 50 ℃ of following vacuumize 10h.Is to mix final vacuum at 2: 1 to be sealed in the glass container with sulphur and polypyrrole by mass ratio, and insulation 4 hours under 150 ℃ of conditions then obtains sulfur content and be sulphur-Pt/Polypyrrole composite material (SPT1) of 56% behind the natural cooling.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Test result is seen table 1.
Embodiment 2
Raw-material drying such as embodiment 1.With mass ratio is that to obtain sulfur content by the method for embodiment 1 behind 1: 1 sulphur and the polypyrrole mixing be sulphur-Pt/Polypyrrole composite material (SPT2) of 40%.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Test result is seen table 1.Data from table 1 can be found out, compare the bright sulfur electrode, and the cycle performance of composite electrode has had large increase.
Embodiment 3
Raw-material drying such as embodiment 1.140 ℃ of complete fusions, quench cooled in air or water is dissolved in CS with it then with sulphur
2In, obtain the filtrating of sulfur-bearing 10% after the filtration.An amount of polypyrrole nanotube is immersed the CS of above sulphur
2Solution stirs and left standstill 20 minutes after 10 minutes, and it is sulphur-Pt/Polypyrrole composite material (SPI1) of 15% that the product after will filtering then promptly obtains sulfur content at 50 ℃ of following vacuum dryings.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Test result is seen table 1.
Embodiment 4
Sulphur-the Pt/Polypyrrole composite material that obtains among an amount of embodiment 3 (SPI1) is immersed the CS of sulfur-bearing about 10%
2Solution, obtaining sulfur content by the method for embodiment 3 is sulphur-polypyrrole material (SPI2) of 24%.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Test result is seen table 1.
Embodiment 5
By the synthetic method of polypyrrole nanotube in the embodiment, be that monomer has synthesized the polyaniline nano pipe with aniline.Raw-material drying such as embodiment 1.Be that to obtain sulfur content by the method for embodiment 1 behind 1: 1 sulphur and the polyaniline mixing be sulphur-polyaniline composite material (S-PAnl) of 40% with mass ratio.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Test result is seen table 1.
Embodiment 6
Press the CS of method configuration sulfur-bearing about 10% among the embodiment 3
2Solution.Then an amount of polyaniline nano pipe is immersed in the above solution, stir and left standstill 20 minutes after 10 minutes, it is sulphur-polyaniline composite material (S-PAn2) of 15% that the product after will filtering then promptly obtains sulfur content at 50 ℃ of following vacuum dryings.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Test result is seen table 1.
Embodiment 7
By the synthetic method of polypyrrole nanotube in the embodiment, be that monomer has synthesized the polyaniline nano pipe with aniline.Raw-material drying such as embodiment 1.With mass ratio is that 1: 1 sulphur and polyaniline mixing final vacuum is sealed in the glass container, and insulation 3 hours under 250 ℃ of conditions then obtains sulfur content and be sulphur-polyaniline composite material of 40% behind the natural cooling.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Test result and embodiment 5 are basic identical.
Embodiment 8
By the synthetic method of polypyrrole nanotube in the embodiment, be that monomer has synthesized the polyaniline nano pipe with aniline.Raw-material drying such as embodiment 1.With mass ratio is that 3: 1 sulphur and polyaniline mixing final vacuum is sealed in the glass container, and insulation 6 hours under 200 ℃ of conditions then obtains sulfur content and be sulphur-polyaniline composite material of 50% behind the natural cooling.Electrode preparation method and battery assembling, test condition are all with Comparative Examples 1.Test result and embodiment 5 are basic identical.
Table 1
Data listed from table 1 can find out that the composite positive pole of altogether hot method preparation all has higher capability retention, all is greatly improved than the electrode material in the Comparative Examples.
Related polar solvent C in the foregoing description
2S can be by CCl
4Or toluene is alternative, and the gained composite material is through detecting its result and use polar solvent C
2Basic identical during S.
The foregoing description gained composite material detects through TEM, and its structure all is hollow fiber, and its external diameter is 100～200nm, and internal diameter is 50～80nm.
Claims (10)
1. a lithium-sulfur cell is used composite positive pole, it is characterized in that, is sulphur-conductive polymer nanometer pipe composite positive pole, and described sulphur content looses in the tube-surface be adsorbed in said conductive polymer nanometer pipe and the pipe, forms the filamentary structure of hollow.
2. lithium-sulfur cell as claimed in claim 1 is used composite positive pole, it is characterized in that, the external diameter of said hollow fiber structure is 100～200nm, and the internal diameter of said hollow fiber structure is 50～80nm.
3. lithium-sulfur cell as claimed in claim 1 is used composite positive pole, it is characterized in that, described sulphur accounts for 15～56% of said composite positive pole total weight.
4. lithium-sulfur cell as claimed in claim 1 is used composite positive pole, it is characterized in that, described conducting polymer is selected from polypyrrole, gathers propylamine, polythiophene, polyacetylene or their derivative.
5. use composite positive pole like the described lithium-sulfur cell of arbitrary claim among the claim 1-4, it is characterized in that, described conductive polymer nanometer pipe is synthetic through the selfdecomposition soft template method.
Like the described lithium-sulfur cell of arbitrary claim among the claim 1-5 with the preparation method of composite positive pole; For being total to hot method; May further comprise the steps: mass ratio is (1～3): 1 sublimed sulfur and conductive polymer nanometer pipe mix; Under vacuum or protective atmosphere,, obtain sulphur-conductive polymer nanometer pipe composite positive pole after naturally cooling to room temperature in 150～250 ℃ of insulation 3～6h.
7. lithium-sulfur cell as claimed in claim 6 is characterized in that with the preparation method of composite positive pole described mixed method with conducting polymer and sublimed sulfur is mortar mill or planetary type ball-milling.
Like the described lithium-sulfur cell of arbitrary claim among the claim 1-5 with the preparation method of composite positive pole, be liquid phase sulphur infiltration method, may further comprise the steps:
(1) with the complete fusion of sublimed sulfur, quench cooled in air or water is dissolved in the non-polar solven more then, obtains the solution of sulfur content 8～12wt% after the filtration;
(2) the conductive polymer nanometer pipe is immersed in the solution of step 1 gained, stir and leave standstill after 10～30 minutes, filter the back products therefrom in vacuum or protective atmosphere oven dry down; Obtain sulphur-conductive polymer nanometer pipe composite positive pole.
9. lithium-sulfur cell as claimed in claim 8 is characterized in that with the preparation method of composite positive pole described non-polar solven is selected from CS
2, CCl
4Or toluene.
Like the described lithium-sulfur cell of arbitrary claim among the claim 1-5 with composite positive pole application as positive electrode in lithium-sulfur cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010220208.6A CN102315424B (en) | 2010-07-06 | 2010-07-06 | Composite anode material for lithium sulfur battery, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010220208.6A CN102315424B (en) | 2010-07-06 | 2010-07-06 | Composite anode material for lithium sulfur battery, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102315424A true CN102315424A (en) | 2012-01-11 |
| CN102315424B CN102315424B (en) | 2014-07-16 |
Family
ID=45428369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010220208.6A Expired - Fee Related CN102315424B (en) | 2010-07-06 | 2010-07-06 | Composite anode material for lithium sulfur battery, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102315424B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103247776A (en) * | 2012-02-07 | 2013-08-14 | 苏州宝时得电动工具有限公司 | Preparation method for electrode composite material |
| CN103262302A (en) * | 2010-11-04 | 2013-08-21 | 罗伯特·博世有限公司 | Cathode material for a lithium sulfur battery |
| CN103259000A (en) * | 2013-04-25 | 2013-08-21 | 浙江师范大学 | Polypyrrole hollow microsphere/ sulfur composite material as well as preparation method and application thereof |
| CN104157839A (en) * | 2014-08-22 | 2014-11-19 | 南京中储新能源有限公司 | Polyaniline nanotube-sulfur composite material and secondary battery |
| CN104157829A (en) * | 2014-08-22 | 2014-11-19 | 南京中储新能源有限公司 | Sulfur carbon composite material based on polyaniline nanotubes and preparation method thereof, and secondary battery |
| CN104201336A (en) * | 2014-09-10 | 2014-12-10 | 南京中储新能源有限公司 | Polyaniline nano array-based sulfur composite material, preparation method thereof and secondary battery |
| CN104835966A (en) * | 2015-04-30 | 2015-08-12 | 奇瑞汽车股份有限公司 | Lithium sulfur battery cathode material and preparation method thereof |
| TWI511359B (en) * | 2013-10-17 | 2015-12-01 | Hon Hai Prec Ind Co Ltd | Lithium ion battery active material and method for making the same |
| CN105762341A (en) * | 2016-03-04 | 2016-07-13 | 河源广工大协同创新研究院 | Preparation method of nano-sulfur/annular polypyrrole composite positive electrode material |
| CN105958033A (en) * | 2016-07-04 | 2016-09-21 | 吉林大学 | Preparation method and application of non-graphitizing carbon nano tube/sulfur composite material |
| CN106299317A (en) * | 2016-11-03 | 2017-01-04 | 深圳市沃特玛电池有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof, lithium-sulfur cell |
| CN107275580A (en) * | 2017-07-10 | 2017-10-20 | 华南理工大学 | A kind of long circulation life height ratio capacity lithium sulfur battery anode material and lithium-sulphur cell positive electrode and its preparation |
| CN109256554A (en) * | 2018-09-28 | 2019-01-22 | 河南科技学院 | A kind of sulfide polymer composite material and preparation method and application |
| CN109616647A (en) * | 2018-12-10 | 2019-04-12 | 安徽师范大学 | 3-D ordered multiporous structure hydrogel sulfur loaded particulate composite and preparation method thereof, lithium-sulphur cell positive electrode, lithium-sulfur cell |
| CN109802105A (en) * | 2018-12-24 | 2019-05-24 | 肇庆市华师大光电产业研究院 | A kind of polyaniline nano tube packaging metal nanometer line array/sulphur composite material, controllable method for preparing and application |
| CN112542579A (en) * | 2020-12-24 | 2021-03-23 | 太原理工大学 | Conductive Janus film, preparation method and application of conductive Janus film in preparation of lithium-sulfur battery anode |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3883367A (en) * | 1972-10-19 | 1975-05-13 | Toyoda Chuo Kenkyusho Kk | Sodium-sulfur storage battery |
| CN1396202A (en) * | 2002-04-17 | 2003-02-12 | 中国科学院上海微***与信息技术研究所 | Sulfur/electric conducting polymer composition used as positive electrode of electrochemical power supply and its method |
| CN101070383A (en) * | 2007-02-13 | 2007-11-14 | 同济大学 | Method for preparing poly 1,5-naphthalene diamine nano pipe |
| CN101562261A (en) * | 2009-06-02 | 2009-10-21 | 北京理工大学 | Lithium-sulfur battery and preparation method thereof |
| CN101562244A (en) * | 2009-06-02 | 2009-10-21 | 北京理工大学 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
| CN101740758A (en) * | 2010-01-04 | 2010-06-16 | 北京航空航天大学 | Preparation method of vulcanized conducting polymer composite anode for lithium ion battery |
-
2010
- 2010-07-06 CN CN201010220208.6A patent/CN102315424B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3883367A (en) * | 1972-10-19 | 1975-05-13 | Toyoda Chuo Kenkyusho Kk | Sodium-sulfur storage battery |
| CN1396202A (en) * | 2002-04-17 | 2003-02-12 | 中国科学院上海微***与信息技术研究所 | Sulfur/electric conducting polymer composition used as positive electrode of electrochemical power supply and its method |
| CN101070383A (en) * | 2007-02-13 | 2007-11-14 | 同济大学 | Method for preparing poly 1,5-naphthalene diamine nano pipe |
| CN101562261A (en) * | 2009-06-02 | 2009-10-21 | 北京理工大学 | Lithium-sulfur battery and preparation method thereof |
| CN101562244A (en) * | 2009-06-02 | 2009-10-21 | 北京理工大学 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
| CN101740758A (en) * | 2010-01-04 | 2010-06-16 | 北京航空航天大学 | Preparation method of vulcanized conducting polymer composite anode for lithium ion battery |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103262302A (en) * | 2010-11-04 | 2013-08-21 | 罗伯特·博世有限公司 | Cathode material for a lithium sulfur battery |
| CN103247776A (en) * | 2012-02-07 | 2013-08-14 | 苏州宝时得电动工具有限公司 | Preparation method for electrode composite material |
| CN103247776B (en) * | 2012-02-07 | 2016-02-17 | 苏州宝时得电动工具有限公司 | The preparation method of electrode composite material |
| CN103259000A (en) * | 2013-04-25 | 2013-08-21 | 浙江师范大学 | Polypyrrole hollow microsphere/ sulfur composite material as well as preparation method and application thereof |
| TWI511359B (en) * | 2013-10-17 | 2015-12-01 | Hon Hai Prec Ind Co Ltd | Lithium ion battery active material and method for making the same |
| US9240589B2 (en) | 2013-10-17 | 2016-01-19 | Tsinghua University | Electrode active material of lithium ion battery and method for making the same |
| CN104157829B (en) * | 2014-08-22 | 2016-01-20 | 南京中储新能源有限公司 | A kind of secondary aluminium cell comprising sulphur carbon composite based on polyaniline nanotube |
| CN104157839A (en) * | 2014-08-22 | 2014-11-19 | 南京中储新能源有限公司 | Polyaniline nanotube-sulfur composite material and secondary battery |
| CN104157829A (en) * | 2014-08-22 | 2014-11-19 | 南京中储新能源有限公司 | Sulfur carbon composite material based on polyaniline nanotubes and preparation method thereof, and secondary battery |
| CN104201336A (en) * | 2014-09-10 | 2014-12-10 | 南京中储新能源有限公司 | Polyaniline nano array-based sulfur composite material, preparation method thereof and secondary battery |
| CN104835966A (en) * | 2015-04-30 | 2015-08-12 | 奇瑞汽车股份有限公司 | Lithium sulfur battery cathode material and preparation method thereof |
| CN105762341A (en) * | 2016-03-04 | 2016-07-13 | 河源广工大协同创新研究院 | Preparation method of nano-sulfur/annular polypyrrole composite positive electrode material |
| CN105958033A (en) * | 2016-07-04 | 2016-09-21 | 吉林大学 | Preparation method and application of non-graphitizing carbon nano tube/sulfur composite material |
| CN105958033B (en) * | 2016-07-04 | 2018-07-06 | 吉林大学 | A kind of preparation method and application of non-graphitized carbon nanotube/sulphur composite material |
| CN106299317A (en) * | 2016-11-03 | 2017-01-04 | 深圳市沃特玛电池有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof, lithium-sulfur cell |
| CN107275580A (en) * | 2017-07-10 | 2017-10-20 | 华南理工大学 | A kind of long circulation life height ratio capacity lithium sulfur battery anode material and lithium-sulphur cell positive electrode and its preparation |
| CN107275580B (en) * | 2017-07-10 | 2020-05-22 | 华南理工大学 | Lithium-sulfur battery positive electrode material with long cycle life and high specific capacity, lithium-sulfur battery positive electrode and preparation of lithium-sulfur battery positive electrode |
| CN109256554A (en) * | 2018-09-28 | 2019-01-22 | 河南科技学院 | A kind of sulfide polymer composite material and preparation method and application |
| CN109616647A (en) * | 2018-12-10 | 2019-04-12 | 安徽师范大学 | 3-D ordered multiporous structure hydrogel sulfur loaded particulate composite and preparation method thereof, lithium-sulphur cell positive electrode, lithium-sulfur cell |
| CN109616647B (en) * | 2018-12-10 | 2021-09-28 | 安徽师范大学 | Three-dimensional ordered porous hydrogel-loaded sulfur particle composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN109802105A (en) * | 2018-12-24 | 2019-05-24 | 肇庆市华师大光电产业研究院 | A kind of polyaniline nano tube packaging metal nanometer line array/sulphur composite material, controllable method for preparing and application |
| CN112542579A (en) * | 2020-12-24 | 2021-03-23 | 太原理工大学 | Conductive Janus film, preparation method and application of conductive Janus film in preparation of lithium-sulfur battery anode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102315424B (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102315424B (en) | Composite anode material for lithium sulfur battery, preparation method and application thereof | |
| Mwizerwa et al. | Sulfur-embedded FeS2 as a high-performance cathode for room temperature all-solid-state lithium–sulfur batteries | |
| CN102208608B (en) | Preparation method of carbon-sulfur composite material for lithium ion battery carbon cathode material | |
| Sun et al. | Sulfur-rich polymeric materials with semi-interpenetrating network structure as a novel lithium–sulfur cathode | |
| Lin et al. | Lithium–sulfur batteries: from liquid to solid cells | |
| Wu et al. | Improvement of rate and cycle performence by rapid polyaniline coating of a MWCNT/sulfur cathode | |
| CN102820454B (en) | Electrode composite material and preparation method thereof, positive pole, there is this anodal battery | |
| CN102945947B (en) | Preparation method of flexible binding agent-free self-support combination electrode | |
| Zhuang et al. | β‐molybdenum carbide/carbon nanofibers as a shuttle inhibitor for lithium‐sulfur battery with high sulfur loading | |
| CN109103399B (en) | Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery | |
| CN110247047B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| Feng et al. | Synthesis and electrochemical properties of MoO3/C nanocomposite | |
| CN109817963B (en) | Fe7Se8Preparation method and application of nano particle/nitrogen-doped carbon nanofiber composite material | |
| CN104157860B (en) | sodium-selenium cell and preparation method thereof | |
| Gao et al. | Flexible and hierarchically structured sulfur composite cathode based on the carbonized textile for high-performance Li–S batteries | |
| Liu et al. | Recent Advances in Cathode Materials for Room‐Temperature Sodium− Sulfur Batteries | |
| Yang et al. | Flexible SnTe/carbon nanofiber membrane as a free-standing anode for high-performance lithium-ion and sodium-ion batteries | |
| CN105355877A (en) | Graphene-metal oxide composite negative electrode material and preparation method therefor | |
| CN105161722A (en) | Porous carbon nanofiber membrane for positive electrode material of lithium-sulfur battery and preparation method thereof | |
| CN104600249A (en) | Preparation methods of nanometer porous metal and nanometer porous metal and lithium-sulfur battery positive pole material | |
| CN107579233A (en) | A kind of metal-doped silicon oxide molecular sieve/sulphur carbon complex and its preparation method and application | |
| CN106898746A (en) | Hierarchical porous structure nano-sized carbon/sulphur composite and the application in lithium-sulfur cell are prepared by raw material of Hawaii shell | |
| Tang et al. | Nickel fibers/sulfur composites cathode with enhanced electrochemical performance for rechargeable lithium-sulfur batteries | |
| Li et al. | Ultrafine Sb2S3@ carbon-nanofibers for fast and stable sodium storage | |
| Yu et al. | Promoting polysulfide redox kinetics by Co9S8 nanoparticle-embedded in N-doped carbon nanotube hollow polyhedron for lithium sulfur batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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 |
Granted publication date: 20140716 Termination date: 20160706 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |