CN103972510A - Preparation method of sulfurized polyacrylonitrile anode material used for lithium secondary battery - Google Patents
Preparation method of sulfurized polyacrylonitrile anode material used for lithium secondary battery Download PDFInfo
- Publication number
- CN103972510A CN103972510A CN201410194569.6A CN201410194569A CN103972510A CN 103972510 A CN103972510 A CN 103972510A CN 201410194569 A CN201410194569 A CN 201410194569A CN 103972510 A CN103972510 A CN 103972510A
- Authority
- CN
- China
- Prior art keywords
- polyacrylonitrile
- preparation
- sulfurized
- sulfurized polyacrylonitrile
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/604—Polymers containing aliphatic main chain polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a sulfurized polyacrylonitrile anode material used for a lithium secondary battery, and belongs to the technical field of materials. The preparation method is that sulfur and polyacrylonitrile are dissolved in dimethyl sulfoxide to have a crosslinking conjugation reaction and then are carbonized in a nitrogen environment at a temperature of 500 DEG C to obtain the sulfurized polyacrylonitrile material. The sulfur content of the sulfurized polyacrylonitrile material obtained through the preparation method is remarkably increased, the sulfur is distributed evenly, and the sulfurized polyacrylonitrile material has a graphite crystal structure and is remarkably improved in conductivity and stability. In the electrochemical test, the sulfurizedpolyacrylonitrile material shows the discharge quality specific capacity up to 1312mAh.g<-1> and the sulfur utilization rate up to 98.3%, and keeps 77% of the cycling stability of the maximum performance after 60 cycles under the conditions of 0.5C charge-discharge rate and 45 discharge cycles. The results show that the sulfurized polyacrylonitrile material prepared according to the method is an active material suitable for a lithium sulfur battery.
Description
Technical field
The invention belongs to material technology field, in particular to a kind of preparation method of chargeable lithium sulfur battery anode material, particularly a kind of homogeneous solvent legal system is for the method for sulfurized polyacrylonitrile material.
Background technology
The operation principle of chargeable lithium-sulfur cell is the Reversible redox reaction between sulphur and lithium.Because it has with low cost, cycle performance advantages of higher, therefore no matter at scientific domain or industrial circle, the whole world has a large amount of R&D institutions and personnel being devoted to exploitation (Ji et al., 2009 of lithium-sulfur cell; Jeong et al., 2013; Zhao et al., 72013).At present, the technical bottleneck of lithium-sulfur cell is the Design & preparation of sulfenyl positive electrode.Particularly, traditional lithium-sulfur cell exists active material loss and lithium sulphur polymer to be dissolved in problem (Sun et al., 2012 such as redox reciprocal reaction that electrolyte causes; Evers et al., 2012).In order to reduce these unfavorable factors; modal strategy is exactly by elemental sulfur being distributed in porous carbon matrix; as carbon nano-tube, hollow carbon granules, graphene/graphene oxide sheet material and other porous carbon materials etc., form sulphur-carbon composite positive electrode material (Xiao et al., 2013; Wang et al., 2013; Jayaprakash et al.2011).
Operation principle from sulfenyl positive electrode, in sulfenyl positive electrode, should contain the element sulphur being evenly distributed in a large number, element sulphur should fully embed among the active porosity of carbon matrix and with carbon matrix and produce stronger affinity interaction to obtain higher capacitance and good cycle characteristics.Yet; with current synthetic technology level, to meet above all standards and still be full of challenge; its main technology barrier has following two aspects: on the one hand, and (Park M., 2012 that sulphur-carbon composite is normally prepared from by sulphur being poured into carbon matrix under high temperature or liquid-phase condition; Lee K., 2012).But be subject to the restriction of carbon matrix loose structure and surface chemistry, a little less than the interaction very on sulphur and carbon matrix surface, cause sulphur skewness in carbon matrix, thereby cause the chemical property of lithium-sulfur cell to be also restricted.On the other hand, in charge and discharge cycles, the phenomenon that the sulphur of embedding is filtered off from carbon matrix is also difficult to avoid (Lee K., 2012; Li G.et al.).Therefore, most improvement strategy is to be all achieved to reduce loss and the structural instability of sulphur by designing and preparing New Type of Carbon host material.For example, some researchers utilize hollow or surface modification material with carbon element to strengthen affinity interaction (Jayaprakash N., 2011 between sulphur and carbon matrix; Li G., 2012; Lee K., 2012).Although these reports are considered to have potentiality improving aspect the utilance of sulphur, these materials still existence and stability is poor, sulfur content is low and practical application in the shortcomings such as processing characteristics is limited.Recently, have and report that polyacrylonitrile is used to prepare sulfur-bearing char-forming material to obtain sulphur positive electrode (Hwang T., 2013 of high stability as carbon matrix precursor; Guo, J., 2013).In the derivative sulphur positive electrode obtaining of polyacrylonitrile, thereby producing chemical crosslinking, the material with carbon element of sulfur molecule and conduction forms stable sulphur positive electrode.Yet, being subject to the restriction of solid phase reaction condition, polyacrylonitrile can not mix with sulphur, will cause this material to have lower sulfur content and poor reappearance (Wang L., et al., 2012).In order to tackle these significant challenge, the extensive work in design of material field is expected to for development of new technology, to prepare the high-performance sulfenyl positive electrode of lithium-sulfur cell.
Be subject to the inspiration of silicon carbide/polypropylene nitrile material, the present invention has designed a kind of novel method for synthesizing, in order to prepare the sulfurized polyacrylonitrile material of high, the Well-recovered and stable chemical performance of sulfur content.This preparation method's key point is to using that dimethyl sulfoxide (DMSO) is as solvent, and it can dissolve polyacrylonitrile and sulphur and form uniform liquid phase systems.This liquid-phase reaction system can impel two kinds of materials to form the sulphur-polyacrylonitrile polymer of crosslinked shape, then through calcine carbonization in nitrogen environment, finally obtains good stability, sulfurized polyacrylonitrile material that sulfur content is high.Finally, by detecting sulfurized polyacrylonitrile material as the feasibility of lithium-sulfur cell positive electrode, prove that sulfurized polyacrylonitrile material prepared by the method has higher capacitance and cyclical stability.
Summary of the invention
The object of the invention is to the defect for existing high temperature solid-state synthetic method, a kind of preparation method of homogeneous solvent method synthesized high-performance secondary lithium batteries sulfurized polyacrylonitrile positive electrode is provided.The method of the invention can reduce reaction temperature, improves the crosslinking degree between raw molecule, and product has excellent chemical property.
The object of the invention is to be achieved through the following technical solutions.
A preparation method for secondary lithium batteries sulfurized polyacrylonitrile positive electrode, specifically comprises the steps:
(1) polyacrylonitrile is dissolved in dimethyl sulfoxide (DMSO) to magnetic agitation 20～60 minutes, the solution that formation concentration is 25～50g/L;
(2) Cosan is added to above-mentioned solution, magnetic agitation 20～60 minutes, the concentration that makes sulphur in solution is 100～200g/L;
(3) solution after above-mentioned dispersion is placed in to 100～250 ℃ of oil baths and adds thermal response 10～30 hours, form homogeneous phase solution;
(4) after adding thermal response and finishing, above-mentioned solution is placed in to the vacuum environment of 80 ℃, removes dimethyl sulfoxide (DMSO) wherein, obtain sulfurized polyacrylonitrile material presoma;
(5) above-mentioned sulfurized polyacrylonitrile material precursor is transferred to Muffle furnace, at N
2under protection, be heated to 200～550 ℃ of carbonizations 1～
12 hours, naturally cooling after both sulfurized polyacrylonitrile positive electrode.
In technique scheme, described polyacrylonitrile can be polyacrylonitrile pressed powder, can be also polyacrylonitrile fibre.
In technique scheme, the described reaction temperature of step (3) is optimized for 150～200 ℃, and the reaction time is optimized for 12～20 hours.
In technique scheme, in the described homogeneous phase solution of step (3), solute is the compound that sulphur and polyacrylonitrile are cross-linked to form.
In technique scheme, the described carbonation reaction temperature of step (4) is optimized for 400～500 ℃, and the reaction time is optimized for 4～8 hours.
The present invention compared with prior art, has the following advantages:
(1) the present invention is that polyacrylonitrile and sulphur are crosslinked compound, with low cost in dimethyl sulfoxide (DMSO), environmentally safe.
(2) the present invention adopts the method for the solution of liquid phase to carry out mixed material, makes reaction raw materials in liquid phase environment, reach the even mixing on atomic level, thereby avoids the generation of impurity phase, and sulphur is more evenly distributed in polyacrylonitrile.
(3) in product sulfurized polyacrylonitrile material of the present invention, sulfur content is higher, and mass fraction can reach more than 49%, stable chemical performance.
(4) the present invention is simple to operate, and raw material is easy to get, and is easy to large-scale industrial and produces.
(5) product sulfurized polyacrylonitrile material capacitance of the present invention is high, and good cycling stability is suitable as anode material of lithium battery very much.
Accompanying drawing explanation
Fig. 1 is the thermogravimetric analysis collection of illustrative plates of the invention process example 1 product;
Fig. 2 is the Fourier transform infrared spectroscopy collection of illustrative plates of the invention process example 1 product;
Fig. 3 is the Raman spectrum collection of illustrative plates of the invention process example 1 product;
Fig. 4 is the X ray diffracting spectrum of the invention process example 1 product;
Fig. 5 is the cyclic voltammogram of the invention process example 1 product, and wherein charge-discharge magnification is 0.5C;
Fig. 6 is the charging and discharging curve of the invention process example 1 product, and wherein charge-discharge magnification is 0.5C;
Fig. 7 is cycle performance and coulomb efficiency curve of the invention process example 1 product, and wherein charge-discharge magnification is 0.5C;
Fig. 8 is charging/discharging voltage curve (a) and the high rate performance curve (b) of the invention process example 1 product, and wherein charge-discharge magnification is changed to 2C from 0.2C.
Embodiment
For a better understanding of the present invention, below in conjunction with embodiment and accompanying drawing, the present invention is further explained.But it should be noted that, embodiment is only for the present invention is further expalined, and the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
Get 1g polyacrylonitrile powder and be dissolved in 30mL dimethyl sulfoxide (DMSO), magnetic agitation 20 minutes, adds after 4g Cosan magnetic agitation 20 minutes again.After stirring finishes, the oil bath that solution is placed in to 200 ℃ adds thermal response 12 hours, makes polyacrylonitrile and sulfur-crosslinked combination, forms homogeneous phase solution.After reaction finishes, solution is proceeded to vacuum drying oven, 80 ℃ of vacuum dryings 1 hour, remove the dimethyl sulfoxide (DMSO) in solution, obtain sulfurized polyacrylonitrile material presoma.Proceed to again Muffle furnace and be filled with N
2protection, is heated to 450 ℃ of carbonizations 4 hours, both must sulfurized polyacrylonitrile material after naturally cooling.As reference group, 1g polyacrylonitrile powder is dissolved in to 30mL dimethyl sulfoxide (DMSO), but does not add Cosan.By above-mentioned work flow, prepare reference group virgin pp nitrile material again.
Fig. 1 is shown in by the thermogravimetric analysis collection of illustrative plates of product sulfurized polyacrylonitrile material and virgin pp nitrile material, known by two curves in comparison diagram, utilizes the sulfurized polyacrylonitrile material sulfur content that the method prepares to be about 49%.The Fourier transform infrared spectroscopy spectrogram of product sulfurized polyacrylonitrile material and virgin pp nitrile material is shown in Fig. 2, as seen from the figure, and at 500-1100cm
-1lower wave number district, sulfurized polyacrylonitrile material has the characteristic peak that some virgin pp nitrile material does not have, for example 513cm
-1and 670cm
-1the characteristic peak going out belongs to respectively the stretching vibration of S-S key and C-S key in sulfurized polyacrylonitrile material, shows polyacrylonitrile and crosslinked combination of sulphur in sulfurized polyacrylonitrile material.From the Raman spectrum spectrogram (Fig. 3) of product, can know, carburizing reagent makes sulfurized polyacrylonitrile material presoma produce dehydrogenation and pi-pi accumulation, makes end product sulfurized polyacrylonitrile material have graphite-like structure.The X-ray diffractogram of product sulfurized polyacrylonitrile material and virgin pp nitrile material and raw material polyacrylonitrile is shown in Fig. 4, by contrast, can find out, the S8 orthorhombic structure of sulphur disappears, and has also illustrated that sulphur and polyacrylonitrile have produced crosslinked action.In addition, from X-ray diffractogram, can also show that polyacrylonitrile can produce graphite-like pi-pi accumulation in carbonisation, thereby make sulfurized polyacrylonitrile material there is good conductivity.The cycle performance of this sulfurized polyacrylonitrile positive electrode is shown in Fig. 7, and as shown in Figure 7, under the discharge-rate of 0.5C, the high energy of capacitance reaches 1312 mAhg
-1, after circulating 60 weeks, capability retention still has 77%.All results show above, and sulfurized polyacrylonitrile material has excellent chemical property and structural stability.
Embodiment 2
Get 10g polyacrylonitrile powder and be dissolved in 350mL dimethyl sulfoxide (DMSO), magnetic agitation 30 minutes, adds after 45g Cosan magnetic agitation 30 minutes again.After stirring finishes, the oil bath that solution is placed in to 250 ℃ adds thermal response 18 hours, makes polyacrylonitrile and sulfur-crosslinked combination, forms homogeneous phase solution.After reaction finishes, solution is proceeded to vacuum drying oven, 80 ℃ of vacuum dryings 2 hours, remove the dimethyl sulfoxide (DMSO) in solution, obtain sulfurized polyacrylonitrile material presoma.Proceed to again Muffle furnace and be filled with N
2protection, is heated to 500 ℃ of carbonizations 6 hours, both must sulfurized polyacrylonitrile material after naturally cooling.
Embodiment 3
Get 5g polyacrylonitrile fibre, be dissolved in 150mL dimethyl sulfoxide (DMSO) after chopping, magnetic agitation 45 minutes, adds after 25g Cosan magnetic agitation 45 minutes again.After stirring finishes, the oil bath that solution is placed in to 250 ℃ adds thermal response 20 hours, makes polyacrylonitrile and sulfur-crosslinked combination, forms homogeneous phase solution.After reaction finishes, solution is proceeded to vacuum drying oven, 80 ℃ of vacuum dryings 1.5 hours, remove the dimethyl sulfoxide (DMSO) in solution, obtain sulfurized polyacrylonitrile material presoma.Proceed to again Muffle furnace and be filled with N
2protection, is heated to 450 ℃ of carbonizations 5 hours, both must sulfurized polyacrylonitrile material after naturally cooling.
Claims (5)
1. a preparation method for secondary lithium batteries sulfurized polyacrylonitrile positive electrode, is characterized in that comprising the steps:
(1) polyacrylonitrile is dissolved in dimethyl sulfoxide (DMSO) to magnetic agitation 20～60 minutes, the solution that formation concentration is 25～50g/L;
(2) Cosan is added to above-mentioned solution, magnetic agitation 20～60 minutes, the concentration that makes sulphur in solution is 100～200g/L;
(3) solution after above-mentioned dispersion is placed in to 100～250 ℃ of oil baths and adds thermal response 10～30 hours, form homogeneous phase solution;
(4) after adding thermal response and finishing, above-mentioned solution is placed in to the vacuum environment of 80 ℃, removes dimethyl sulfoxide (DMSO) wherein, obtain sulfurized polyacrylonitrile material presoma;
(5) above-mentioned SPC material precursor is transferred to Muffle furnace, at N
2under protection, be heated to 200～550 ℃ of carbonizations 1～12 hour, naturally cooling after both sulfurized polyacrylonitrile positive electrode.
2. the preparation method of secondary lithium batteries sulfurized polyacrylonitrile positive electrode according to claim 1, is characterized in that described polyacrylonitrile can be polyacrylonitrile pressed powder, can be also polyacrylonitrile fibre.
3. the preparation method of secondary lithium batteries sulfurized polyacrylonitrile positive electrode according to claim 1, is characterized in that the described reaction temperature of step (3) is optimized for 150～200 ℃, and the reaction time is optimized for 12～20 hours.
4. the preparation method of secondary lithium batteries sulfurized polyacrylonitrile positive electrode according to claim 1, is characterized in that in the described homogeneous phase solution of step (3), solute is the compound that sulphur and polyacrylonitrile are cross-linked to form.
5. the preparation method of secondary lithium batteries sulfurized polyacrylonitrile positive electrode according to claim 1, is characterized in that the described carbonation reaction temperature of step (4) is optimized for 400～500 ℃, and the reaction time is optimized for 4～8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410194569.6A CN103972510B (en) | 2014-05-09 | 2014-05-09 | Preparation method of sulfurized polyacrylonitrile anode material used for lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410194569.6A CN103972510B (en) | 2014-05-09 | 2014-05-09 | Preparation method of sulfurized polyacrylonitrile anode material used for lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103972510A true CN103972510A (en) | 2014-08-06 |
| CN103972510B CN103972510B (en) | 2017-05-10 |
Family
ID=51241765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410194569.6A Expired - Fee Related CN103972510B (en) | 2014-05-09 | 2014-05-09 | Preparation method of sulfurized polyacrylonitrile anode material used for lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103972510B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2016054865A1 (en) * | 2014-10-09 | 2016-04-14 | 江苏华东锂电技术研究院有限公司 | Method for preparing sulfur-based positive electrode material |
| WO2016095707A1 (en) * | 2014-12-19 | 2016-06-23 | 江苏华东锂电技术研究院有限公司 | Preparation method for sulfur-based composite cathode material |
| CN106661149A (en) * | 2014-08-07 | 2017-05-10 | 罗伯特·博世有限公司 | Sulfur-pan composite, a method for preparing said composite, and an electrode and a lithium-sulfur battery comprising said composite |
| CN106920937A (en) * | 2017-03-30 | 2017-07-04 | 青岛亨迈新能源有限公司 | A kind of preparation method of electrode composite material |
| CN110400963A (en) * | 2018-05-14 | 2019-11-01 | 宁波致轻电池有限公司 | A kind of metallic sodium or Na-K alloy cathode/sulfurized polyacrylonitrile anode secondary cell and its manufacturing method |
| CN116948064A (en) * | 2023-09-20 | 2023-10-27 | 河南师范大学 | Method for preparing vulcanized polyacrylonitrile anode material for lithium sulfur battery by template method |
| CN116948064B (en) * | 2023-09-20 | 2024-05-28 | 河南师范大学 | Method for preparing vulcanized polyacrylonitrile anode material for lithium sulfur battery by template method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399339A (en) * | 2010-09-08 | 2012-04-04 | 清华大学 | Preparation method of sulfurized polyacrylonitrile |
| WO2013182353A1 (en) * | 2012-06-08 | 2013-12-12 | Robert Bosch Gmbh | Method for the production of a polyacrylonitrile-sulfur composite material |
| CN103531748A (en) * | 2012-07-06 | 2014-01-22 | 清华大学 | Method for preparing active material of lithium ion battery electrode |
-
2014
- 2014-05-09 CN CN201410194569.6A patent/CN103972510B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399339A (en) * | 2010-09-08 | 2012-04-04 | 清华大学 | Preparation method of sulfurized polyacrylonitrile |
| WO2013182353A1 (en) * | 2012-06-08 | 2013-12-12 | Robert Bosch Gmbh | Method for the production of a polyacrylonitrile-sulfur composite material |
| CN103531748A (en) * | 2012-07-06 | 2014-01-22 | 清华大学 | Method for preparing active material of lithium ion battery electrode |
Non-Patent Citations (1)
| Title |
|---|
| ZHONGSHENG WEN等: "Fabrication and Electrochemical Performance of Polyacrylonitrile-S/Carbon Composite as Cathodefor Lithium Ion Batteries", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106661149A (en) * | 2014-08-07 | 2017-05-10 | 罗伯特·博世有限公司 | Sulfur-pan composite, a method for preparing said composite, and an electrode and a lithium-sulfur battery comprising said composite |
| WO2016054865A1 (en) * | 2014-10-09 | 2016-04-14 | 江苏华东锂电技术研究院有限公司 | Method for preparing sulfur-based positive electrode material |
| WO2016095707A1 (en) * | 2014-12-19 | 2016-06-23 | 江苏华东锂电技术研究院有限公司 | Preparation method for sulfur-based composite cathode material |
| 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 |
| CN106920937A (en) * | 2017-03-30 | 2017-07-04 | 青岛亨迈新能源有限公司 | A kind of preparation method of electrode composite material |
| CN110400963A (en) * | 2018-05-14 | 2019-11-01 | 宁波致轻电池有限公司 | A kind of metallic sodium or Na-K alloy cathode/sulfurized polyacrylonitrile anode secondary cell and its manufacturing method |
| CN110400963B (en) * | 2018-05-14 | 2021-03-30 | 宁波致轻电池有限公司 | Secondary battery of metal sodium or sodium-potassium alloy cathode/polyacrylonitrile sulfide anode and manufacturing method thereof |
| CN116948064A (en) * | 2023-09-20 | 2023-10-27 | 河南师范大学 | Method for preparing vulcanized polyacrylonitrile anode material for lithium sulfur battery by template method |
| CN116948064B (en) * | 2023-09-20 | 2024-05-28 | 河南师范大学 | Method for preparing vulcanized polyacrylonitrile anode material for lithium sulfur battery by template method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103972510B (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109449404B (en) | Sulfur-nitrogen doped carbon nanofiber-MXene composite material for lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN109599546A (en) | Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same | |
| CN103972510A (en) | Preparation method of sulfurized polyacrylonitrile anode material used for lithium secondary battery | |
| CN106025200A (en) | Preparation method and application of nitrogen-doped MXene battery anode material | |
| CN103700859A (en) | Graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material for cathode of lithium sulfur battery, as well as preparation method and application of graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material | |
| CN106099109B (en) | A kind of preparation method and applications of asphaltic base hard charcoal nanometer sheet | |
| CN109616639B (en) | Hard carbon coated expanded microcrystalline graphite material, preparation method thereof and application thereof in sodium-ion battery | |
| CN109755540B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN104766967A (en) | Preparation method of S/C composite material used in positive pole of Li-S battery | |
| CN104269555A (en) | Soft carbon anode material for lithium-ion power and energy storage battery as well as preparation method and application of soft carbon anode material | |
| CN115020643A (en) | Biomass-based hard carbon, preparation method thereof and application thereof in sodium-ion battery | |
| CN113948681B (en) | Biomass-based hard carbon compound composite material and preparation method and application thereof | |
| CN109167077B (en) | Phosphorus-doped porous carbon-oxygen reduction catalyst and preparation method and application thereof | |
| CN105047929A (en) | Lithium ion battery anode material with porous structure and preparation method of lithium ion battery anode material | |
| CN104362319A (en) | Preparation method of porous tin-carbon composite negative material | |
| CN102110813B (en) | Graphite material at negative pole of lithium ion battery and preparation method thereof | |
| CN104528685A (en) | Sulfur-carbon-doped material and preparation method thereof | |
| CN104377346B (en) | Method for preparing modified graphite negative electrode material of sodium ion battery | |
| CN101880042B (en) | Artificial graphite microspheres for preparing cathode of lithium ion battery and preparation method thereof | |
| CN106299258A (en) | A kind of highdensity graphite cell negative material and preparation method thereof | |
| KR101790699B1 (en) | Method for synthesis of anode material using active carbon and pitch prepared by chemical activation | |
| CN105702938A (en) | Iron-based oxide lithium ion battery negative electrode material and preparation method and application thereof | |
| CN111883368B (en) | Pine nut shell derived carbon material/triazine polymer derived carbon material, preparation method and application thereof, and double-carbon sodium ion hybrid capacitor | |
| CN106684367B (en) | Low-temperature petroleum coke negative electrode material coated with nitrogen-containing polymer pyrolytic carbon and preparation method thereof | |
| CN102005559A (en) | Method for preparing artificial graphite cathode material for lithium ion 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170510 Termination date: 20180509 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |