CN101562244A - Method for preparing elemental sulfur composite material used by lithium secondary battery - Google Patents
Method for preparing elemental sulfur composite material used by lithium secondary battery Download PDFInfo
- Publication number
- CN101562244A CN101562244A CNA2009100851366A CN200910085136A CN101562244A CN 101562244 A CN101562244 A CN 101562244A CN A2009100851366 A CNA2009100851366 A CN A2009100851366A CN 200910085136 A CN200910085136 A CN 200910085136A CN 101562244 A CN101562244 A CN 101562244A
- Authority
- CN
- China
- Prior art keywords
- elemental sulfur
- composite material
- lithium secondary
- secondary battery
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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 method for preparing an elemental sulfur composite material used by the positive electrode of a lithium secondary battery, which belongs to the field of electrochemical batteries. The composite material consists of a carbon material with good electric conductivity, high specific surface area and strong adsorptivity and elemental sulfur. The method comprises the following steps: mixing the elemental sulfur and the carbon material evenly and sufficiently, and then filling the mixture into a specially-designed stainless steel sealable tank capable of vacuumizing; and adopting a sealed zone heating method to melt sublimate the elemental sulfur in the presence of vacuum or inert gas, and then depositing the elemental sulfur on the carbon material substrate to form a composite product with a uniform structure. The elemental sulfur composite material prepared by the method has high electrochemical activity, large discharge specific capacity and good battery cycle performance, and has wide application prospect in the fields of the lithium secondary batteries, lithium-sulfur batteries and the like.
Description
Technical field
The present invention relates to a kind of preparation method of anode materials for lithium secondary cells of high-energy-density.Specifically, a kind of electro-chemical activity height, elemental sulfur composite material that specific discharge capacity is big have been prepared.This composite material, is compound to elemental sulfur and forms composite material in the material with carbon element as matrix with the good material with carbon element of electric conductivity, belongs to field of electrochemical batteries.
Background technology
In recent years, along with the continuous progress of science and technology, the fast development of various electronic products requires used chemical power source to have characteristics such as light weight, volume is little, capacity is big.Though, improve the exploitation that the energy density of battery must be leaned on new material by a relatively large margin by improving the performance that existing battery material preparation and cell making process can improve battery to a certain extent.
In the battery system of numerous researchs, the metal lithium-sulfur cell is considered to tool application potential.Elemental sulfur theoretical specific capacity as positive active material is 1675mAh/g, and specific energy is that 2600Wh/kg (generates Li after lithium metal and the sulphur complete reaction
2S), be higher than existing lithium rechargeable battery material LiCoO far away
2, LiMnO
2And LiFePO
4Deng.Simultaneously the elemental sulfur positive electrode has the source and enriches low price, environmentally friendly, advantage such as battery security is good.Yet also there are a lot of problems in the development of lithium-sulfur cell.
Elemental sulfur at room temperature is typical electronic and ion insulator (5 * 10
-3025 ℃ of S/cm), generally need to add a large amount of conductive agents when practical application, this has reduced the specific capacity of electrode integral body to a great extent; And the sulphur reduction generates Li
2The process of S is a multistep reaction, and many lithium sulfides of product are soluble in organic liquid electrolyte in the middle of it, and a large amount of dissolvings of many lithium sulfides can cause the active material of a part to run off, and also can cause the increase of electrolyte viscosity and the reduction of ionic conductivity simultaneously.The many lithium sulfides that have been partly dissolved diffuse to negative pole also can with lithium generation self discharge reaction, further worsen the performance of battery, this a series of problem has all caused the electrode active material utilance low and cycle performance of battery is poor.
In order to solve above problem, there is suggestion to adopt organic sulfur compound or sulfur compound to replace elemental sulfur, such as PDDTB, PDTDA, PABTH, FeS
2With CuS etc., but thereby the theoretical specific capacity of this compounds has limited the application of this class material less than 30% of elemental sulfur.Can increase its conductivity and can suppress the dissolving of part discharging product at elemental sulfur surface coated with conductive polymer such as polyaniline, polypyrrole, but the specific discharge capacity of battery is not greatly enhanced and this method cost is higher, environment is produced pollute.In order to improve the cycle life of lithium-sulfur cell, announced a series of with glycol dimethyl ether, 1, the electrolyte of organic solvents such as 3-dioxolane, oxolane, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and their mixed solvent, thus this kind solvent can suppress the cycle performance that the dissolving of elemental sulfur discharging product improves battery to a certain extent.Along with the development of polymer and gel electrolyte, adopt pure solid-state electrolyte and, can suppress the dissolving of discharging product largely, but problems such as the conductivity of elemental sulfur electrode own are unresolved in conjunction with special battery design technology.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of cathode plate for lithium secondary battery, by the compound cycle life that improves the electrode active material utilance and then improve battery of elemental sulfur with the high power capacity elemental sulfur composite material.Cause the low reason of elemental sulfur active material utilization to mainly contain the dissolving of electrode conductivuty difference and discharging product.For this reason, the invention provides a kind of method for preparing electro-chemical activity height, elemental sulfur composite material that specific capacity is big.The prepared composite material of this method is made up of two parts: the one, and the material with carbon element that electric conductivity is good; Another part is the elemental sulfur of electro-chemical activity.Also be that this composite material is matrix with the material with carbon element, the elemental sulfur heating sublimation is spread then be deposited in the material with carbon element, form the combination product of even structure.
Content of the present invention comprises: as matrix, the mode by sealing segmentation heating is deposited on elemental sulfur in the hole or gap of material with carbon element equably with the good material with carbon element of electric conductivity; Heating process adopts the stainless steel sealed reaction jar of the vacuum-pumping of particular design, the combination product that the advantage of this method is accurately to control the sulfur content of composite material and can makes even structure; Material with carbon element with loose structure can reduce the particle of active material sulphur, thereby improves the utilance of elemental sulfur; The good electric conductivity of material with carbon element will help to overcome the problem of elemental sulfur poor electric conductivity, and its higher specific surface area, powerful adsorption capacity can suppress the dissolving loss of discharging product, thereby improve the utilance of active material, improve the cycle performance of battery.
Its concrete preparation process of elemental sulfur composite material according to above mentality of designing is as follows:
(1) take by weighing a certain amount of material with carbon element, material with carbon element comprises: carbon nano-tube, carbon nano-fiber, active carbon, carbon aerogels, carbon black etc.;
(2) take by weighing a certain amount of elemental sulfur, elemental sulfur is sublimed sulfur or high purity sulphur;
(3) elemental sulfur in material with carbon element in the step (1) and the step (2) is fully mixed, the content of elemental sulfur is 25%～95% in the mixture;
(4) mixture is packed in the stainless steel hermetically sealed can of vacuum-pumping of particular design, then by bleeding or the mode of exhaust makes mixture be in vacuum or back sealing in the environment that inert gas exists is arranged.Inert gas is Ar or N
2
(5) mixture in the heating steps (4) makes elemental sulfur fusing and diffuses in the hole or gap of material with carbon element, heating and temperature control between 150～200 ℃, constant temperature 4～10 hours;
(6) elevated temperature makes the elemental sulfur distillation and further deposits in the material with carbon element matrix, and temperature range is 300～400 ℃, constant temperature 2～5 hours;
(7) naturally cool to room temperature, obtain elemental sulfur composite material.
The advantage that the inventive method is outstanding is to have adopted the mode that seals the segmentation heating that elemental sulfur fusing distillation is spread then when preparing elemental sulfur composite material to be deposited in the material with carbon element matrix.Compare with existent method, this method can realize in vacuum or the environment in the presence of inert gas, can accurately control the content of elemental sulfur in the composite material, in hermetically sealed can, can make elemental sulfur and material with carbon element fully react even, thereby the material that adds can be fully used, and avoided the waste of material.
For the chemical property of the elemental sulfur composite material that detects the inventive method preparation, the present invention has prepared chargeable lithium battery with this composite material as positive pole, and its composition comprises: positive pole, negative pole, electrolyte and barrier film is characterized in that:
(1) Zheng Ji composition comprises: positive electrode active materials, electric conducting material and adhesive.Wherein positive electrode active materials adopts aforesaid elemental sulfur composite material;
(2) negative pole is lithium metal or lithium alloy such as Li, Li-Sn, Li-Si, Li-Al;
(3) electrolyte is liquid electrolyte, solid electrolyte or gel electrolyte.
The chargeable lithium battery of above-mentioned preparation is is at room temperature discharged and recharged with the current density of 100mA/g, and elemental sulfur active material specific discharge capacity is 500-1500mAh/g, and average discharge volt is 2.1V (vs.Li/Li
+), the utilance of active material is between 60-90%, and battery also keeps higher specific capacity after 50 weeks of circulation, shown good cyclical stability, and prepared chargeable lithium battery energy density is higher than 300Wh/kg.
The elemental sulfur composite material of the inventive method preparation has solved the problem that elemental sulfur poor electric conductivity, discharging product dissolving are run off to a certain extent, thereby has improved the capacity characteristic and the cycle life of battery.And this preparation method is simple, and is with low cost, and the material price that is adopted is cheap, and with environmental friendliness, the battery overcharging resisting ability of making is strong, and the security performance of battery is good, thereby has a good application prospect.
Description of drawings
Fig. 1 is the hermetically sealed can of the designed vacuum-pumping of the inventive method;
Fig. 2 is the SEM figure of the elemental sulfur composite material of employing the inventive method preparation;
Fig. 3 is the discharge curve first during as lithium battery anode for the elemental sulfur composite material that adopts the inventive method preparation;
Fig. 4 is the cycle performance of battery figure during as lithium battery anode for the elemental sulfur composite material that adopts the inventive method preparation.
Embodiment
Embodiment 1
With multi-walled carbon nano-tubes (nanometer port, Shenzhen) and elemental sulfur (100 orders, Aldrich) putting into agate mortar at 5: 95 by mass ratio fully grinds evenly, mixture is packed in the stainless steel sealed reaction jar of vacuum-pumping of particular design, with vacuum pump with the jar back sealing that is evacuated.Place chamber type electric resistance furnace to be warming up to 150 ℃ and keep 10h to make elemental sulfur fusing and diffuse to the hole or the gap of multi-walled carbon nano-tubes the retort after the sealing, then temperature is risen to 300 ℃ and keep 5h to make the sulfur vapor of distillation further deposit to the surface of multi-walled carbon nano-tubes, naturally cool to room temperature and obtain sulphur/carbon nano tube compound material.Sulfur content is 95% in this composite material.The specific area of the multi-walled carbon nano-tubes that calculates through the adsorption desorption thermoisopleth of nitrogen is 175.93m
2/ g, the material specific area that obtains after compound with elemental sulfur is reduced to 1.96m
2/ g, it is less that self-enclosed possibility takes place the carbon nano-tube pore structure in heat-treatment process, so elemental sulfur to have deposited in the hole of multi-walled carbon nano-tubes or the gap by distillation be the basic reason that causes the material specific area to descend significantly.
This composite material and acetylene black, Kynoar (PVDF) are mixed by mass ratio at 70: 20: 10, and (NMP) is solvent with the N-N-methyl-2-2-pyrrolidone N-, with the speed ball milling 8h of 300rpm, is uniformly coated on the collector Al paper tinsel in stainless steel jar mill.Obtain the elemental sulfur combination electrode.With this electrode is work electrode, metal lithium sheet is to electrode, Celgrad2300 is a barrier film, 1mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)/glycol dimethyl ether (DME)+1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into battery for electrolyte.
The open circuit voltage of battery is 3.08V, and at room temperature the current density with 100mA/g discharges and recharges, and the first discharge specific capacity of material is 1487.0mAh/g, and the utilance of sulphur reaches 88.9%.2 tangible discharge platforms have appearred on discharge curve, respectively about 2.3V and 2.0V.50 times circulation back specific discharge capacity also remains on 913.7mAh/g, has demonstrated good cyclical stability.
Embodiment 2
With multi-walled carbon nano-tubes (nanometer port, Shenzhen) and elemental sulfur (100 orders, Aldrich) putting into agate mortar at 30: 70 by mass ratio fully grinds evenly, mixture is packed in the stainless steel sealed reaction jar of vacuum-pumping of particular design, continue to feed argon gas 30min to discharge the air of the inside, prevent that sulphur is at high temperature oxidized.Place chamber type electric resistance furnace to be warming up to 200 ℃ and keep 4h to make elemental sulfur fusing and diffuse to the hole or the gap of multi-walled carbon nano-tubes the retort of sealing, then temperature is risen to 400 ℃ and keep 2h to make the sulfur vapor of distillation further deposit to the surface of multi-walled carbon nano-tubes, naturally cool to room temperature and obtain sulphur/carbon nano tube compound material.Sulfur content is 70% in this composite material.The specific area of the multi-walled carbon nano-tubes that calculates through the adsorption desorption thermoisopleth of nitrogen is 175.93m
2/ g, the material specific area that obtains after compound with elemental sulfur is reduced to 5.33m
2/ g, it is less that self-enclosed possibility takes place the carbon nano-tube pore structure in heat-treatment process, so elemental sulfur to have deposited in the hole of multi-walled carbon nano-tubes or the gap by distillation be the basic reason that causes the material specific area to descend significantly.
This composite material and acetylene black, polyethylene glycol oxide (PEO) are mixed by mass ratio at 70: 20: 10, are solvent with the deionized water, with the speed ball milling 4h of 300rpm, are uniformly coated on the collector Al paper tinsel in stainless steel jar mill.Obtain the elemental sulfur combination electrode.With this electrode is work electrode, and metal lithium sheet is to electrode, and Celgrad2300 is a barrier film, and 1M PP14-TFSI il electrolyte is that electrolyte is assembled into battery.
The open circuit voltage of battery is 2.93V, and at room temperature the current density with 100mA/g discharges and recharges, and the first discharge specific capacity of material is 1189.1mAh/g, and 50 times circulation back specific discharge capacity also remains on 634.1mAh/g.
Embodiment 3
(specific area is 1485m with active carbon
2/ g, average pore size is 1.76nm) and elemental sulfur (100 orders, Aldrich) put into agate mortar at 75: 25 by mass ratio and fully grind evenly, mixture is packed in the stainless steel sealed reaction jar of vacuum-pumping of particular design, with vacuum pump with the jar back sealing that is evacuated.Place chamber type electric resistance furnace to be warming up to 180 ℃ and keep 8h to make elemental sulfur fusing and diffuse to the micropore of active carbon the retort after the sealing, then temperature is risen to 350 ℃ and keep 3h that the sulfur vapor of distillation is further deposited in the micropore of active carbon, naturally cool to room temperature and obtain sulphur/absorbent charcoal composite material.Sulfur content is 25% in this composite material.It is 495m that composite material is carried out the specific area test result
2/ g, that self-enclosed possibility takes place is very little for active carbon pore structure in heat-treatment process, and therefore the reason that causes the material specific area to descend significantly is because elemental sulfur has been deposited in the micropore of active carbon by distillation.In the process of heating, the sulphur of molten state, especially Sheng Hua sulfur vapor diffuse in the micropore of active carbon, are adsorbed in the micropore firmly in the process of cooling off owing to active carbon higher specific surface area and huge adsorption capacity make elemental sulfur.
This composite material and acetylene black, Kynoar (PVDF) are mixed by mass ratio at 70: 20: 10, and (NMP) is solvent with the N-N-methyl-2-2-pyrrolidone N-, with the speed ball milling 8h of 300rpm, is uniformly coated on the collector Al paper tinsel in stainless steel jar mill.Obtain the elemental sulfur combination electrode.With this electrode is work electrode, metal lithium sheet is to electrode, Celgrad2300 is a barrier film, 1mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)/glycol dimethyl ether (DME)+1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into battery for electrolyte.
Composite material shows at the cyclic voltammetry curve between 1V～3V exist 2 reduction peak near 2.05V and 2.35V, exists 1 oxidation peak near 2.4V.At room temperature the current density with 100mA/g discharges and recharges battery, and the first discharge specific capacity of material is 1352.5mAh/g, and the utilance of sulphur reaches 80.9%.40 times circulation back specific discharge capacity also remains on 800.7mAh/g, shows good cyclical stability.
Embodiment 4
With carbon nano-fiber and elemental sulfur (100 orders, Aldrich) putting into agate mortar at 20: 80 by mass ratio fully grinds evenly, mixture is packed in the stainless steel sealed reaction jar of vacuum-pumping of particular design, continue to feed argon gas 30min to discharge the air of the inside, prevent that sulphur is at high temperature oxidized.Place chamber type electric resistance furnace to be warming up to 150 ℃ and keep 8h the retort of sealing, then temperature is risen to 300 ℃ and keep 4h, naturally cool to room temperature and obtain sulphur/absorbent charcoal composite material.Sulfur content is 80% in this composite material.
This composite material and acetylene black, LA133 aqueous binder are mixed by mass ratio at 70: 20: 10, are solvent with the deionized water, with the speed ball milling 4h of 300rpm, are uniformly coated on the collector Al paper tinsel in stainless steel jar mill.Obtain the elemental sulfur combination electrode.With this electrode is work electrode, and metal lithium sheet is to electrode, and electrolyte adopts PVDF-HFP and DME-DOL-LiTFSI gel electrolyte, is assembled into battery.
At room temperature the current density with 100mA/g discharges and recharges battery, and the first discharge specific capacity of material is 1284.3mAh/g, and 40 times circulation back specific discharge capacity also remains on 730.6mAh/g, shows good cyclical stability.
Embodiment 5
With carbon black and elemental sulfur (100 orders, Aldrich) putting into agate mortar at 50: 50 by mass ratio fully grinds evenly, mixture is packed in the stainless steel sealed reaction jar of vacuum-pumping of particular design, continues to feed nitrogen 30min to discharge the air of the inside, prevents that sulphur is at high temperature oxidized.Place chamber type electric resistance furnace to be warming up to 200 ℃ and keep 6h the retort of sealing, then temperature is risen to 350 ℃ and keep 3h, naturally cool to room temperature and obtain sulphur/absorbent charcoal composite material.Sulfur content is 50% in this composite material.The first discharge specific capacity of this material is 1173.6mAh/g, and 40 times circulation back specific discharge capacity also remains on 680.5mAh/g, shows good cyclical stability.
Claims (10)
1. a cathode plate for lithium secondary battery is characterized in that with the preparation method of elemental sulfur composite material:
(1) takes by weighing elemental sulfur and material with carbon element, and it is mixed;
(2) mixture is packed in the stainless steel hermetically sealed can;
(3) mixture in the heated sealant retort makes elemental sulfur fusing and diffuses in the material with carbon element matrix;
(4) elevated temperature makes elemental sulfur that distillation take place and further is deposited in the material with carbon element matrix;
(5) naturally cool to room temperature, obtain elemental sulfur composite material.
2. a kind of cathode plate for lithium secondary battery according to claim 1 preparation method of elemental sulfur composite material, it is characterized in that: described elemental sulfur is sublimed sulfur or high purity sulphur.
3. the cathode plate for lithium secondary battery according to claim 1 preparation method of elemental sulfur composite material is characterized in that: described material with carbon element is selected from the group of carbon nano-tube, carbon nano-fiber, active carbon, carbon aerogels, carbon black composition.
4. a kind of cathode plate for lithium secondary battery according to claim 1 preparation method of elemental sulfur composite material, it is characterized in that: by percentage to the quality, the content of elemental sulfur is 25%～95% in the described mixture.
5. a kind of cathode plate for lithium secondary battery according to claim 1 is characterized in that with the preparation method of elemental sulfur composite material mixture is in the vacuum environment in the described step 2.
6. a kind of cathode plate for lithium secondary battery according to claim 1 preparation method of elemental sulfur composite material is characterized in that: mixture is in the environment of inert gas existence in the described step 2.
7. a kind of cathode plate for lithium secondary battery according to claim 6 preparation method of elemental sulfur composite material, it is characterized in that: described inert gas is Ar or N
2
8. a kind of cathode plate for lithium secondary battery according to claim 1 is characterized in that with the preparation method of elemental sulfur composite material: in the described step 3 heating and temperature control between 150～200 ℃, constant temperature 4～10 hours.
9. a kind of cathode plate for lithium secondary battery according to claim 1 is characterized in that with the preparation method of elemental sulfur composite material: in the described step 4 heating and temperature control between 300～400 ℃, constant temperature 2～5 hours.
10. one kind is used for the hermetically sealed can that the described a kind of cathode plate for lithium secondary battery of claim 1 is used the preparation method of elemental sulfur composite material, it is characterized in that: described hermetically sealed can is the stainless steel manufacturing, volume is between 25～200ml, and vacuum-pumping and charge into inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100851366A CN101562244A (en) | 2009-06-02 | 2009-06-02 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100851366A CN101562244A (en) | 2009-06-02 | 2009-06-02 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101562244A true CN101562244A (en) | 2009-10-21 |
Family
ID=41220941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100851366A Pending CN101562244A (en) | 2009-06-02 | 2009-06-02 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101562244A (en) |
Cited By (52)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101719545A (en) * | 2009-12-16 | 2010-06-02 | 北京理工大学 | Anode composite material of lithium sulfur battery and preparation method thereof |
| CN101867038A (en) * | 2010-06-08 | 2010-10-20 | 南开大学 | Method for preparing anode composite material for lithium sulfur secondary batteries |
| CN102185127A (en) * | 2011-04-07 | 2011-09-14 | 武汉理工大学 | Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery |
| CN102201567A (en) * | 2011-04-18 | 2011-09-28 | 武汉工程大学 | Preparation method for anode of lithium-sulfur battery |
| CN102263257A (en) * | 2011-06-28 | 2011-11-30 | 中国科学院金属研究所 | High energy flexible electrode material and preparation method thereof and application thereof in storage battery |
| CN102280630A (en) * | 2011-07-04 | 2011-12-14 | 中国科学院过程工程研究所 | Sulphur-graphene composite cathode material and manufacturing method thereof |
| CN102315424A (en) * | 2010-07-06 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Composite anode material for lithium sulfur battery, preparation method and application thereof |
| CN102522542A (en) * | 2011-12-14 | 2012-06-27 | 上海交通大学 | Elemental sulfur composite material containing graphene and preparation method thereof |
| CN102522530A (en) * | 2011-12-27 | 2012-06-27 | 钟馨稼 | Nano-sulfur composite cathode material for rare earth lithium-sulfur battery, and preparation method thereof |
| CN102593433A (en) * | 2012-02-27 | 2012-07-18 | 清华大学 | Directional carbon nano-tube composite cathode material for lithium-sulfur secondary battery |
| CN102738448A (en) * | 2011-04-12 | 2012-10-17 | 通用汽车环球科技运作有限责任公司 | Encapsulated sulfur cathode for lithium ion battery |
| CN102800865A (en) * | 2012-08-28 | 2012-11-28 | 吴永胜 | Lithium battery with total solid ions for conducting power |
| CN102969481A (en) * | 2012-12-11 | 2013-03-13 | 武汉大学 | Sulfur/carbon composite material for lithium-sulfur secondary battery and preparation method thereof |
| CN103000864A (en) * | 2012-10-25 | 2013-03-27 | 北京理工大学 | Sulfur composite cathode material and preparation method thereof |
| CN103050729A (en) * | 2012-12-28 | 2013-04-17 | 大连理工大学 | Lithium sulfur battery |
| CN103178247A (en) * | 2013-03-22 | 2013-06-26 | 中南大学 | Sulfur/carbon composite material and preparation method thereof |
| CN103178242A (en) * | 2013-03-25 | 2013-06-26 | 中国科学院上海硅酸盐研究所 | Graphene-sulfur composite material used as positive material of lithium-sulfur battery and preparation method of graphene-sulfur composite material |
| WO2013097116A1 (en) * | 2011-12-28 | 2013-07-04 | Chung Winston | Nano-sulphur composite positive pole material for rare earth lithium sulphur battery and method for preparing same. |
| CN103210525A (en) * | 2010-11-26 | 2013-07-17 | 株式会社爱发科 | Positive electrode for lithium sulfur secondary battery, and method for forming same |
| CN103236560A (en) * | 2013-04-16 | 2013-08-07 | 浙江大学 | Lithium-sulfur battery sulfur/carbon composite positive electrode material, preparation method and applications thereof |
| CN103531759A (en) * | 2013-09-23 | 2014-01-22 | 广州市香港科大***研究院 | Two-step adsorption preparation method of high magnification sulphur/mesoporous and microporous carbon HAC (honeycomb activated carbon) lithium sulphur battery anode composite material |
| CN103560232A (en) * | 2013-09-30 | 2014-02-05 | 南京工业大学 | Preparation method of S-C positive pole composite material of high cycle performance lithium sulfur battery |
| CN103746101A (en) * | 2013-12-18 | 2014-04-23 | 广西科技大学 | Carbon-sulfur composite positive pole material and preparation method thereof |
| CN103746097A (en) * | 2013-12-20 | 2014-04-23 | 广西科技大学 | Preparation method for lanthanum-doped lithium-sulfur positive electrode material |
| CN103762364A (en) * | 2014-02-12 | 2014-04-30 | 上海理工大学 | Sulfur-based lithium ion battery electrode material and preparation method thereof |
| CN104218219A (en) * | 2014-09-28 | 2014-12-17 | 南京中储新能源有限公司 | Carbon aerogel sulfenyl composite cathode and preparation and application thereof |
| CN104752725A (en) * | 2015-03-16 | 2015-07-01 | 山东玉皇新能源科技有限公司 | Cathode material for high-capacity graphene lithium sulphur battery and preparation method of cathode material |
| CN104882586A (en) * | 2015-06-01 | 2015-09-02 | 常州大学 | Super-thick sulfur electrode based lithium sulfur battery and production method thereof |
| CN104934569A (en) * | 2015-05-08 | 2015-09-23 | 南昌大学 | Preparation method of positive pole piece of ternary composite lithium-sulfur battery |
| CN105374999A (en) * | 2015-10-16 | 2016-03-02 | 广东烛光新能源科技有限公司 | Preparation method of sulfur-containing electrode material |
| US9281515B2 (en) | 2011-03-08 | 2016-03-08 | Gholam-Abbas Nazri | Lithium battery with silicon-based anode and silicate-based cathode |
| CN105449170A (en) * | 2014-08-13 | 2016-03-30 | 清华大学 | Method for preparing high-sulfur-content positive electrode material used for lithium-sulfur secondary battery |
| CN105576189A (en) * | 2014-11-11 | 2016-05-11 | 天津大学 | Sulfur electrode of lithium-sulfur battery and preparation method thereof |
| CN105591073A (en) * | 2014-10-23 | 2016-05-18 | 深圳华粤宝电池有限公司 | A cathode material used for secondary lithium batteries and a preparing method thereof |
| US9362560B2 (en) | 2011-03-08 | 2016-06-07 | GM Global Technology Operations LLC | Silicate cathode for use in lithium ion batteries |
| CN105900268A (en) * | 2013-10-18 | 2016-08-24 | 株式会社Lg化学 | Carbon nanotube-sulfur composite comprising carbon nanotube aggregates, and method for preparing same |
| CN106159267A (en) * | 2016-09-12 | 2016-11-23 | 贵州梅岭电源有限公司 | A kind of preparation method of sulfur carbon composite |
| CN106532043A (en) * | 2016-12-29 | 2017-03-22 | 西安理工大学 | Preparation method of carbon gel-loaded sulfur positive electrode material for lithium-sulfur battery |
| CN106637090A (en) * | 2016-12-29 | 2017-05-10 | 西安理工大学 | Method for loading substances easy to sublimate in porous materials |
| CN106631153A (en) * | 2016-12-29 | 2017-05-10 | 西安理工大学 | Method for loading subliming matters in aerogel material |
| CN106784713A (en) * | 2016-12-29 | 2017-05-31 | 西安理工大学 | A kind of preparation method of lithium sulfur battery anode material |
| CN106784770A (en) * | 2017-02-28 | 2017-05-31 | 南开大学 | The lithium magnesium alloy of content of magnesium high is the lithium-sulfur rechargeable battery of negative pole |
| CN106848384A (en) * | 2017-03-10 | 2017-06-13 | 合肥中航新能源技术研究院有限责任公司 | A kind of long-life lithium sulphur electrokinetic cell of high-energy-density |
| CN106910883A (en) * | 2016-02-03 | 2017-06-30 | 张琴 | The preparation method of lithium-sulfur cell |
| CN107768654A (en) * | 2012-10-26 | 2018-03-06 | 苏州宝时得电动工具有限公司 | The preparation method of electrode composite material, positive pole, the battery with the positive pole |
| CN108023062A (en) * | 2017-12-04 | 2018-05-11 | 大连理工大学 | A kind of lithium sulfur battery anode material |
| CN109216658A (en) * | 2018-10-10 | 2019-01-15 | 北京科技大学 | A kind of preparation method of the lithium-sulphur cell positive electrode of the additive containing nanometer aluminium powder |
| CN109301230A (en) * | 2018-11-13 | 2019-02-01 | 南昌大学 | A kind of composite anode material for lithium sulfur battery and preparation method thereof |
| CN109411732A (en) * | 2018-11-05 | 2019-03-01 | 桑顿新能源科技有限公司 | A kind of preparation method of the nucleocapsid cladding compound lithium sulfur battery anode material of sulphur-carbon nanotube |
| CN109599541A (en) * | 2018-11-15 | 2019-04-09 | 北京长城华冠汽车科技股份有限公司 | A kind of preparation method and lithium-sulfur cell of phosphorous carbon nanotube/sulphur composite material |
| CN112142034A (en) * | 2020-09-27 | 2020-12-29 | 武汉理工大学 | Preparation method of sulfur/carbon aerogel composite material |
| CN114784261A (en) * | 2022-06-21 | 2022-07-22 | 宜宾锂宝新材料有限公司 | Lithium battery positive electrode material and preparation method thereof |
-
2009
- 2009-06-02 CN CNA2009100851366A patent/CN101562244A/en active Pending
Cited By (77)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101719545A (en) * | 2009-12-16 | 2010-06-02 | 北京理工大学 | Anode composite material of lithium sulfur battery and preparation method thereof |
| CN101719545B (en) * | 2009-12-16 | 2014-07-02 | 北京理工大学 | Anode composite material of lithium sulfur battery and preparation method thereof |
| CN101867038A (en) * | 2010-06-08 | 2010-10-20 | 南开大学 | Method for preparing anode composite material for lithium sulfur secondary batteries |
| CN101867038B (en) * | 2010-06-08 | 2012-07-04 | 南开大学 | Method for preparing anode composite material for lithium sulfur secondary batteries |
| CN102315424A (en) * | 2010-07-06 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Composite anode material for lithium sulfur battery, preparation method and application thereof |
| CN102315424B (en) * | 2010-07-06 | 2014-07-16 | 中国科学院上海硅酸盐研究所 | Composite anode material for lithium sulfur battery, preparation method and application thereof |
| CN103210525A (en) * | 2010-11-26 | 2013-07-17 | 株式会社爱发科 | Positive electrode for lithium sulfur secondary battery, and method for forming same |
| CN103210525B (en) * | 2010-11-26 | 2015-11-25 | 株式会社爱发科 | Lithium-sulfur rechargeable battery positive pole and forming method thereof |
| US9882202B2 (en) | 2010-11-26 | 2018-01-30 | Ulvac, Inc. | Positive electrode for lithium-sulfur secondary battery and method of forming the same |
| US9281515B2 (en) | 2011-03-08 | 2016-03-08 | Gholam-Abbas Nazri | Lithium battery with silicon-based anode and silicate-based cathode |
| US9362560B2 (en) | 2011-03-08 | 2016-06-07 | GM Global Technology Operations LLC | Silicate cathode for use in lithium ion batteries |
| CN102185127A (en) * | 2011-04-07 | 2011-09-14 | 武汉理工大学 | Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery |
| CN102738448B (en) * | 2011-04-12 | 2015-03-25 | 通用汽车环球科技运作有限责任公司 | Encapsulated sulfur cathode for lithium ion battery |
| CN102738448A (en) * | 2011-04-12 | 2012-10-17 | 通用汽车环球科技运作有限责任公司 | Encapsulated sulfur cathode for lithium ion battery |
| CN102201567A (en) * | 2011-04-18 | 2011-09-28 | 武汉工程大学 | Preparation method for anode of lithium-sulfur battery |
| CN102263257B (en) * | 2011-06-28 | 2013-08-07 | 中国科学院金属研究所 | High energy flexible electrode material and preparation method thereof and application thereof in storage battery |
| CN102263257A (en) * | 2011-06-28 | 2011-11-30 | 中国科学院金属研究所 | High energy flexible electrode material and preparation method thereof and application thereof in storage battery |
| CN102280630B (en) * | 2011-07-04 | 2014-09-24 | 中国科学院过程工程研究所 | Sulphur-graphene composite cathode material and manufacturing method thereof |
| CN102280630A (en) * | 2011-07-04 | 2011-12-14 | 中国科学院过程工程研究所 | Sulphur-graphene composite cathode material and manufacturing method thereof |
| CN102522542A (en) * | 2011-12-14 | 2012-06-27 | 上海交通大学 | Elemental sulfur composite material containing graphene and preparation method thereof |
| US20130161557A1 (en) * | 2011-12-27 | 2013-06-27 | Winston CHUNG | Nano-Sulfur Composite Anode Material for Rare Earth Lithium-Sulfur Battery and its Preparation Method Thereof |
| US8858840B2 (en) * | 2011-12-27 | 2014-10-14 | Winston CHUNG | Nano-sulfur composite anode material for rare earth lithium-sulfur battery and its preparation method thereof |
| CN102522530A (en) * | 2011-12-27 | 2012-06-27 | 钟馨稼 | Nano-sulfur composite cathode material for rare earth lithium-sulfur battery, and preparation method thereof |
| CN102522530B (en) * | 2011-12-27 | 2014-08-20 | 雷天电池技术有限公司 | Nano-sulfur composite cathode material for rare earth lithium-sulfur battery, and preparation method thereof |
| WO2013097116A1 (en) * | 2011-12-28 | 2013-07-04 | Chung Winston | Nano-sulphur composite positive pole material for rare earth lithium sulphur battery and method for preparing same. |
| EP2784859A4 (en) * | 2011-12-28 | 2014-11-12 | Winston Chung | Nano-sulphur composite positive pole material for rare earth lithium sulphur battery and method for preparing same. |
| EP2784859A1 (en) * | 2011-12-28 | 2014-10-01 | Chung, Winston | Nano-sulphur composite positive pole material for rare earth lithium sulphur battery and method for preparing same. |
| CN102593433A (en) * | 2012-02-27 | 2012-07-18 | 清华大学 | Directional carbon nano-tube composite cathode material for lithium-sulfur secondary battery |
| CN102800865A (en) * | 2012-08-28 | 2012-11-28 | 吴永胜 | Lithium battery with total solid ions for conducting power |
| CN103000864A (en) * | 2012-10-25 | 2013-03-27 | 北京理工大学 | Sulfur composite cathode material and preparation method thereof |
| CN107768654A (en) * | 2012-10-26 | 2018-03-06 | 苏州宝时得电动工具有限公司 | The preparation method of electrode composite material, positive pole, the battery with the positive pole |
| CN102969481A (en) * | 2012-12-11 | 2013-03-13 | 武汉大学 | Sulfur/carbon composite material for lithium-sulfur secondary battery and preparation method thereof |
| CN103050729A (en) * | 2012-12-28 | 2013-04-17 | 大连理工大学 | Lithium sulfur battery |
| CN103178247B (en) * | 2013-03-22 | 2015-04-29 | 中南大学 | Sulfur/carbon composite material and preparation method thereof |
| CN103178247A (en) * | 2013-03-22 | 2013-06-26 | 中南大学 | Sulfur/carbon composite material and preparation method thereof |
| CN103178242A (en) * | 2013-03-25 | 2013-06-26 | 中国科学院上海硅酸盐研究所 | Graphene-sulfur composite material used as positive material of lithium-sulfur battery and preparation method of graphene-sulfur composite material |
| CN103236560B (en) * | 2013-04-16 | 2016-06-08 | 浙江大学 | A kind of sulfur/carbon composite anode material of lithium-sulfur cell and its preparation method and application |
| CN103236560A (en) * | 2013-04-16 | 2013-08-07 | 浙江大学 | Lithium-sulfur battery sulfur/carbon composite positive electrode material, preparation method and applications thereof |
| CN103531759A (en) * | 2013-09-23 | 2014-01-22 | 广州市香港科大***研究院 | Two-step adsorption preparation method of high magnification sulphur/mesoporous and microporous carbon HAC (honeycomb activated carbon) lithium sulphur battery anode composite material |
| CN103531759B (en) * | 2013-09-23 | 2015-09-02 | 广州市香港科大***研究院 | Two step absorption preparation methods of high magnification sulphur/middle microporous carbon HAC anode composite material of lithium sulfur battery |
| CN103560232A (en) * | 2013-09-30 | 2014-02-05 | 南京工业大学 | Preparation method of S-C positive pole composite material of high cycle performance lithium sulfur battery |
| US9911975B2 (en) | 2013-10-18 | 2018-03-06 | Lg Chem, Ltd. | Carbon nanotube-sulfur composite comprising carbon nanotube aggregates, and method for preparing same |
| CN105900268A (en) * | 2013-10-18 | 2016-08-24 | 株式会社Lg化学 | Carbon nanotube-sulfur composite comprising carbon nanotube aggregates, and method for preparing same |
| CN103746101B (en) * | 2013-12-18 | 2016-03-30 | 广西科技大学 | A kind of carbon sulphur composite positive pole and preparation method thereof |
| CN103746101A (en) * | 2013-12-18 | 2014-04-23 | 广西科技大学 | Carbon-sulfur composite positive pole material and preparation method thereof |
| CN103746097A (en) * | 2013-12-20 | 2014-04-23 | 广西科技大学 | Preparation method for lanthanum-doped lithium-sulfur positive electrode material |
| CN103762364A (en) * | 2014-02-12 | 2014-04-30 | 上海理工大学 | Sulfur-based lithium ion battery electrode material and preparation method thereof |
| CN103762364B (en) * | 2014-02-12 | 2016-03-23 | 上海理工大学 | A kind of sulfenyl lithium ion battery electrode material and preparation method thereof |
| CN105449170A (en) * | 2014-08-13 | 2016-03-30 | 清华大学 | Method for preparing high-sulfur-content positive electrode material used for lithium-sulfur secondary battery |
| CN104218219A (en) * | 2014-09-28 | 2014-12-17 | 南京中储新能源有限公司 | Carbon aerogel sulfenyl composite cathode and preparation and application thereof |
| CN105591073A (en) * | 2014-10-23 | 2016-05-18 | 深圳华粤宝电池有限公司 | A cathode material used for secondary lithium batteries and a preparing method thereof |
| CN105576189A (en) * | 2014-11-11 | 2016-05-11 | 天津大学 | Sulfur electrode of lithium-sulfur battery and preparation method thereof |
| CN104752725A (en) * | 2015-03-16 | 2015-07-01 | 山东玉皇新能源科技有限公司 | Cathode material for high-capacity graphene lithium sulphur battery and preparation method of cathode material |
| CN104934569A (en) * | 2015-05-08 | 2015-09-23 | 南昌大学 | Preparation method of positive pole piece of ternary composite lithium-sulfur battery |
| CN104882586B (en) * | 2015-06-01 | 2018-07-17 | 常州大学 | A kind of lithium-sulfur cell and preparation method thereof based on super thick sulfur electrode |
| CN104882586A (en) * | 2015-06-01 | 2015-09-02 | 常州大学 | Super-thick sulfur electrode based lithium sulfur battery and production method thereof |
| CN105374999A (en) * | 2015-10-16 | 2016-03-02 | 广东烛光新能源科技有限公司 | Preparation method of sulfur-containing electrode material |
| CN105374999B (en) * | 2015-10-16 | 2019-03-08 | 广东烛光新能源科技有限公司 | A kind of preparation method of sulfur-bearing electrode material |
| CN106910883B (en) * | 2016-02-03 | 2019-12-06 | 张琴 | Preparation method of lithium-sulfur battery |
| CN106910883A (en) * | 2016-02-03 | 2017-06-30 | 张琴 | The preparation method of lithium-sulfur cell |
| CN106159267A (en) * | 2016-09-12 | 2016-11-23 | 贵州梅岭电源有限公司 | A kind of preparation method of sulfur carbon composite |
| CN106637090B (en) * | 2016-12-29 | 2019-09-27 | 西安理工大学 | A method of loading easy sublimate in the porous material |
| CN106637090A (en) * | 2016-12-29 | 2017-05-10 | 西安理工大学 | Method for loading substances easy to sublimate in porous materials |
| CN106631153B (en) * | 2016-12-29 | 2020-02-18 | 西安理工大学 | Method for loading easily sublimable substance in aerogel material |
| CN106532043A (en) * | 2016-12-29 | 2017-03-22 | 西安理工大学 | Preparation method of carbon gel-loaded sulfur positive electrode material for lithium-sulfur battery |
| CN106784713A (en) * | 2016-12-29 | 2017-05-31 | 西安理工大学 | A kind of preparation method of lithium sulfur battery anode material |
| CN106532043B (en) * | 2016-12-29 | 2019-11-22 | 西安理工大学 | A kind of preparation method of carbon gel sulfur loaded-lithium sulfur battery anode material |
| CN106631153A (en) * | 2016-12-29 | 2017-05-10 | 西安理工大学 | Method for loading subliming matters in aerogel material |
| CN106784770A (en) * | 2017-02-28 | 2017-05-31 | 南开大学 | The lithium magnesium alloy of content of magnesium high is the lithium-sulfur rechargeable battery of negative pole |
| CN106848384A (en) * | 2017-03-10 | 2017-06-13 | 合肥中航新能源技术研究院有限责任公司 | A kind of long-life lithium sulphur electrokinetic cell of high-energy-density |
| CN108023062A (en) * | 2017-12-04 | 2018-05-11 | 大连理工大学 | A kind of lithium sulfur battery anode material |
| CN109216658A (en) * | 2018-10-10 | 2019-01-15 | 北京科技大学 | A kind of preparation method of the lithium-sulphur cell positive electrode of the additive containing nanometer aluminium powder |
| CN109411732A (en) * | 2018-11-05 | 2019-03-01 | 桑顿新能源科技有限公司 | A kind of preparation method of the nucleocapsid cladding compound lithium sulfur battery anode material of sulphur-carbon nanotube |
| CN109301230A (en) * | 2018-11-13 | 2019-02-01 | 南昌大学 | A kind of composite anode material for lithium sulfur battery and preparation method thereof |
| CN109599541A (en) * | 2018-11-15 | 2019-04-09 | 北京长城华冠汽车科技股份有限公司 | A kind of preparation method and lithium-sulfur cell of phosphorous carbon nanotube/sulphur composite material |
| CN112142034A (en) * | 2020-09-27 | 2020-12-29 | 武汉理工大学 | Preparation method of sulfur/carbon aerogel composite material |
| CN114784261A (en) * | 2022-06-21 | 2022-07-22 | 宜宾锂宝新材料有限公司 | Lithium battery positive electrode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101562244A (en) | Method for preparing elemental sulfur composite material used by lithium secondary battery | |
| Zhao et al. | Redox mediator assists electron transfer in lithium–sulfur batteries with sulfurized polyacrylonitrile cathodes | |
| CN101719545B (en) | Anode composite material of lithium sulfur battery and preparation method thereof | |
| CN106450102A (en) | Modified graphite separator for lithium-sulfur battery, preparation method of modified graphite separator and lithium-sulfur battery | |
| CN110148787B (en) | Electrolyte for improving capacity of lithium-sulfur battery and lithium-sulfur battery | |
| CN103579590A (en) | Preparation method for coating anode material of lithium battery | |
| CN102969481A (en) | Sulfur/carbon composite material for lithium-sulfur secondary battery and preparation method thereof | |
| CN101562261A (en) | Lithium-sulfur battery and preparation method thereof | |
| CN101740754B (en) | Preparation method of composite anode material for lithium element sulphur secondary battery | |
| CN103811731A (en) | Graphene-sulfur composite electrode material, preparation method and application thereof | |
| CN105514378A (en) | Lithium-sulfur battery positive-pole composite material with imitated cellular structure and preparation method thereof | |
| CN102088086A (en) | High-voltage lithium ion battery anode, lithium ion battery using same and preparation method of high-voltage lithium ion battery anode | |
| CN109256554B (en) | Vulcanized polymer composite material and preparation method and application thereof | |
| CN110611084B (en) | Lithium-sulfur secondary battery with long cycle life and 100% coulombic efficiency | |
| CN114373982B (en) | Liquid ether organic electrolyte-based low-negative electrode secondary sodium battery and preparation method thereof | |
| CN102324550A (en) | Semi-liquid lithium-sulfur battery | |
| CN105047861A (en) | Sulfur-carbon composite material and preparation method thereof | |
| CN103367791A (en) | Novel lithium ion battery | |
| CN105703003A (en) | Comb-shaped polymer, electrolyte and composite electrode for lithium battery, and applications of electrolyte and composite electrode | |
| CN111934020B (en) | High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof | |
| Medabalmi et al. | Lithium salt of biphenyl tetracarboxylate as an anode material for Li/Na-ion batteries | |
| CN111082054B (en) | Lithium-sulfur battery positive electrode material, positive electrode, preparation and application thereof | |
| Wu et al. | Tetrathiafulvalene as a multifunctional electrolyte additive for simultaneous interface amelioration, electron conduction, and polysulfide redox regulation in lithium-sulfur batteries | |
| CN109244335A (en) | A kind of polyimide diaphragm lithium-sulfur cell and preparation method thereof | |
| CN110556537B (en) | Method for improving electrochemical performance of anion-embedded electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20091021 |