CN102324507B - Preparation method for lithium-sulfur battery composite anode material - Google Patents
Preparation method for lithium-sulfur battery composite anode material Download PDFInfo
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- CN102324507B CN102324507B CN201110269592.3A CN201110269592A CN102324507B CN 102324507 B CN102324507 B CN 102324507B CN 201110269592 A CN201110269592 A CN 201110269592A CN 102324507 B CN102324507 B CN 102324507B
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Abstract
The present invention discloses a preparation method for a lithium-sulfur battery composite anode material. The preparation method comprises the following steps: (1) chemically activating vapor deposited carbon fiber through a solid base; (2) uniformly mixing the activated vapor deposited carbon fiber and a sulfur; (3) heating and holding in the presence of the inert atmosphere, such that the sulfur enters pores of the vapor deposited carbon fiber through a capillary action to obtain the sulfur-vapor deposited carbon fiber composite material. According to the present invention, the used vapor deposited carbon fiber has excellent electrical conductivity, good mechanical property and large aspect ratio, such that the natural three-dimensional conductive network is easily formed so as to improve the conductivity of the sulfur electrode, and improve the cycle performance of the lithium-sulfur battery.
Description
Technical field
The invention belongs to new energy materials field, be specifically related to a kind of composite anode material for lithium sulfur battery preparation method.
Background technology
Traditional resource and the energy are day by day in short supply, environmental problem is on the rise, and develop the energy strategy emphasis that new forms of energy and new energy storage and switch technology have become various countries, and electric automobile are realized one of focus being concerned of new energy technology especially.The key of electric automobile success or not is battery.For electric automobile being pushed to industry, just need develop battery and the required supplementary material of high-energy-density, high-specific-power, energy quick charge, life-span length, safety, low environment pollution, reasonable price.
Lithium ion battery has that specific energy is high, stable operating voltage, memory-less effect, have extended cycle life and the advantage such as environmental pollution is little, thereby becomes the focus of electrokinetic cell research.At present the most ripe, most widely used general, the most successful battery of commercialization of technology is cobalt acid lithium (LiCoO
2) material cell, its theoretical specific capacity is 274 mAh/g, but lithium cobaltate cathode material cost is high, fail safe is on the low side.LiMn2O4 (LiMn
2o
4) and LiFePO4 (LiFePO
4) the relative cobalt acid of material lithium has stronger price advantage, but their theoretical specific capacity is not high: LiFePO4 is 176 mAh/g, and LiMn2O4 is 148 mAh/g.These materials can not meet the requirement of high-energy-density, therefore need exploitation to have high power capacity, high-energy-density and good reversible novel anode material or battery system.
Lithium-sulfur cell has height ratio capacity (1675 mAh/g) and high-energy-density (2600 Wh/kg).In addition, take sulphur as positive electrode make it in source, the aspect such as cost, environmental friendliness also shows incomparable advantage.Lithium-sulfur cell is the chemical power source of future generation that has development potentiality and application prospect.
At present, there are several very large problems in lithium-sulfur cell: elemental sulfur and final discharging product are the insulators of electronics and ion; Intermediate product polysulfide in discharge process is dissolved in electrolyte, causes irreversible loss and the capacity attenuation of active material.For this reason, how to improve conductivity in the anodal cyclic process of sulphur, improve the distribution of sulphur, the diffusion that suppresses polysulfide is the research emphasis of sulfenyl positive electrode.
For lithium sulfur battery anode material researchers, done more work.Wherein, material with carbon element has the features such as outstanding conductivity, high specific area and microcellular structure, material with carbon element and sulphur are compounded with to the diffusion that is beneficial to the conductivity of raising sulphur positive pole, the distribution of improving sulphur and inhibition polysulfide, thereby sulphur carbon composite anode material is researcher's favor extremely.
(the Electrochemical Acta such as W.Zheng; 2006; 51:1330-1335.) sulphur is mixed with the ratio of 5: 1 with carbon nano-tube; under argon gas atmosphere protection; first be heated to 150 ℃ of insulation 10h sulphur is entered in carbon nano-tube pipe under capillary force, be then heated to 350 ℃ of insulation 4h to evaporate the sulphur at carbon nano-tube outer wall.Adopt 1MLiPF
6/ EC: DMC: EMC (volume ratio 1: 1: 1) electrolyte, is assembled into after battery with lithium sheet, according to the speed that discharges and recharges of 60mA/g, tests, and the initial specific capacity of battery is 700mAh/g.Sulphur and carbon nano-tube are compounded with and are beneficial to the conductivity that improves electrode, but carbon nano-tube is not easy to disperse, in the aggravation of easily reuniting of the preparation process of composite material, affect being uniformly distributed of sulphur content cloth, limited the performance of battery first discharge specific capacity.
Wang J. etc. (carbon 2008,46:229-235.) by sodium metasilicate and sucrose with certain proportion mixing copolymerization mesoporous carbon.Adopt 200 ℃ of insulation 6h, then the heating cycle of 300 ℃ of insulation 3h is total to hot sulphur and mesoporous carbon mixture, prepares sulphur carbon composite.Adopting EMITFSI ionic liquid and LiTFSI lithium salts is electrolyte, is assembled into after battery according to the charging and discharging currents density measurement of 50mA/g, and battery first discharge specific capacity reaches 1200mAh/g, and after 50 circulations, Capacitance reserve is more than 500mAh/g.Adopt mesoporous carbon and the compound first discharge specific capacity of sulphur to be greatly improved, but capacity attenuation is very fast.
Jia-jia Chen etc. (Electrochemical Acta, 2010,55:8062-8066.) adopt exchange of solvent legal system for sulphur/carbon/carbon nano tube compound anode material.After carbon nano-tube is put into red fuming nitric acid (RFNA) purification process, be dispersed in lauryl sodium sulfate, sulphur is dissolved in oxolane.Two kinds of solution are mixed in certain proportion, and strong agitation.With distilled water, repeatedly clean away lauryl sodium sulfate, obtain the composite material that carbon nano tube surface covers sulphur.While discharging and recharging with the current density of 300mA/g, the about 1200mAh/g of specific capacity first of battery.
Chinese patent (CN 101891930A) has been announced sulfur-based composite anode material of a kind of carbon nanotubes and preparation method thereof.Acrylonitrile itaconic acid monomer is compound in carbon nano tube surface original position, mixing with sulphur, then by heat treatment, sulphur is dispersed in the matrix of acrylonitrile itaconic acid copolymer dehydrocyclization formation.After forming battery, circulate 30 Capacitance reserves more than 600mAh/g.This method is conducive to the dispersion of carbon nano-tube and being uniformly distributed of sulphur, but synthesis technique is complicated.
(the Journal of Power Sources such as Wang Jiazhao, 2011,196,7030-7034.) adopt solvent-thermal method to synthesize Graphene, then by Graphene and sulphur vapour deposition is compound makes the composite material that sulfur content is 22wt.%, after being assembled into battery, with 50mA/g current density, carry out constant current charge-discharge test, battery first discharge specific capacity reaches 1611mAh/g, and after 40 circulations, Capacitance reserve is at 600mAh/g.The specific capacity first of battery approaches theoretical value, but capacity attenuation is serious.
Summary of the invention
Existing lithium-sulfur cell cycle performance is poor, one of them reason be sulfur electrode in cyclic process conductivity variation, therefore maintain the stable conductive network of electrode significant.The Carbon Materials adopting in existing research has carbon black, carbon nano-tube and mesoporous carbon etc., they all have good conductivity, but carbon nano-tube is not easy to disperse, affected the dispersed of sulphur, carbon black and mesoporous carbon are all nano-sized powders or microballoon, in cyclic process, easily reunite, aggravated the deterioration of sulfur electrode performance.For this problem, we propose vapor-grown carbon fibers to apply to the electrode of lithium-sulfur cell.Vapour deposition carbon fiber has the advantages such as good conductivity, draw ratio is large, thermal conductivity is good, between them, can be barricaded as natural network by bridge, is conducive to the diffusion of electrical conductivity and lithium ion.In addition, the draw ratio that carbon fiber is large can strengthen collector, bonding agent and active material particle between engaging force, the meaning positive to the stable generation of electrode structure.
In order to improve the capacity of sulphur positive pole, bring into play, improve lithium-sulfur cell cycle performance, the invention provides a kind of lithium-sulfur battery composite anode material preparation method.
Object of the present invention is achieved through the following technical solutions:
A kind of preparation method of lithium-sulfur battery composite anode material comprises the following steps:
(1) vapour deposition carbon fiber is mixed with mass ratio with solid base for 1: 1～1: 5; under inert atmosphere protection; heating and thermal insulation 1～4h at 600～1000 ℃, extremely neutral with diluted acid and deionized water washing after taking out, the vapour deposition carbon fiber after dry activation.
(2) the vapour deposition carbon fiber after activation is mixed with sulphur, the organic solvent of take takes out after solvent ball milling 1～5h, ultrasonic dispersion 5～60min, vacuumize at 40～90 ℃;
(3) under inert atmosphere protection, mixture after ball milling is incubated to 4～10h within the scope of 120～400 ℃, cool to room temperature with the furnace and obtain composite positive pole.
Vapour deposition carbon fiber diameter 50～200nm that the present invention preferably uses, length 5～20 μ m.It has outstanding conductivity, good mechanical properties and large draw ratio, easily forms natural three-dimensional conductive network.Vapour deposition carbon fiber can directly directly be buied from the market, the diameter of the Jiang cause company of the X series that the diameter of Japanese Zhao He company is 50～150nm as adopted and the serial vapour deposition carbon fiber of S ，Huo TaiWan, China company is the vapour deposition carbon fiber of 100～200nm series etc.
The preferred embodiment of the invention be the mass ratio of vapour deposition carbon fiber after sulphur and activation is controlled to 1: 3～be advisable at 10: 1.
The preferred embodiment of the invention also comprises:
The solid base material using is one or several in potassium hydroxide, NaOH, lithium hydroxide.
Inert atmosphere is a kind of in nitrogen, argon gas or two kinds.
Diluted acid is a kind of in watery hydrochloric acid, dilute sulfuric acid, rare nitric acid.
Organic solvent medium is one or more in acetone, isopropyl alcohol, n-butanol, normal propyl alcohol, absolute ethyl alcohol.
Sulphur is a kind of in sublimed sulfur, elementary sulfur or two kinds.
The resulting composite positive pole of the present invention, the mass content of sulphur in composite material is 15%～70%.
A kind of lithium-sulfur battery composite anode material preparation method of the present invention, has following advantage:
(1) a kind of lithium-sulfur battery composite anode material of the present invention.By with solid base activation vapour deposition carbon fiber, make carbon fiber form micropore and mesopore, increased specific area and the pore volume of carbon fiber.Compound by vapour deposition carbon fiber after activation and sulphur are heated altogether, be conducive to the performance of vapour deposition carbon fiber high conductivity, and improve the distribution of sulphur.The vapour deposition carbon fiber with big L/D ratio be difficult for to be reunited, and their bridges are taken and formed three-dimensional conductive network, be conducive to the infiltration of electrolyte, the diffusion of lithium ion and cyclic process electrode structure stable.
(2) composite sulfur that adopts the present invention to prepare is anodal is assembled into button cell with cathode of lithium, and under room temperature, when 0.2C (335mA/g) constant current charge-discharge, first discharge specific capacity reaches 1350mAh/g, and the Capacitance reserve that circulates after 50 times is at 600mAh/g.The compound specific discharge capacity that improves battery of vapour deposition carbon fiber and sulphur, has improved the cycle performance of battery to a certain extent.
(3) the present invention adopts thermal process, is easy in industrial enforcement.There is the advantages such as synthetic method is simple, utilization rate of raw materials is high, the pattern of material composition is controlled.
Accompanying drawing explanation
Fig. 1 is the XRD figure of vapour deposition carbon fiber (a) after the activation obtaining by embodiment 2, sulphur-vapour deposition carbon fibre composite (b) and sulphur (c).
Fig. 2 is the lithium-sulfur battery composite anode material FESEM photo obtaining by embodiment 3.
Fig. 3 is the lithium-sulfur battery composite anode material that obtains by the embodiment 3 cycle performance curve in lithium-sulfur cell.
Fig. 4 is the lithium-sulfur battery composite anode material that obtains by the embodiment 4 first charge-discharge curve in lithium-sulfur cell.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not restricted to the protection range of invention.
Embodiment 1
With the alkali charcoals of 3: 1, than mixing NaOH and gas phase deposit carbon fiber, after mixing, put into resistance furnace and heat.Under nitrogen protection, after heating and thermal insulation 2h, cool to room temperature at 900 ℃ with the furnace and take out.With in dilute sulfuric acid and potassium hydroxide, then with deionized water washing to neutral, the vapour deposition carbon fiber after dry activation at 110 ℃ then.
By potassium hydroxide, activate, the specific area of vapour deposition carbon fiber obviously increases.After 900 ℃ of activation, carbon fiber specific area is 41.1m
2/ g, pore volume is 0.201m
3/ g.
Vapour deposition carbon fiber after activation is mixed with the mass ratio of elementary sulfur with 3: 1, puts into ball grinder,, the acetone of take takes out after solvent ball milling 2h, ultrasonic dispersion 15min, vacuumize at 60 ℃.
Under argon gas atmosphere protection, mixture after ball milling is warming up to 155 ℃ of insulation 6h, take out after cooling to room temperature with the furnace.Gained composite positive pole, its sulfur content is 17.2wt.%.
Electrochemical property test:
All preparations in the following manner of electrode slice and button cell assembling thereof: the prepared vapour deposition carbon fiber/sulphur of embodiment 1 composite material, conductive black Super P, bonding agent PVDF are evenly mixed according to mass ratio at 8: 1: 1, drip appropriate solvent (NMP), after grinding to form uniform sizing material, be coated in aluminum foil current collector 60 ℃ of vacuumize 15h.Strike out the electrode slice that diameter is 10mm.Take metal lithium sheet as negative pole, be assembled into CR2025 button cell in being full of the glove box of argon gas, at room temperature (25 ℃) carry out constant current charge-discharge test with 0.2C, and first discharge specific capacity is 1163mAh/g.At room temperature with 0.05C, carry out constant current charge-discharge test, first discharge specific capacity is 1203mAh/g.
With the alkali charcoal ratios of 4: 1, take potassium hydroxide and gas phase deposit carbon fiber, mix.Under argon gas atmosphere protection, heating and thermal insulation 2h at 800 ℃, cools to room temperature with the furnace and takes out.With in watery hydrochloric acid and potassium hydroxide, then with deionized water washing to neutral, the vapour deposition carbon fiber at 120 ℃ after dry activation.In argon gas atmosphere, at 800 ℃, after activation, vapour deposition carbon fiber specific area is 40.4m
2/ g, pore volume is 0.160m
3/ g.
Vapour deposition carbon fiber after activation is mixed with the mass ratio of sublimed sulfur with 3: 1, puts into ball grinder,, the absolute ethyl alcohol of take takes out after solvent ball milling 2h, disperses 10min to obtain suspended nitride, by suspended nitride vacuumize at 55 ℃.
In argon gas atmosphere, mixture after ball milling is warming up to 155 ℃ of insulation 6h, cool to room temperature with the furnace and obtain sulphur-vapour deposition carbon fiber composite positive pole.Its sulfur content is 15.1wt.%.
Fig. 1 is the XRD figure of vapour deposition carbon fiber after lithium-sulfur battery composite anode material, sulphur, activation.As seen from the figure, the collection of illustrative plates of composite material is very similar to carbon fiber, and the characteristic peak of sulphur only embodies a little to some extent at a place.
Embodiment 3
Vapour deposition carbon fiber (according to embodiment 2 method gained) after activation is mixed with the mass ratio of sublimed sulfur with 3: 2, put into ball grinder, the absolute ethyl alcohol of take takes out after solvent ball milling 2h, put into the ultrasonic dispersion of beaker 12min and obtain suspended nitride, by suspended nitride vacuumize at 57 ℃.
In argon gas atmosphere, mixture after ball milling is warming up to 155 ℃ of insulation 6h, cool to room temperature with the furnace.Gained sulphur/vapour deposition carbon fibre composite sulfur content is 28.4wt.%.
Fig. 2 is embodiment 2 composite positive pole SEM figure.The consistent appearance of vapour deposition carbon fiber after the pattern of composite material and activation, does not see the bulky grain sulphur of deposition, and the bridge that well intersects between composite fiber is taken.
Electrode preparation and electrochemical property test method are identical with embodiment 1.
According to the lithium-sulfur battery composite anode material 0.2C charge-discharge test of embodiment 3 preparation, its first discharge specific capacity is 1350mAh/g, and the Capacitance reserve after 50 times that circulates, at 600mAh/g, is shown in Fig. 3.
Embodiment 4
Alkali charcoals ratio with 3: 1 mixes NaOH and gas phase deposit carbon fiber.Under nitrogen atmosphere protection, after heating and thermal insulation 2h, cool to room temperature with the furnace at 800 ℃ and take out.With in dilute sulfuric acid and potassium hydroxide, then with deionized water washing to neutral, the vapour deposition carbon fiber after dry activation.In nitrogen atmosphere, after 800 ℃ of activation, carbon fiber specific area is 47.8m
2/ g, pore volume is 0.186m
3/ g.
Vapour deposition carbon fiber after activation is mixed with the mass ratio of elementary sulfur with 1: 5,, the absolute ethyl alcohol of take takes out after solvent ball milling 3h, ultrasonic dispersion 12min, vacuumize at 55 ℃.
In argon gas atmosphere, mixture after ball milling is warming up to 155 ℃ of insulation 6h, then continue to be warming up to 300 ℃ of insulation 1.5h, cool to room temperature with the furnace and obtain composite positive pole.Its sulfur content is 30.3wt.%.
Electrode preparation and electrochemical property test method are identical with embodiment 1.
According to the lithium-sulfur battery composite anode material 0.2C charge-discharge test of embodiment 3 preparations, its first discharge specific capacity is 1310mAh/g, sees Fig. 4.
Embodiment 5
With the alkali charcoal ratios of 2.5: 1, take lithium hydroxide and gas phase deposit carbon fiber, mix.Under argon gas atmosphere protection, in 700 ℃ of heating and thermal insulation 2h, cool to room temperature with the furnace and take out.With in dilute sulfuric acid and potassium hydroxide, then with deionized water washing to neutral, the vapour deposition carbon fiber at 120 ℃ after dry activation.In argon gas atmosphere, at 800 ℃, after activation, vapour deposition carbon fiber specific area is 34.4m
2/ g, pore volume is 0.147m
3/ g.
Vapour deposition carbon fiber after activation is mixed with the mass ratio of sublimed sulfur with 1: 10, and the acetone of take takes out after solvent ball milling 3h, ultrasonic dispersion 20min, vacuumize at 58 ℃.
In nitrogen atmosphere, mixture after ball milling is warming up to 155 ℃ of insulation 6h, be then warming up to 300 ℃ of insulation 3h, cool to room temperature with the furnace and obtain composite positive pole.Composite material sulfur content is 46.8wt.%.
Electrode preparation and electrochemical property test method are identical with embodiment 1.
According to the lithium-sulfur battery composite anode material 0.2C charge-discharge test of embodiment 4 preparations, its first discharge specific capacity is 1236mAh/g.
Claims (7)
1. a lithium-sulfur battery composite anode material preparation method, is characterized in that, preparation method comprises the following steps:
(1) vapour deposition carbon fiber is evenly mixed with mass ratio 1:1～1:5 with solid base, under inert atmosphere protection, heating and thermal insulation 1～4h at 600～1000 ℃, extremely neutral with diluted acid and deionized water washing after taking out, the vapour deposition carbon fiber after 90～150 ℃ of dry activation; The solid base using is one or several in potassium hydroxide, NaOH, lithium hydroxide;
(2) the vapour deposition carbon fiber after activation is mixed with sulphur, the organic solvent of take takes out after solvent ball milling 1～5h, ultrasonic dispersion 5～60min, vacuumize at 40～90 ℃;
(3) under inert atmosphere protection, mixture after ball milling is incubated to 4～10h within the scope of 120～400 ℃, cool to room temperature with the furnace, obtain sulphur for lithium-sulfur cell/vapour deposition carbon fiber composite positive pole.
2. a kind of lithium-sulfur battery composite anode material preparation method according to claim 1, is characterized in that: the vapour deposition carbon fiber diameter 50～200nm of use, length 5～20 μ m.
3. according to a kind of lithium-sulfur battery composite anode material preparation method described in claim 1 or 2, it is characterized in that: described sulphur is 1:3～10:1 with the mass ratio of the rear vapour deposition carbon fiber of activation.
4. a kind of lithium-sulfur battery composite anode material preparation method according to claim 1, is characterized in that: described organic solvent is one or more in acetone, isopropyl alcohol, n-butanol, normal propyl alcohol, absolute ethyl alcohol.
5. a kind of lithium-sulfur battery composite anode material preparation method according to claim 1, is characterized in that: sulphur used is sublimed sulfur.
6. a kind of lithium-sulfur battery composite anode material preparation method according to claim 1, is characterized in that: described inert atmosphere is a kind of in nitrogen, argon gas or two kinds.
7. a kind of lithium-sulfur battery composite anode material preparation method according to claim 1, is characterized in that: described diluted acid is one or several in watery hydrochloric acid, dilute sulfuric acid, rare nitric acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891292A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for preparing composite anode material of lithium-sulfur battery |
| CN105283983B (en) | 2012-11-19 | 2018-08-31 | 苏里亚·S·莫甘缇 | Carbon is perfused in sulphur for secondary battery material |
| CN103187560B (en) * | 2013-03-30 | 2016-02-24 | 浙江工业大学 | A kind of sulphur carbon composite of imitative animal sclay texture and application thereof |
| CN103219517B (en) * | 2013-04-15 | 2015-01-21 | 中南大学深圳研究院 | Preparation method for nitrogen-doped porous carbon sphere-sulfur composite positive material |
| CN103700818A (en) * | 2013-12-20 | 2014-04-02 | 复旦大学 | Sulfur-carbon composite material with nitrogen-doped porous carbon nanofiber net-shaped structure, as well as preparation method and application of composite material |
| CN104201389B (en) * | 2014-08-20 | 2016-07-06 | 中南大学 | A kind of preparation method of lithium selenium cell positive pole |
| CN104600266B (en) * | 2015-01-09 | 2017-01-18 | 上海大学 | Method for preparing carbon fibre cloth loaded sulphur composite material |
| CN104900880B (en) * | 2015-06-03 | 2017-07-11 | 中国地质大学（武汉） | A kind of lithium-sulfur battery composite anode material and preparation method thereof |
| CN105932235B (en) * | 2016-05-05 | 2018-10-23 | 北京化工大学 | A kind of lithium sulfur battery anode material and preparation method thereof based on galapectite |
| CN105826540B (en) * | 2016-06-03 | 2018-10-02 | 合肥工业大学 | A kind of lithium-sulfur cell composite positive pole and the preparation method and application thereof |
| CN106025216B (en) * | 2016-06-16 | 2018-10-09 | 广东工业大学 | Lithium sulfur battery anode material, preparation method and lithium-sulfur cell |
| CN108511723B (en) * | 2018-04-03 | 2020-06-09 | 中南大学 | Cobalt manganate/NC/S composite material, preparation method thereof and application of cobalt manganate/NC/S composite material as positive electrode material of lithium-sulfur secondary battery |
| CN109860532A (en) * | 2018-12-18 | 2019-06-07 | 南京信息工程大学 | A kind of lithium-sulfur cell peanut shell carbon/sulphur anode composite preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384556A (en) * | 2002-04-17 | 2002-12-11 | 中国科学院上海微***与信息技术研究所 | Composite single substance sulphur nano-material for positive electrode of secondary electrochemical power supply and its prepn |
| CN102163720A (en) * | 2011-02-12 | 2011-08-24 | 中南大学 | Lithium sulfide-porpous carbon compound positive material for lithium ion battery and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100551005B1 (en) * | 2003-10-21 | 2006-02-13 | 삼성에스디아이 주식회사 | Positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising same |
-
2011
- 2011-09-10 CN CN201110269592.3A patent/CN102324507B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384556A (en) * | 2002-04-17 | 2002-12-11 | 中国科学院上海微***与信息技术研究所 | Composite single substance sulphur nano-material for positive electrode of secondary electrochemical power supply and its prepn |
| CN102163720A (en) * | 2011-02-12 | 2011-08-24 | 中南大学 | Lithium sulfide-porpous carbon compound positive material for lithium ion battery and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| J.L.Wang 等.Sulfur–carbon nano-composite as cathode for rechargeable lithium battery based on gel electrolyte.《Electrochemistry Communications》.2002,第4卷(第6期),第499-502页. |
| Sulfur–carbon nano-composite as cathode for rechargeable lithium battery based on gel electrolyte;J.L.Wang 等;《Electrochemistry Communications》;20020630;第4卷(第6期);第499-502页 * |
| 张治安等.活性炭的制备及其在有机超级电容器中的应用.《电子元件与材料》.2007,第26卷(第11期),第12-16页. |
| 活性炭的制备及其在有机超级电容器中的应用;张治安等;《电子元件与材料》;20071130;第26卷(第11期);第12-16页 * |
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