CN102593433A - Directional carbon nano-tube composite cathode material for lithium-sulfur secondary battery - Google Patents
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Abstract
The invention discloses a directional carbon nano-tube composite cathode material for a lithium-sulfur secondary battery. A structure consisting of carbon nano-tubes with orientation, namely the directional carbon nano-tubes is used as a framework of the material, a carbon nano-tube/sulfur composite material is obtained by compounding, and the composite material can be used as the cathode material of the lithium-sulfur secondary battery. In a conductive network constructed by using disordered carbon nano-tubes, the contact resistance at a lap joint of the carbon nano-tubes in the conductive network is always greatly increased by the load of sulfur; however, with the adoption of the directional carbon nano-tubes, an electron channel contacts a current collector through one carbon nano-tube, so that the generation of a large amount of contact resistance is avoided, and an efficient conductive network is provided. Meanwhile, an ordered pore structure of a directional carbon nano-tube electrode also ensures that an ion channel is smooth, so that the cathode material has high cycle performance, is a high-performance cathode material, and is expected to promote further enhancement of the performance of the lithium-sulfur secondary battery and the industrial application of the lithium-sulfur secondary battery.
Description
Invention field
The present invention relates to a kind of positive electrode of lithium-sulfur rechargeable battery, relate in particular to a kind of aligned carbon nanotube composite positive pole of lithium-sulfur rechargeable battery.
Background technology
Modern electronics industry development constantly promotes the performance of portable set, also energy content of battery density has been proposed increasingly high requirement; On the other hand, battery for electric automobile has also proposed high requirement to the battery of high-energy-density.The performance of existing lithium ion battery can not satisfy the requirement of these equipment gradually, and it is imperative to develop new high-specific energy battery system.
Sulphur is a kind of positive electrode with high theoretical specific capacity, and theoretical capacity can reach 1672mAh/g, and the battery theoretical energy density of forming with cathode of lithium can reach 2600Wh/kg.And having cheapness, numerous advantages such as nontoxic, is the one type of novel electrode material that receives extensive concern.But owing to the insulating properties of sulfur materials itself and with the highly dissoluble of lithium reaction intermediate in electrolyte the sulphur positive electrode of lithium-sulfur cell is decayed seriously in charge and discharge process, and have higher self-discharge rate, influenced its large-scale application.In order to overcome the defective that elemental sulfur exists; Present numerous researcher adopts compound mode that sulfur electrode is carried out modification; Sulphur/carbon composite, and the preparation of sulphur/polymer composites have been carried out respectively, through improving conductivity and the immobilization role of sulphur simple substance having been improved the anodal charge-discharge performance of sulphur to a certain extent.For instance: Nazar etc. are compound through sulphur and mesoporous carbon, utilize the migration of mesopore orbit restriction polysulfide, obtained electrode material (Ji X, Lee K T, the Nazar LF.Nat Mater.2009 of superior performance; 8 (6): 500-6.); Wang Jiulin etc. have been through having realized partly solidified to sulphur with sulphur and polyacrylonitrile are compound, thereby have improved performances such as cyclical stability (Wang JL, Yang J, Xie JY, the Xu NX.Adv Mater.2002 of electrode; 14 (13-14): 963-5.; Wang Jiulin, Yang Jun separates sparkling and crystal-clearly, wait publication number: CN 1384556).
CNT is used as conductive additive and is widely used in the lithium ion battery as one type of tubular material with superior electrical conductivity.The report (Han SC, Song MS, Lee H, the et al.J Electrochem Soc.2003 that use CNT to add material for conduction are also arranged in the manufacturing process of lithium-sulfur cell sulfur electrode; 150 (7): A889.; Wei W, Wang J, Zhou L, et al.Electrochem Commun.2011; 13 (5): 399-402.).Yet; Mostly the carbon nanotube conducting skeleton that in electrode material, uses at present is that unordered shape and length of carbon nanotube are lower; The load that the disordered carbon nanotube makes up sulphur in the conductive network often causes conductive network significantly to improve at CNT lap-joint contact resistance, fails to give full play to the tubular material advantage of CNT.If the aligned carbon nanotube that can adopt the approximate formation that is arranged in parallel of CNT then can make full use of its higher specific surface area as the anodal conducting matrix grain of sulphur, the good c direction of principal axis conductivity and the duct of homogeneous are that electrode material provides good ion channel; And the use of aligned carbon nanotube makes electron channel pass through a CNT to contact with collector, avoided the generation of a large amount of contact resistances, conductive network efficiently is provided.Simultaneously, the orderly pore structure of aligned carbon nanotube electrode has also ensured unobstructed ion channel.In the electrode material of load elemental sulfur as active material, owing to have more excellent conductivity and ion channel, material embodies than significant advantage in high electric current charge and discharge process.Meanwhile; The orderly pore passage structure of this macroscopic view also provides a foundation structure of being convenient to carry out the electrode material structure control; Can make up aligned carbon nanotube-sulphur-polymeric system electrode material with labyrinth; For utilizing the high theoretical capacity performance of sulfur materials better, overcome that problem such as polysulfide dissolving provides new way in the charge and discharge process.
This shows,, then be expected to further promote the chemical property of electrode material, further promote the large-scale application of lithium-sulfur rechargeable battery if can develop a kind of lithium-sulfur rechargeable battery electrode material based on aligned carbon nanotube.
Summary of the invention
The objective of the invention is to change the many present situations of carrying out of CNT interpolation in the present lithium-sulfur rechargeable battery with ordered form; Propose a kind of with the thinking of high-sequential aligned carbon nanotube as sulphur positive electrode skeleton; Can make full use of aligned carbon nanotube surface, orderly advantage such as pore passage structure, and with elemental sulfur or the polymer/compound acquisition high-performance lithium of sulphur active material sulfur rechargeable battery anode material.
The present invention provides a kind of aligned carbon nanotube composite positive pole structure of lithium-sulfur rechargeable battery, and this material structure has following characteristic:
1) a kind of aligned carbon nanotube composite positive pole that is used for lithium-sulfur rechargeable battery; It is characterized in that this material composition as follows: skeleton is an aligned carbon nanotube film; Be compounded with active electrode material therebetween, the mass ratio of aligned carbon nanotube and active material is 1: 0.1～50; Said active material is elemental sulfur or polymer and sulphur composite material.
Said structure 1) aligned carbon nanotube is the approximate forming array shape macroscopic body that is arranged in parallel of CNT in, and its thickness is between 1～2000 micron, and the CNT caliber that constitutes aligned carbon nanotube is between 1～100 nanometer.
Said structure 1) or 2) in polymer and the sulphur composite material polymer be in polyaniline, polyacrylonitrile, polypyrrole, polythiophene, PEO and the polyethylene glycol one or more.
Said structure 1) in the electrode material, in the active material in sulphur and the polymer mass ratio of carbon be 1: 0～5.
The present invention compares prior art; Have following advantage and high-lighting effect: the present invention adopts the framework material of aligned carbon nanotube as the lithium-sulfur rechargeable battery anode material; Shortcomings such as conducting matrix grain conductivity deficiency and duct be random have been overcome in original material; Significantly improved the conductivity of framework material, the aligned carbon nanotube skeleton has improved the whole chemical property of electrode material also for positive electrode provides orderly and controlled pore passage structure simultaneously.The aligned carbon nanotube material also provides possibility for the electrode material that utilizes elemental sulfur, sulphur/polymer composites structure to have orderly three-dimensional structure; And be expected to for suppressing lithium-sulfur cell technology barriers such as polysulfide migration new solution is provided, help to advance the practicability of lithium-sulfur rechargeable battery sulphur positive electrode.
Description of drawings
The sulphur combination electrode scanning electron microscopy of the aligned carbon nanotube preparation that thermal chemical vapor deposition method obtains on Fig. 1 silicon chip.
The sulphur combination electrode top high power scanning electron microscopy of the aligned carbon nanotube preparation that thermal chemical vapor deposition method obtains on Fig. 2 silicon chip, the elemental sulfur distribution of material is between CNT.
Fig. 3 aligned carbon nanotube/sulphur and the disordered carbon nanotube/sulphur combination electrode performance in the large current density electrical testing of battery relatively.
The aligned carbon nanotube side CNT of the chemical vapor deposition processes that swims on Fig. 4 quartz plate preparation is arranged scanning electron microscopy.
Embodiment:
A kind of aligned carbon nanotube composite positive pole that is used for lithium-sulfur rechargeable battery is made up of aligned carbon nanotube skeleton and sulfur-bearing positive electrode active materials; Wherein aligned carbon nanotube obtains at substrate surfaces such as quartz, silicon chips through swim chemical vapour deposition (CVD) or TCD thermochemical deposition method, and its thickness is at 1～2000 micron, and the CNT caliber that constitutes aligned carbon nanotube is between 1～100 nanometer.Aligned carbon nanotube is separable into suitable dimension from the substrate after separating and is used for follow-up compound, test or battery production.The aligned carbon nanotube material has excellent conducting performance and mechanical property, makes based on the electrode material of aligned carbon nanotube and can bring into play high rate performance preferably.
The preparation of positive electrode is by the compound realization of active material on aligned carbon nanotube; For example: elemental sulfur can be through sulphur heating and melting back loading in aligned carbon nanotube; Elemental sulfur is gasified back loading in aligned carbon nanotube, also can carry out the liquid phase load to aligned carbon nanotube through the solution of sulphur; Sulphur/polymer composites also can be through first composition polymer after the sulfur loaded in aligned carbon nanotube, or the mode of first composition polymer back loading sulphur is packed in the hole of aligned carbon nanotube in aligned carbon nanotube.Wherein polymer is one or more in polyaniline, polyacrylonitrile, polypyrrole, polythiophene, PEO and the polyethylene glycol.In the active material in sulphur and the polymer mass ratio of carbon be 1: 0～5; The mass ratio of CNT and active material is 1: 0.1～50 in the combination electrode material.Polymer can also realized the selective deposition on the aligned carbon nanotube c direction of principal axis through means such as in-situ polymerization or electro-deposition during to the aligned carbon nanotube area load, and the suitable structure of restriction polysulfide diffusion is provided.
Because aligned carbon nanotube has mechanical strength preferably; The electrode material that preparation is accomplished keeps the film like structures of aligned carbon nanotube, and unordered binding agent and aluminum foil current collector can directly be carried out the Integration Assembly And Checkout of battery after the process drying and other steps as electrode slice.This electrode has the favorable conductive network configuration, and the duct is orderly simultaneously, and integral body provides better electronics and ion channel; It is the outstanding lithium-sulfur rechargeable battery electrode material of a kind of performance.
Can further understand the present invention from following examples, but the present invention not only is confined to following examples.
Embodiment 1: adopt the thermal chemical vapor deposition process to prepare aligned carbon nanotube at the silicon chip surface that is coated with catalyst, this carbon nano-tube film thickness is about 100 microns, and the CNT caliber is 8 nanometers (accompanying drawings 1).This aligned carbon nanotube film is peeled off from silicon chip surface; And with the sublimed sulfur powder 155 ℃ down altogether heat be compounded to form positive electrode, the top electron micrograph shows that sulphur content is distributed between the hole of aligned carbon nanotube (accompanying drawing 2).The mass ratio of aligned carbon nanotube and active material elemental sulfur is 1: 10.Prepared disordered carbon nanotube/elemental sulfur composite material with identical mass ratio, and mixed with binding agent and to film in aluminium foil surface positive electrode sample as a comparison.The assembling test result shows that aligned carbon nanotube/sulphur composite positive pole not only embodies higher circulation volume, especially when high electric current discharges and recharges, has significant advantage (accompanying drawing 3).
Embodiment 2: utilize and swim chemical vapor deposition processes at quartz plate surface preparation aligned carbon nanotube film, the thickness of film is 1000 microns, and the CNT caliber is 100 nanometers in the aligned carbon nanotube, and approximate being arranged in parallel forms array structure (accompanying drawing 4).This aligned carbon nanotube film is separated from quartz surfaces, and carry out the electrochemical deposition of polyaniline as work electrode, the polyaniline for preparing is deposited in the aligned carbon nanotube.After the cleaning, adopt the carbon disulfide solution of sulphur that the aligned carbon nanotube film is flooded, treat that the carbon disulfide volatilization both had been able to polymer, the sulphur mixture is the positive electrode of active material.This material is carried out 250 ℃, and the heat treatment under the inert ambient environment makes sulphur and polyaniline part Cheng Jian.In this active material; The mass ratio of carbon is 1: 0.5 in sulphur and the polymer; The mass ratio of active material and aligned carbon nanotube is 1: 1, and this electrode material has the initial electrochemistry capacitance of 846mAh/g in electro-chemical test; And after 100 circulations, keep the capacity of 632mAh/g, present higher specific capacity and more excellent cyclical stability.
Embodiment 3: utilize the thermal chemical vapor deposition process to prepare aligned carbon nanotube at the silicon chip surface that is coated with catalyst, carbon nano-tube film thickness is 10 microns, and the CNT caliber is 1 nanometer.This aligned carbon nanotube film is peeled off from silicon chip surface; And in three-electrode system, carry out the electrochemical deposition of polypyrrole as work electrode; Take out and clean back and polyethylene glycol, sublimed sulfur admixture of powder; Heat refers to that 180 ℃ make polyethylene glycol and sublimed sulfur powder melts altogether in inert atmosphere, forms compound with aligned carbon nanotube/polypyrrole structure.In this material, sulphur/polyethylene glycol/polypyrrole is an active material, and sulphur, carbon mass ratio are 1: 1 in the active material.The mass ratio of aligned carbon nanotube and active material is 1: 0.1.
Embodiment 4: utilize the chemical vapor deposition processes that swims to prepare aligned carbon nanotube film, the thickness of film is 500 microns, CNT caliber 50 nanometers.This aligned carbon nanotube is placed chloroformic solution; Add the chloroform monomer and pass through the ferric trichloride initiated polymerization; Take out aligned carbon nanotube and obtain aligned carbon nanotube/polythiophene compound, add sublimed sulfur powder and PEO powder, be heated to 150 ℃ of ducts that make sulphur and PEO get into aligned carbon nanotube under the vacuum; Formation is skeleton with the aligned carbon nanotube, and polythiophene, PEO, sulphur are the positive electrode of active material.The mass ratio of sulphur and carbon is 1: 5 in this active material.The mass ratio of aligned carbon nanotube and active material is 1: 50.
Embodiment 5: utilize the chemical vapor deposition processes that swims to prepare aligned carbon nanotube film, the thickness of film is 60 microns, and the CNT caliber is 30 nanometers.This aligned carbon nanotube film is peeled off from silicon chip surface, and aligned carbon nanotube is flooded, remove dimethyl formamide, obtain aligned carbon nanotube/polyacrylonitrile compound through vacuumize with the dimethyl formamide solution of polyacrylonitrile.Sublimed sulfur is dissolved in the carbon disulfide, and aligned carbon nanotube/polyacrylonitrile compound is carried out load, stay aligned carbon nanotube after the carbon disulfide volatilization, polyacrylonitrile, the positive electrode that sulphur is formed.In the active material that wherein polyacrylonitrile and sulphur constitute, the mass ratio of sulphur and carbon is 1: 0.1; The mass ratio of aligned carbon nanotube and active material is 1: 3.This electrode material has the initial electrochemistry capacitance of 759mAh/g in electro-chemical test, and after 100 circulations, keeps the capacity of 653mAh/g, presents higher specific capacity and more excellent cyclical stability.
Embodiment 6: utilize the chemical vapor deposition processes that swims to prepare aligned carbon nanotube film, the thickness of film is 2000 microns, and the CNT caliber is 50 nanometers.This aligned carbon nanotube film is peeled off from silicon chip surface, and aligned carbon nanotube is flooded, remove dimethyl formamide, obtain aligned carbon nanotube/PEO compound through vacuumize with the dimethyl formamide solution of PEO.Sublimed sulfur is dissolved in the carbon disulfide, and aligned carbon nanotube/PEO compound is carried out load, stay aligned carbon nanotube after the carbon disulfide volatilization, PEO, the positive electrode that sulphur is formed.In the active material that wherein PEO and sulphur constitute, the mass ratio of sulphur and carbon is 1: 0.05; The mass ratio of aligned carbon nanotube and active material is 1: 20.This electrode material has the initial electrochemistry capacitance of 935mAh/g in electro-chemical test, and after 100 circulations, keeps the capacity of 751mAh/g, presents higher specific capacity and more excellent cyclical stability.
Embodiment 7: utilize the thermal chemical vapor deposition process to prepare aligned carbon nanotube film, the thickness of film is 1 micron, and the CNT caliber is 3 nanometers.This aligned carbon nanotube film is peeled off from silicon chip surface, and aligned carbon nanotube is flooded, remove chloroform, obtain aligned carbon nanotube/polypyrrole compound through vacuumize with the chloroformic solution of polypyrrole.Sublimed sulfur is dissolved in the carbon disulfide, and aligned carbon nanotube/polypyrrole compound is carried out load, stay aligned carbon nanotube after the carbon disulfide volatilization, polypyrrole, the positive electrode that sulphur is formed.In the active material that wherein polypyrrole and sulphur constitute, the mass ratio of sulphur and carbon is 1: 0.01; The mass ratio of aligned carbon nanotube and active material is 1: 30.This electrode material has the initial electrochemistry capacitance of 837mAh/g in electro-chemical test, and after 100 circulations, keeps the capacity of 697mAh/g, presents higher specific capacity and more excellent cyclical stability.
Embodiment 8: utilize the chemical vapor deposition processes that swims to prepare aligned carbon nanotube film, the thickness of film is 150 microns, CNT caliber 80 nanometers.This aligned carbon nanotube is placed chloroformic solution; Add the chloroform monomer and pass through the ferric trichloride initiated polymerization; Take out aligned carbon nanotube and obtain aligned carbon nanotube/polythiophene compound, add sublimed sulfur powder and PEO powder, be heated to 150 ℃ of ducts that make sulphur and polyaniline get into aligned carbon nanotube under the vacuum; Formation is skeleton with the aligned carbon nanotube, and polythiophene, polyaniline, sulphur are the positive electrode of active material.The mass ratio of sulphur and carbon is 1: 2 in this active material.The mass ratio of aligned carbon nanotube and active material is 1: 5.
Embodiment 9: adopt the thermal chemical vapor deposition process to prepare aligned carbon nanotube at the silicon chip surface that is coated with catalyst, this carbon nano-tube film thickness is about 30 microns, and the CNT caliber is 10 nanometers.This aligned carbon nanotube film is peeled off from silicon chip surface; And with the sublimed sulfur powder 155 ℃ down altogether heat be compounded to form positive electrode.The mass ratio of aligned carbon nanotube and active material elemental sulfur is 1: 0.3.Then at surperficial spin coating polyaniline film, as the lithium-sulfur cell electrode material.
Embodiment 10: utilize and swim chemical vapor deposition processes at quartz plate surface preparation aligned carbon nanotube film, the thickness of film is 200 microns, and the CNT caliber is 20 nanometers in the aligned carbon nanotube.This aligned carbon nanotube film is separated from quartz surfaces, and carry out the electrochemical deposition of polyaniline as work electrode, the polyaniline for preparing is deposited in the aligned carbon nanotube.After the cleaning, and with the sublimed sulfur powder 155 ℃ down altogether heat be compounded to form positive electrode.In this active material, the mass ratio of carbon is 1: 0.08 in sulphur and the polymer, and the mass ratio of active material and aligned carbon nanotube is 1: 0.7.
Claims (4)
1. aligned carbon nanotube composite positive pole that is used for lithium-sulfur rechargeable battery; It is characterized in that this material composition as follows: skeleton is an aligned carbon nanotube film; Be compounded with active electrode material therebetween, the mass ratio of aligned carbon nanotube and active material is 1: 0.1～50; Said active material is elemental sulfur or polymer and sulphur composite material.
2. according to the aligned carbon nanotube composite positive pole of the described a kind of lithium-sulfur rechargeable battery of claim 1; It is characterized in that: said aligned carbon nanotube is the approximate forming array shape macroscopic body that is arranged in parallel of CNT; Its thickness is between 1～2000 micron, and the CNT caliber that constitutes aligned carbon nanotube is between 1～100 nanometer.
3. according to the aligned carbon nanotube composite positive pole of claim 1 or 2 described a kind of lithium-sulfur rechargeable batteries, it is characterized in that: polymer is one or more in polyaniline, polyacrylonitrile, polypyrrole, polythiophene, PEO and the polyethylene glycol in said polymer and the sulphur composite material.
4. according to the aligned carbon nanotube composite positive pole of the described a kind of lithium-sulfur rechargeable battery of claim 3, it is characterized in that: in the said electrode material, in the active material in sulphur and the polymer mass ratio of carbon be 1: 0～5.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474619A (en) * | 2013-08-20 | 2013-12-25 | 东南大学 | Carbon nanotube bundle based flexible lithium sulphur battery electrode as well as preparation method and application thereof |
| CN104078652A (en) * | 2014-05-23 | 2014-10-01 | 南京中储新能源有限公司 | Carbon nano tube sulfur anode and secondary aluminium cell with same as anode material |
| CN104157878A (en) * | 2014-08-22 | 2014-11-19 | 南京中储新能源有限公司 | Carbon nanotube array-nano polyaniline-sulfur composite positive electrode, and preparation method and application thereof |
| CN104201356A (en) * | 2014-09-09 | 2014-12-10 | 南京中储新能源有限公司 | Carbon nanotube array-polypyrrole-sulfur composite material |
| CN104201355A (en) * | 2014-09-05 | 2014-12-10 | 南京中储新能源有限公司 | Conductive polymer coated carbon-sulfur composite positive electrode, preparation method thereof and secondary battery |
| CN104218230A (en) * | 2014-09-24 | 2014-12-17 | 南京中储新能源有限公司 | Carbon nano tube sponge conducting polymer composite cathode for secondary battery |
| TWI511359B (en) * | 2013-10-17 | 2015-12-01 | Hon Hai Prec Ind Co Ltd | Lithium ion battery active material and method for making the same |
| CN106058151A (en) * | 2016-08-12 | 2016-10-26 | 深圳博磊达新能源科技有限公司 | Carbon nanotube/nano sulfur/polyaniline composite electrode, and preparation method and application thereof |
| CN106711427A (en) * | 2017-02-22 | 2017-05-24 | 清华大学深圳研究生院 | Anode material for lithium sulfur battery and using method thereof |
| CN110556509A (en) * | 2019-08-14 | 2019-12-10 | 南京大学 | Method for performing surface protection and passivation treatment on metallic lithium cathode by using fluorine-containing organic matter, product and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040131937A1 (en) * | 2003-01-06 | 2004-07-08 | Ga-Lane Chen | Lithium ion battery comprising nanomaterials |
| CN101562244A (en) * | 2009-06-02 | 2009-10-21 | 北京理工大学 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
| 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 |
| CN102263221A (en) * | 2011-06-23 | 2011-11-30 | 复旦大学 | Oriented CNT (carbon nano tube)/polymer composite membrane as well as preparing method and application thereof |
-
2012
- 2012-02-27 CN CN201210046593.6A patent/CN102593433B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040131937A1 (en) * | 2003-01-06 | 2004-07-08 | Ga-Lane Chen | Lithium ion battery comprising nanomaterials |
| CN101562244A (en) * | 2009-06-02 | 2009-10-21 | 北京理工大学 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
| CN102263221A (en) * | 2011-06-23 | 2011-11-30 | 复旦大学 | Oriented CNT (carbon nano tube)/polymer composite membrane as well as preparing method and application thereof |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of power sources》 20071011 Hao Zhang et al "Electrochemical properties of ultra-long，aligned，carbon nanotube array electrode in organic electrolyte" 第477页左栏第2段至第右栏第1段，第478页左栏第2段 1-4 第 172卷, 第1期 * |
| HAO ZHANG ET AL: ""Electrochemical properties of ultra-long，aligned，carbon nanotube array electrode in organic electrolyte"", 《JOURNAL OF POWER SOURCES》, vol. 172, no. 1, 11 October 2007 (2007-10-11) * |
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| CN103474619A (en) * | 2013-08-20 | 2013-12-25 | 东南大学 | Carbon nanotube bundle based flexible lithium sulphur battery electrode as well as preparation method and application thereof |
| CN103474619B (en) * | 2013-08-20 | 2015-10-07 | 东南大学 | A kind of flexible lithium sulphur battery electrode based on carbon tube bank and preparation method thereof and application |
| TWI511359B (en) * | 2013-10-17 | 2015-12-01 | Hon Hai Prec Ind Co Ltd | Lithium ion battery active material and method for making the same |
| US9240589B2 (en) | 2013-10-17 | 2016-01-19 | Tsinghua University | Electrode active material of lithium ion battery and method for making the same |
| CN104078652A (en) * | 2014-05-23 | 2014-10-01 | 南京中储新能源有限公司 | Carbon nano tube sulfur anode and secondary aluminium cell with same as anode material |
| CN104157878A (en) * | 2014-08-22 | 2014-11-19 | 南京中储新能源有限公司 | Carbon nanotube array-nano polyaniline-sulfur composite positive electrode, and preparation method and application thereof |
| CN104201355A (en) * | 2014-09-05 | 2014-12-10 | 南京中储新能源有限公司 | Conductive polymer coated carbon-sulfur composite positive electrode, preparation method thereof and secondary battery |
| CN104201356A (en) * | 2014-09-09 | 2014-12-10 | 南京中储新能源有限公司 | Carbon nanotube array-polypyrrole-sulfur composite material |
| CN104218230A (en) * | 2014-09-24 | 2014-12-17 | 南京中储新能源有限公司 | Carbon nano tube sponge conducting polymer composite cathode for secondary battery |
| CN106058151A (en) * | 2016-08-12 | 2016-10-26 | 深圳博磊达新能源科技有限公司 | Carbon nanotube/nano sulfur/polyaniline composite electrode, and preparation method and application thereof |
| CN106711427A (en) * | 2017-02-22 | 2017-05-24 | 清华大学深圳研究生院 | Anode material for lithium sulfur battery and using method thereof |
| CN110556509A (en) * | 2019-08-14 | 2019-12-10 | 南京大学 | Method for performing surface protection and passivation treatment on metallic lithium cathode by using fluorine-containing organic matter, product and application |
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