CN106299282A - Nitrogen-doped carbon nanotube sulfur composite material and preparation method thereof - Google Patents
Nitrogen-doped carbon nanotube sulfur composite material and preparation method thereof Download PDFInfo
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- CN106299282A CN106299282A CN201610798267.9A CN201610798267A CN106299282A CN 106299282 A CN106299282 A CN 106299282A CN 201610798267 A CN201610798267 A CN 201610798267A CN 106299282 A CN106299282 A CN 106299282A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011593 sulfur Substances 0.000 title claims abstract description 44
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 3
- 239000003792 electrolyte Substances 0.000 abstract 2
- 238000007599 discharging Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a nitrogen-doped carbon nanotube sulfur composite material and a preparation method thereof. The method comprises the steps of acidizing the carbon nano tube, and carrying out polymerization reaction with amines to obtain a dark green precursor; placing the precursor in a tube furnace, and treating the precursor in a nitrogen atmosphere to obtain a nitrogen-doped carbon nanotube; and carrying out ball milling and mixing treatment on the nitrogen-doped carbon nanotube and sulfur according to the mass ratio of 1: 10-3: 7 to obtain the nitrogen-doped carbon nanotube-sulfur composite material. The nitrogen-doped carbon nanotube sulfur composite material prepared by the method of the invention shows better performance when being used in a lithium sulfur battery: the nitrogen doping can play a certain role in catalyzing and adsorbing the fracture and generation of S-S bonds in the charging and discharging processes, and reduces the dissolution of intermediate products in electrolyte, so that the electrolyte has better multiplying power and cycle performance.
Description
Technical field
The invention belongs to anode material of lithium battery field, specifically a kind of nitrogen-doped carbon nanometer pipe sulfur composite and preparation
Method.
Background technology
Along with the fast development of economy and improving constantly of human living standard, energy problem and environmental problem are increasingly drawn
Playing the attention of people, development Renewable resource and green energy resource have become as problem demanding prompt solution.Secondary cell is at new forms of energy
Exploitation in play indispensable role.And along with the fast development of various portable electric appts, the mankind couple
The energy density of battery proposes new requirement.Therefore develop various novel high specific energy batteries and become the task of top priority.
Positive electrode current material is to compete the fiercest and that market capacity is maximum territory in lithium ion battery market.Positive electrode
Expensive, this is the immediate cause of limiting lithium ion cell range of application.Lithium ion anode material is broadly divided into stratiform at present
The LiMO of structure2LiMn2O4 (the LiMn of (M=Co, Ni, Mn), spinel structure2O4), ternary metal composite oxide positive pole material
Material (such as LiFePO4, manganio richness lithium material).LiCoO at present2Positive electrode commercialization, but exist poor heat stability,
Shortcomings such as anti-over-charging ability, and Elements C o belongs to rare element, price comparison high, and metal Co can cause environmental pollution
And human body is had a certain impact；And the LiNiO of stratified material2There is the shortcoming that preparation is harsher；By contrast, point is brilliant
The advantages such as it is good that the LiMn2O4 of stone structure has safety, and voltage is high, low cost, environmental protection, but it is poor to there is high-temperature behavior, should not store
Etc. shortcoming.As relatively low due to its electronic conductance and ionic conductance all ratios in LiFePO4, have a strong impact on LiFePO4 at power current
Application in pond.In novel electrochemical energy storage system, lithium-sulfur cell is with elemental sulfur as positive electrode, and lithium metal is negative pole,
Theoretical specific energy is up to 2600Wh/kg, is the battery system that the energy density in addition to lithium-air battery generally acknowledged at present is the highest.
The running voltage of lithium-sulfur cell is 2.1V, adapts with the voltage range of the current various market demands, is having most of generally acknowledging at present
One of secondary cell system of development prospect.
There is a lot of problem directly as positive electrode in sulfur simple substance: electronic conductance and the ionic conductance of elemental sulfur are the lowest；
Before and after discharge and recharge, the change in volume of reactant and product is bigger, causes positive electrode efflorescence in charge and discharge process, activity
Material comes off；" effect of shuttling back and forth " that the polysulfide of the solubility produced in charge and discharge process is caused.
Summary of the invention
It is an object of the invention to the defect overcoming prior art to exist, it is provided that a kind of nitrogen-doped carbon nanometer pipe sulfur composite wood
Material and preparation method.The method is effectively doped with the nitrogen element of 1～4% in CNT, improves carbon nano tube surface
Reactivity site, significantly improve circulation and the high rate performance of CNT sulfur composite.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of nitrogen-doped carbon nanometer pipe sulfur composite, it is characterised in that it is by nitrogen-doped carbon nanometer pipe skeleton and attached
The sulfur composition in nitrogen-doped carbon nanometer pipe surface or inside, wherein nitrogen element mass percent is 1～4%；The quality hundred of sulfur
Proportion by subtraction is 60～92%.
Another object of the present invention is to provide the preparation method of a kind of nitrogen-doped carbon nanometer pipe sulfur composite, bag
Include following steps:
(1) CNT is mixed by the mass ratio of 1:20～100 with concentrated hydrochloric acid, be placed in stir process on magnetic stirring apparatus
1-6h, is placed in 45～90 DEG C of baking ovens process 18～24h, obtains the CNT of sense dough；
(2) according to the mass ratio addition official energy CNT of dough, amine and catalyst Ammonium persulfate., the stirring of 1:1-7
Uniformly, be placed in thermostat water bath, react at 40～80 DEG C be changed into solution colour blackish green；After reaction terminates, filter
Washing and drying is also ground, and obtains bottle green presoma；
(3) bottle green presoma is placed in tube furnace, processes 2～4h in a nitrogen atmosphere at 700～900 DEG C, obtain
Nitrogen-doped carbon nanometer pipe；
(4) according to the ratio of 1:10～3:7, nitrogen-doped carbon nanometer pipe is carried out ball milling with sulfur to mix, and at 150～160 DEG C
Process 4～8h, obtain nitrogen-doped carbon nanometer pipe sulfur composite.
Preferably, the raw material carbon nanotube diameter that described step (1) is used 5～100nm, specific surface area 50～
300m2/g。
Preferably, at least one during described step (2) amine substance is aniline, a diphenylamines.
Preferably, described step (3) nitrogen-doped carbon nanometer pipe caliber is 5～100nm, and specific surface area is 100～400m2/
g。
Preferably, described step (2) catalyst Ammonium persulfate. addition is 7～14 times of carbon nanotubes.
Preferably, described step (4) sulfur is for Sublimed Sulfur, and purity is more than 99.5%.
Preferably, described step (2) catalyst Ammonium persulfate. addition is 7～14 times of carbon nanotubes.
Beneficial effects of the present invention: the nitrogen-doped carbon nanometer pipe sulfur composite that the present invention obtains has higher specific capacity
And cycle performance.This kind of method is effectively doped with the nitrogen-atoms of 1～4% in CNT, improves carbon nano tube surface
Reactivity site, significantly improve circulation and high rate performance.
Accompanying drawing explanation
Fig. 1 is the SEM of the nitrogen-doped carbon nanometer pipe of the embodiment of the present invention 1 preparation.
Fig. 2 is the TEM of the nitrogen-doped carbon nanometer pipe of the embodiment of the present invention 1 preparation.
Fig. 3 is the high rate performance figure of the nitrogen-doped carbon nanometer pipe sulfur composite of the embodiment of the present invention 1 preparation.
Fig. 4 is the cycle performance figure of the nitrogen-doped carbon nanometer pipe sulfur composite of the embodiment of the present invention 1 preparation.
Detailed description of the invention
With specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1
CNT, concentrated hydrochloric acid are mixed with the mass ratio of 1:20, is placed in stir process 2h on magnetic stirring apparatus, is placed in 80
DEG C baking oven processes 24h, obtains the CNT of sense dough；
The mass ratio addition official energy CNT of dough, a diphenylamines and catalyst Ammonium persulfate., persulfuric acid according to 1:7
Ammonium addition is 7 times of carbon nanotubes, stirs, and is placed in thermostat water bath, reacts to solution colour at 60 DEG C
It is changed into blackish green；After reaction terminates, filtration washing is dried and is ground, and obtains bottle green presoma；
Bottle green presoma is placed in tube furnace, processes 2h in a nitrogen atmosphere at 900 DEG C, obtain nitrogen-doped carbon nanometer
Pipe；
According to the mass ratio of 3:7, nitrogen-doped carbon nanometer pipe is carried out ball milling with sulfur mix, and process 5h at 155 DEG C, obtain
Nitrogen-doped carbon nanometer pipe sulfur composite (NCNT-S).
Comparative example 1
According to the mass ratio of 3:7, CNT is carried out ball milling with sulfur mix, and process 5h at 155 DEG C, obtain carbon nanometer
Pipe sulfur composite (CNT-S).
Nitrogen-doped carbon nanometer pipe sulfur composite embodiment 1 prepared characterizes, and is assembled into 2016 type button electricity
Pond carries out electro-chemical test, and Fig. 1 is the SEM figure of nitrogen-doped nanometer pipe.Fig. 2 is the TEM of nitrogen-doped carbon nanometer pipe sulfur composite.
Can be seen that from a and have on the surface of carbon pipe one layer of color deep, for the clad stayed after polyaniline carbonization, can from b
To find out that the carbon layers having thicknesses stayed after carbon tube-surface polyaniline carbonization is at about 10nm.Fig. 3 is that nitrogen-doped carbon nanometer pipe sulfur is multiple
The high rate performance of condensation material, after the CNT after N doping is compound with sulfur, discharge capacity reaches 1100mAh/g first,
Under the electric current density of 2A/g, discharge capacity is 567mAh/g；What is more important is under the electric current density of 5A/g and 10A/g, electric
Still there is the capacity of 518mAh/g and 425mAh/g in pond, and this is that the CNT before doping is beyond one's reach result.Fig. 4 is comparative example
The cycle performance of composite before and after adulterating with embodiment 1, under the electric current density of 1A/g, after the activation that first five encloses, holds
Amount is respectively 797mAh/g, 835mAh/g, and after the circulation of 200 circles, capacity is respectively 471mAh/g, 608mAh/g, capacity
Conservation rate is respectively 60.5%, 78.7%；After the circulation of 400 circles, capability retention is 427mAh/g, 607mAh/g, holds
Amount conservation rate is 53.6%, 78.7%；After the circulation of 500 circles, capacity is respectively 401mAh/g, 599mAh/g, and capacity is protected
Holdup is respectively 41.1%, 66.4%, and after nitrating, its cycle performance is greatly improved.
Embodiment 2
CNT, concentrated hydrochloric acid are mixed with the ratio of 1:50, is placed in stir process 6h on magnetic stirring apparatus, is placed in 45 DEG C
Baking oven processes 20h, obtains the CNT of sense dough；
According to the ratio addition official energy CNT of dough, aniline and the catalyst Ammonium persulfate. of 1:1, Ammonium persulfate. adds
Amount is 7 times of carbon nanotubes, stirs, and is placed in thermostat water bath, reacts to solution colour and be changed at 40 DEG C
Blackish green；After reaction terminates, filtration washing is dried and is ground, and obtains bottle green presoma；
Bottle green presoma is placed in tube furnace, processes 4h in a nitrogen atmosphere at 700 DEG C, obtain nitrogen-doped carbon nanometer
Pipe；
According to the mass ratio of 3:7, nitrogen-doped carbon nanometer pipe is carried out ball milling with sulfur mix, and process 4h at 150 DEG C, obtain
Nitrogen-doped carbon nanometer pipe sulfur composite.
Embodiment 3
CNT, concentrated hydrochloric acid are mixed with the ratio of 1:100, is placed in stir process 1h on magnetic stirring apparatus, is placed in 90
DEG C baking oven processes 18h, obtains the CNT of sense dough；
According to the ratio addition official energy CNT of dough, aniline and the catalyst Ammonium persulfate. of 1:3, Ammonium persulfate. adds
Amount is 10 times of carbon nanotubes, stirs, and is placed in thermostat water bath, reacts to solution colour and be changed at 80 DEG C
Blackish green；After reaction terminates, filtration washing is dried and is ground, and obtains bottle green presoma；
Bottle green presoma is placed in tube furnace, processes 3h in a nitrogen atmosphere at 800 DEG C, obtain nitrogen-doped carbon nanometer
Pipe；
According to the mass ratio of 1:10, nitrogen-doped carbon nanometer pipe is carried out ball milling with sulfur mix, and process 8h at 160 DEG C, obtain
Nitrogen-doped carbon nanometer pipe sulfur composite.
Above content is only citing made for the present invention and explanation, and affiliated those skilled in the art are to being retouched
The specific embodiment stated makes various amendment or supplements or use similar mode to substitute, without departing from the design of invention
Or surmount scope defined in the claims, protection scope of the present invention all should be belonged to.
Claims (7)
1. a nitrogen-doped carbon nanometer pipe sulfur composite, it is characterised in that it is by nitrogen-doped carbon nanometer pipe skeleton and attachment
Sulfur composition in nitrogen-doped carbon nanometer pipe surface or inside, wherein nitrogen element mass percent is 1～4%；The percent mass of sulfur
Ratio is 60～92%.
2. the preparation method of a nitrogen-doped carbon nanometer pipe sulfur composite, it is characterised in that comprise the following steps:
(1) CNT is mixed by the mass ratio of 1:20～100 with concentrated hydrochloric acid, be placed in stir process 1-on magnetic stirring apparatus
6h, is placed in 45～90 DEG C of baking ovens process 18～24h, obtains the CNT of sense dough；
(2) according to the mass ratio addition official energy CNT of dough, amine and the catalyst Ammonium persulfate. of 1:1-7, stir,
Be placed in thermostat water bath, react at 40～80 DEG C be changed into solution colour blackish green；After reaction terminates, filtration washing dries
Dry doubling grinds, and obtains bottle green presoma；
(3) bottle green presoma is placed in tube furnace, processes 2～4h in a nitrogen atmosphere at 700～900 DEG C, obtain nitrogen and mix
Miscellaneous CNT；
(4) according to the ratio of 1:10～3:7, nitrogen-doped carbon nanometer pipe is carried out ball milling with sulfur to mix, and 150～160 DEG C of process
4～8h, obtain nitrogen-doped carbon nanometer pipe sulfur composite.
The preparation method of nitrogen-doped carbon nanometer pipe sulfur composite the most according to claim 2, it is characterised in that described step
Suddenly the raw material carbon nanotube diameter that (1) is used is 5～100nm, and specific surface area is 50～300m2/g。
The preparation method of nitrogen-doped carbon nanometer pipe sulfur composite the most according to claim 2, it is characterised in that described step
Suddenly at least one during (2) amine substance is aniline, a diphenylamines.
The preparation method of nitrogen-doped carbon nanometer pipe sulfur composite the most according to claim 2, it is characterised in that described step
Suddenly (3) nitrogen-doped carbon nanometer pipe caliber is 5～100nm, and specific surface area is 100～400m2/g。
The preparation method of nitrogen-doped carbon nanometer pipe sulfur composite the most according to claim 2, it is characterised in that described step
Suddenly (2) catalyst Ammonium persulfate. addition is 7～14 times of carbon nanotubes.
The preparation method of nitrogen-doped carbon nanometer pipe sulfur composite the most according to claim 2, it is characterised in that described step
Suddenly (4) sulfur is for Sublimed Sulfur, and purity is more than 99.5%.
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| CN110729436A (en) * | 2018-07-17 | 2020-01-24 | 南京理工大学 | Heteroatom-doped carbon nanotube modified carbon fiber paper and preparation method and application thereof |
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| CN113675387A (en) * | 2021-07-15 | 2021-11-19 | 南京信息工程大学 | Sulfur-carbon composite material, preparation method and application thereof |
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| CN106876673A (en) * | 2017-03-10 | 2017-06-20 | 哈尔滨工业大学 | The method that one-step method prepares titanium dioxide and the double-deck core shell structure lithium sulfur battery anode material of cladding altogether of Graphene |
| CN106876673B (en) * | 2017-03-10 | 2019-06-11 | 哈尔滨工业大学 | The method that one-step method prepares the core-shell structure lithium sulfur battery anode material that titanium dioxide and graphene bilayer coat altogether |
| CN109921041A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of preparation and application of base metal N doping carbon nanotubes elctro-catalyst |
| CN109921041B (en) * | 2017-12-12 | 2021-10-08 | 中国科学院大连化学物理研究所 | Preparation and application of non-noble metal nitrogen-doped hollow carbon nanotube electrocatalyst |
| CN110729436A (en) * | 2018-07-17 | 2020-01-24 | 南京理工大学 | Heteroatom-doped carbon nanotube modified carbon fiber paper and preparation method and application thereof |
| CN110729436B (en) * | 2018-07-17 | 2022-10-28 | 南京理工大学 | Heteroatom-doped carbon nanotube modified carbon fiber paper and preparation method and application thereof |
| CN110858644B (en) * | 2018-08-24 | 2021-04-02 | 清华大学 | Positive electrode, method for producing same, and battery using same |
| CN110858651B (en) * | 2018-08-24 | 2021-04-02 | 清华大学 | Carbon nanotube composite structure and preparation method thereof |
| US11111147B2 (en) | 2018-08-24 | 2021-09-07 | Tsinghua University | Carbon nanotube composite structure and method for making the same |
| CN110858651A (en) * | 2018-08-24 | 2020-03-03 | 清华大学 | Carbon nanotube composite structure and preparation method thereof |
| CN110858644A (en) * | 2018-08-24 | 2020-03-03 | 清华大学 | Positive electrode, method for producing same, and battery using same |
| CN111362254A (en) * | 2020-03-17 | 2020-07-03 | 广西师范大学 | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material |
| CN111362254B (en) * | 2020-03-17 | 2022-07-05 | 广西师范大学 | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material |
| CN111675208A (en) * | 2020-06-08 | 2020-09-18 | 齐鲁工业大学 | Sulfur-nitrogen doped hollow carbon nanotube composite material and preparation method and application thereof |
| CN111675208B (en) * | 2020-06-08 | 2023-02-03 | 齐鲁工业大学 | Sulfur-nitrogen doped hollow carbon nanotube composite material and preparation method and application thereof |
| CN113675387A (en) * | 2021-07-15 | 2021-11-19 | 南京信息工程大学 | Sulfur-carbon composite material, preparation method and application thereof |
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