CN106356555B - The preparation method of the sulphur composite positive pole of the dual modification of carbon nano tube/conducting polymer - Google Patents
The preparation method of the sulphur composite positive pole of the dual modification of carbon nano tube/conducting polymer Download PDFInfo
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Abstract
The present invention relates to electrode material synthesis technical fields, specifically disclose a kind of preparation method of the composite sulfur positive electrode of the dual modification of carbon nano tube/conducting polymer of 3D structure, this method is with carbon nanotube, polyaniline and sulphur are substrate, pass through hydro-thermal method, liquid phase synthesizing method and heat treatment and etc., the sulphur composite positive pole with 3D structure is prepared, it is easy that the electrode material combines conducting polymer preparation, the advantages of chemical confinement and carbon nanotube 3D conductive network skeleton, effectively modifies sulphur, for having good cycle in lithium-sulfur cell, the advantages that high rate performance is good, in mobile communication and Portable digital product, electric car, the related fieldss such as energy storage device have broad application prospects.Entire process process is relatively simple, and reaction condition is more mild and environmental-friendly, is easy to industrialization large-scale production.
Description
Technical field
The invention belongs to electrode material synthesis technical fields, and in particular to a kind of long-life, height ratio capacity and have 3D
The preparation method of the sulphur composite positive pole of the dual modification of the carbon nano tube/conducting polymer of structure.
Background technique
With the rapid development of science and technology, people propose many requirements to mobile electronic device: safer, faster, electric
Tankage is bigger, stand-by time is longer.And conventional lithium ion battery positive electrode such as LiFePO4 (170mAh*g-1) etc., by
Further develop in lower theoretical specific capacity, limiting its.Lithium-sulfur cell is because having very high specific capacity
(1673mAh*g-1) and energy density (2600Wh*kg-1) extensive concern of people is caused, but be positive material with elemental sulfur
The lithium-sulfur cell of material also have the shortcomings that it is some hinder its commercialized paces, be in particular in the following aspects:
1. the insulating properties of elemental sulfur.Elemental sulfur is the insulator of electronics and ion at room temperature, and electronics at room temperature passes
Conductance is 5 × 10-30S*cm-1, ionic conductivity 10-15, cause lithium-sulfur cell internal resistance to increase, active material utilization is low.Cause
This needs to add a large amount of conductive agent (such as acetylene black, Ketjen black) when making electrode, has made the energy density of electrode system
It reduces.
2. the dissolution of polysulfides.Intermediate product polysulfide (the Li that electrochemical reaction generates2Sn, n > 4) and it is being electrolysed
It dissolved in liquid, diffuse to cathode of lithium and reacted therewith, cause " shuttle effect ".In addition, insulating properties insoluble matter Li2S and
Li2S2It is deposited on negative electrode material surface, the electrical contact of active material is caused to deteriorate, cyclical stability decline.
3. the volume change of active material.Elemental sulfur (2.07g/cm-3) and lithium sulfide (1.66g/cm-3) in charge and discharge
Density variation in journey causes about 76% volume change, leads to the destruction of electrode structure.
Therefore, how to hinder the rapid decay, raising cycle performance of battery, raising active material utilization of battery becomes
The emphasis of lithium-sulfur cell research.It wherein, is prepare sulfur-based composite anode material important using carbon material modifying and decorating sulphur anode
One of means.
Carbon material has many advantages, such as high conductivity, multidimensional structure, low in cost, is widely used in including that lithium-sulfur cell exists
Interior many energy fields.Such as Canadian Nazar et al. opens the beginning that meso-porous carbon material is applied to lithium-sulfur cell, it is first
First having synthesized specific surface area is 1976 (m2*g-1), 2.1 (cm of Kong Rongwei3*g-1) mesoporous material CMK-3, then pass through heat treatment
70% sulphur is filled in its duct, the results showed that CMK-3 meso-porous carbon material can be improved the electric conductivity of compound,
Promote the transmission of electronic and ionic, improve active material utilization, the initial discharge specific capacity of CMK-3/S carbon-sulfur compound is up to
1320mAh*g-1(referring to Ji X, Lee K T, Nazar L F.Nat.Mater., 2009,8,500-506.).But due to more
Hole carbon has open cellular structure, and sulphur is equally possible under prolonged charge and discharge electro ultrafiltration and escapes out carbon pores road；In addition,
Most carbon materials are all to lack stronger chemistry between the inactive apolar substance of chemical property and polar lithium sulfide
Active force can not effectively inhibit polysulfides to scatter and disappear in long-range charge and discharge cycles, and shuttle effect occurs.
It is also a kind of important modified method with polymer-modified sulphur composite material in addition to carbon material.Xiao et al. preparation
Then polyaniline pipe coats sulphur on its surface and carries out vulcanization reaction, scattering and disappearing for polysulfides is effectively inhibited, 0.1C's
Specific capacity is maintained at 837mAh*g after current density circulation 100 is enclosed-1(referring to L.Xiao, Y.Cao, J.Xiao, etc.,
Adv.Mater.2012,24,1176-1181.).Chen et al. is wrapped using conducting polymer PEDOT (3,4-rthylene dioxythiophene)
Sulphur nano particle is wrapped up in, in 400mA*g-1Current density under circulation 50 circle, keep 930mAh*g-1Specific capacity (referring to
H.Chen,W.Dong,J.Ge and etc.,Sci.Rep,2013,3,1910.)。
In conclusion single carbon material or polymer each comes with some shortcomings, it is unable to reach the ideal to sulphur
Modification.Therefore, common modification is carried out to sulphur present invention incorporates the advantage of the two, comprehensive carbon material and conducting polymer to change
Property, it solves the problems, such as that lithium-sulfur cell exists, achieves preferable battery performance.
Summary of the invention
It is an object of the invention to overcome existing sulphur positive electrode above shortcomings, one kind is provided and has excellent performance and has
Hope the preparation method of the sulphur combination electrode material of the dual modification of carbon material/conducting polymer of large-scale industrial production.The party
Method is prepared using carbon nanotube, polyaniline and sulphur as substrate by the methods of hydro-thermal method, room temperature liquid phase synthesizing method and heat treatment
High performance sulphur composite positive pole.Present invention technical solution used for the above purpose is specific as follows:
A kind of preparation method of the sulphur composite positive pole of the dual modification of carbon nano tube/conducting polymer of 3D structure, packet
Include following steps:
(1) preparation of amination carbon nanotube (E-CNT): carbon nanotube is distributed in the aqueous solution of ethylenediamine, by solution
It is heated to certain temperature heat preservation and carries out hydro-thermal reaction, be centrifugally separating to obtain amination carbon nanotube after the reaction was completed；
(2) preparation of carbon nanotube-sulfur compound (E-CNT/S): by amination carbon nanotube obtained by step (1) and five water sulphur
Sodium thiosulfate, polyvinylpyrrolidone, sulfuric acid mixing, are centrifugally separating to obtain E-CNT/S compound after stirring a period of time；
(3) preparation of carbon nanotube-sulphur (P@E-CNT/S) compound of polyaniline package: by E-CNT/ obtained by step (2)
S compound, aniline, hydrochloric acid and ammonium persulfate are distributed in deionized water, are centrifugally separating to obtain P@E- after stirring a period of time
CNT/S compound.
According to above scheme, in step (1) first by mass ratio be 1:1-4 ethylenediamine and carbon nanotube be added to from
In sub- water, uniform mixed solution, the guarantor of mixed solution hydro-thermal reaction are obtained with moderate-speed mixer 30-90min by magnetic stirring apparatus
Temperature is 60-120 DEG C, and the insulation reaction time is 2-6h.
According to above scheme, amination carbon nanotube is dispersed first in step (2) in deionized water, to add five water sulphur
Sodium thiosulfate, polyvinylpyrrolidone, sulfuric acid, mixed solution moderate-speed mixer reaction time 2-8h at normal temperature, wherein five water sulphur
Sodium thiosulfate, polyvinylpyrrolidone, sulfuric acid and ethylenediamine mass ratio be 11.7:0.1:2.5-7.5:1.
According to above scheme, E-CNT/S compound is add to deionized water by step (3) first, ultrasonic disperse 30-
90min, then sequentially adds aniline, hydrochloric acid, ammonium persulfate, room temperature moderate-speed mixer mixing 6-18h, wherein aniline, hydrochloric acid, over cure
The mass ratio of sour ammonium and ethylenediamine is 1.22:0.8-4.8:2:1.
According to above scheme, revolving speed when centrifuge separation is that 5000-8000 turns/min, product deionized water and anhydrous second
Alcohol washing, temperature when vacuum drying are 40-80 DEG C, drying time 12-36h, and used hydrochloric acid mass concentration is 37%,
Used h 2 so 4 concentration is 98%.
Sulphur composite positive pole provided by the invention is uniformly interspersed in nano-sulfur by the carbon nanotube Jing Guo amination treatment
In grain, the structure (E-CNT/S) of similar armored concrete is formed.Pretreated amination carbon nanotube is in addition to that can improve compound
Electric conductivity also has numerous functional groups, these functional groups can generate chemical interactions between polysulfides, and reduction is filled
Active material scatters and disappears in discharge process.Again in one layer of conductive polymer polyanaline of E-CNT/S external sheath, at heat of vulcanization
Strong chemical interactions are generated after reason, between polyaniline and elemental sulfur, can be further reduced scattering and disappearing for polysulfides,
And then the stability of composite positive pole microstructure is protected, promote the long-range cycle performance of electrode.
The invention has the benefit that process flow is relatively simple, reaction condition is mild, environmental-friendly, it is easy to industrialize
Large-scale production has energy density height, follows when the sulphur composite positive pole prepared using this method is used for lithium-sulfur cell
The advantages that ring performance is good, high rate performance is good, in mobile communication neck related to Portable digital product, electric car, energy storage device etc.
Domain has broad application prospects.
Detailed description of the invention
Fig. 1 is the scanning electron microscopic picture of each intermediate material in 3 preparation process of the embodiment of the present invention, a E-CNT, b E-
CNT/S, C are P@E-CNT/S.
Fig. 2 is P@E-CNT/S composite material X-ray diffractogram prepared by the embodiment of the present invention 3.
Fig. 3 is that the single electric current of the lithium sulfur battery anode material of the preparation of the embodiment of the present invention 3 at room temperature recycles figure.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment and attached drawing carry out further.Following embodiment is merely to illustrate, and is not constituted a limitation of the invention, on this basis
Any improvement carried out is fallen within the scope of protection of the present invention.
Embodiment 1
0.1g ethylenediamine and 0.1g carbon nanotube are added first in 100mL deionized water, passes through electromagnetic agitation for the first step
Then uniformly mixed solution is fitted into hydrothermal reaction kettle by device moderate-speed mixer mixing 30min, setting drying box reaction condition is
60 DEG C, heating time is to be reacted for 2 hours.After reaction, by product deionized water and dehydrated alcohol centrifuge washing
(5000 revs/min) three times, the sediment that centrifugation obtains is placed in a vacuum drying oven, 12 hours dry under conditions of 40 DEG C,
It obtains amination carbon nanotube (E-CNT), collects spare.
The resulting E-CNT of previous step is distributed in 200mL deionized water by second step, and it is thio to sequentially add five water of 1.17g
The sulfuric acid that sodium sulphate, 0.01g polyvinylpyrrolidone and 0.25g mass concentration are 98%, is stirred by magnetic stirrer middling speed
Mix mixing 2h.After reaction, three times by product deionized water and dehydrated alcohol centrifuge washing (5000 revs/min), it will be centrifuged
The sediment of acquisition is placed in vacuum oven, and dry 12h, obtains amination carbon nanotube/sulfur compound (E- under conditions of 40 DEG C
CNT/S), collect spare.
Above-mentioned E-CNT/S compound is added in 100mL deionized water, ultrasonic disperse 30min by third step, is formed equal
Even solution.Then 0.122g aniline, 0.08g hydrochloric acid (hydrochloric acid mass concentration is 37%) and 0.2g are sequentially added into solution
Ammonium persulfate is mixed 6 hours by magnetic stirrer moderate-speed mixer.After reaction, by product deionized water and anhydrous second
Alcohol centrifuge washing (5000 revs/min) is placed in vacuum oven three times, by the sediment that centrifugation obtains, dry under conditions of 40 DEG C
12 hours amination carbon nanotube/sulfur compounds (P@E-CNT/S) to get polyaniline-coated.
For the carbon nanotube-sulfur compound performance for understanding polyaniline package prepared by embodiment 1, we are made into lithium
Sulphur battery has simultaneously carried out dependence test.First P@E-CNT/S compound, acetylene black and Kynoar according to mass ratio 75:
The proportion of 15:10 is mixed, then suitable N-Methyl pyrrolidone (NMP) is added dropwise thereto, is then mixed, is stirred
Mixing the time is 2 hours.The slurry stirred evenly is coated on aluminium foil, aluminium foil progress vacuum drying treatment is obtained into anode electrode
Piece.Vacuum drying absolute vacuum degree is 100Pa, and 60 DEG C of drying temperature, drying time is 12 hours.Using lithium metal as cathode
Piece, polypropylene porous film are battery diaphragm, and electrolyte prescription is that double trifluoromethanesulfonimide lithiums (LiTFSI) of 1mol/L are molten
Solution is in the mixed solution of 1,3- dioxolane (DOL) and glycol dimethyl ether (DME) (volume ratio 1:1), then adds
Lithium nitrate (the LiNO of 0.1mol/L3), 2025 type button cells are assembled into the glove box of argon atmosphere, then carry out electrochemistry
Performance test (test voltage section is 1.4-2.8V).
Embodiment 2
0.1g ethylenediamine and 0.25g carbon nanotube are added first in 100mL deionized water, is stirred by electromagnetism for the first step
Device moderate-speed mixer mixing 60min is mixed, then uniformly mixed solution is fitted into hydrothermal reaction kettle, drying box reaction condition is set
It is 90 DEG C, heating time is to be reacted for 4 hours.After reaction, by product deionized water and dehydrated alcohol centrifuge washing
(6000 revs/min) three times, the sediment that centrifugation obtains is placed in a vacuum drying oven, 24 hours dry under conditions of 60 DEG C,
It obtains amination carbon nanotube (E-CNT), collects spare.
The resulting E-CNT of previous step is distributed in 200mL deionized water by second step, and it is thio to sequentially add five water of 1.17g
The sulfuric acid that sodium sulphate, 0.01g polyvinylpyrrolidone and 0.5g mass concentration are 98%, passes through magnetic stirrer moderate-speed mixer
Mix 6h.After reaction, three times by product deionized water and dehydrated alcohol centrifuge washing (6000 revs/min), centrifugation is obtained
The sediment taken is placed in vacuum oven, and drying for 24 hours, obtains amination carbon nanotube/sulfur compound (E- under conditions of 60 DEG C
CNT/S), collect spare.
Above-mentioned E-CNT/S compound is added in 100mL deionized water, ultrasonic disperse 60min by third step, is formed equal
Even solution.Then 0.122g aniline, 0.2g hydrochloric acid (hydrochloric acid mass concentration is 37%) and 0.2g are sequentially added into solution
Ammonium persulfate is mixed 10 hours by magnetic stirrer moderate-speed mixer.After reaction, by product deionized water and anhydrous second
Alcohol centrifuge washing (6000 revs/min) is placed in vacuum oven three times, by the sediment that centrifugation obtains, dry under conditions of 60 DEG C
24 hours amination carbon nanotube/sulfur compounds (P@E-CNT/S) to get polyaniline-coated.
The production of lithium-sulfur cell: P@E-CNT/S compound, acetylene black and Kynoar according to mass ratio 75:15:10
Proportion mixed, then suitable N-Methyl pyrrolidone (NMP) is added dropwise into solution, is then mixed, stirred
Time is 2 hours.The slurry stirred evenly is coated on aluminium foil, aluminium foil progress vacuum drying treatment is obtained into anode electrode
Piece.Vacuum drying absolute vacuum degree is 100Pa, and 60 DEG C of drying temperature, drying time is 12 hours.Using lithium metal as cathode
Piece, polypropylene porous film are battery diaphragm, and electrolyte prescription is that double trifluoromethanesulfonimide lithiums (LiTFSI) of 1mol/L are molten
Solution is in the mixed solution of 1,3- dioxolane (DOL) and glycol dimethyl ether (DME) (volume ratio 1:1), then adds 0.1mol/
Lithium nitrate (the LiNO of L3), 2025 type button cells are assembled into the glove box of argon atmosphere, then carry out chemical property survey
Examination (test voltage section is 1.4-2.8V).
Embodiment 3
0.1g ethylenediamine and 0.4g carbon nanotube are added first in 100mL deionized water, passes through electromagnetic agitation for the first step
Then uniformly mixed solution is fitted into hydrothermal reaction kettle by device moderate-speed mixer mixing 90min, setting drying box reaction condition is
120 DEG C, heating time is that 6h is reacted.After reaction, by product deionized water and dehydrated alcohol centrifuge washing (8000
Rev/min) three times, the sediment that centrifugation obtains is placed in a vacuum drying oven, it is 36 hours dry under conditions of 80 DEG C, obtain amine
Carbon nano tube (E-CNT) is collected spare.
The resulting E-CNT of previous step is distributed in 200mL deionized water by second step, and it is thio to sequentially add five water of 1.17g
The sulfuric acid that sodium sulphate, 0.01g polyvinylpyrrolidone and 0.75g mass concentration are 98%, is stirred by magnetic stirrer middling speed
Mix mixing 8h.After reaction, three times by product deionized water and dehydrated alcohol centrifuge washing (8000 revs/min), it will be centrifuged
The sediment of acquisition is placed in vacuum oven, and dry 36h, obtains amination carbon nanotube/sulfur compound (E- under conditions of 80 DEG C
CNT/S), collect spare.
Above-mentioned E-CNT/S compound is added in 100mL deionized water, ultrasonic disperse 90min by third step, is formed equal
Even solution.Then 0.122g aniline, 0.48g hydrochloric acid (hydrochloric acid mass concentration is 37%) and 0.2g are sequentially added into solution
Ammonium persulfate is mixed 15 hours by magnetic stirrer moderate-speed mixer.After reaction, by product deionized water and anhydrous second
Alcohol centrifuge washing (8000 revs/min) is placed in vacuum oven three times, by the sediment that centrifugation obtains, dry under conditions of 80 DEG C
36 hours amination carbon nanotube/sulfur compounds (P@E-CNT/S) to get polyaniline-coated.
The production of lithium-sulfur cell: P@E-CNT/S compound, acetylene black and Kynoar according to mass ratio 75:15:10
Proportion mixed, then suitable N-Methyl pyrrolidone (NMP) is added dropwise, is then mixed, mixing time is 2 small
When.The slurry stirred evenly is coated on aluminium foil, obtains anode electrode piece after carrying out vacuum drying treatment to aluminium foil.Vacuum is dry
Dry absolute vacuum degree is 100Pa, and 60 DEG C of drying temperature, drying time is 12 hours.Using lithium metal as negative electrode tab, polypropylene is more
Pore membrane is battery diaphragm, and electrolyte prescription is that double trifluoromethanesulfonimide lithiums (LiTFSI) of 1mol/L are dissolved in 1,3- dioxy
The mixed solution of pentane (DOL) and glycol dimethyl ether (DME) (volume ratio 1:1), then add the lithium nitrate of 0.1mol/L
(LiNO3), 2025 type button cells are assembled into the glove box of argon atmosphere, then carry out electrochemical property test (test electricity
It is 1.4-2.8V between pressure area).
The appearance structure characterization of SEM, TEM and XRD have been carried out to P@E-CNT/S composite material prepared by the method for the present invention
And the test of chemical property, while having further confirmed that by TGA the load sulfur content of composite material, below with embodiment 3
It is illustrated for test result.
Fig. 1 is the scanning electron microscope (SEM) photograph of each intermediate material in 3 preparation process of the embodiment of the present invention, and wherein 1-a is that amination carbon is received
Mitron, 1-b are carbon nanotube/sulphur composite construction, and 1-c is P@E-CNT/S composite material.From figure 1 it will be seen that by modification
Carbon nanotube is still good to maintain primary tubular structure, and tube wall becomes relative smooth；It such as schemes with compound rear formed of sulphur
The reinforced concrete structure of 1-b finally wraps up polyaniline and is further packaged into composite construction.Fig. 2 is P@E-CNT/S composite material
X-ray diffractogram, it can be seen that is mainly presented is the characteristic diffraction peak (JCPDS No.08-0247) of sulphur.Fig. 3 is P@E-
Current cycle figure of the CNT/S composite material as lithium sulfur battery anode material constant current charge-discharge at room temperature.In 0.2C (1C=
1673mAh*g-1) current density under, for the first time discharge capacity be 1273mAh*g-1, discharge capacity still has after charge and discharge 200 times
763mAh*g-1, coulombic efficiency is close to 100%.This illustrate the material be effectively combined conducting polymer and carbon nanotube for
The modification advantage of sulphur effectively inhibits scattering and disappearing for polysulfides, has stable cycle performance.
Claims (3)
1. a kind of preparation method of the sulphur composite positive pole of the dual modification of carbon nano tube/conducting polymer of 3D structure, special
Sign is, comprising the following steps:
(1) preparation of amination carbon nanotube: carbon nanotube is distributed in the aqueous solution of ethylenediamine, and solution is heated to certain temperature
Degree heat preservation carries out hydro-thermal reaction, is centrifugally separating to obtain amination carbon nanotube after the reaction was completed；
(2) carbon nanotube-sulfur compound preparation: by amination carbon nanotube obtained by step (1) and five water sodium thiosulfate, poly- second
Alkene pyrrolidone, sulfuric acid mixing, are centrifugally separating to obtain carbon nanotube-sulfur compound after stirring a period of time；
(3) carbon nanotube-sulfur compound preparation of polyaniline package: by carbon nanotube-sulfur compound, benzene obtained by step (2)
Amine, hydrochloric acid and ammonium persulfate are distributed in deionized water, are centrifugally separating to obtain the carbon that polyaniline wraps up after stirring a period of time
Nanotube-sulfur compound；
Wherein, ethylenediamine and carbon nanotube that mass ratio is 1:1-4 are add to deionized water first in step (1), are passed through
Magnetic stirring apparatus obtains uniform mixed solution with moderate-speed mixer 30-90min, and the holding temperature of mixed solution hydro-thermal reaction is 60-
120 DEG C, the insulation reaction time is 2-6h；Amination carbon nanotube is dispersed first in step (2) in deionized water, to add five
Water sodium thiosulfate, polyvinylpyrrolidone, sulfuric acid, mixed solution moderate-speed mixer reaction time 2-8h at normal temperature, wherein five
Water sodium thiosulfate, polyvinylpyrrolidone, sulfuric acid and ethylenediamine mass ratio be 11.7:0.1:2.5-7.5:1.
2. the preparation method of sulphur composite positive pole as described in claim 1, it is characterised in that: step (3) first receives carbon
Mitron-sulfur compound is add to deionized water, then ultrasonic disperse 30-90min sequentially adds aniline, hydrochloric acid, persulfuric acid
Ammonium, room temperature moderate-speed mixer mixing 6-18h, wherein the mass ratio of aniline, hydrochloric acid, ammonium persulfate and ethylenediamine is 1.22:0.8-
4.8:2:1。
3. the preparation method of sulphur composite positive pole as described in claim 1, it is characterised in that: revolving speed when centrifuge separation is
5000-8000 turns/min, and product wash with deionized water and dehydrated alcohol, and temperature when vacuum drying is 40-80 DEG C, when drying
Between be 12-36h, used hydrochloric acid mass concentration be 37%, used h 2 so 4 concentration be 98%.
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| CN111092225B (en) * | 2019-11-25 | 2022-12-13 | 华东理工大学 | Self-supporting electrode of lithium-sulfur battery and preparation method thereof |
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| CN116873904A (en) * | 2023-07-10 | 2023-10-13 | 桂林理工大学 | Preparation method of integrated lithium-sulfur battery positive electrode material with coaxial cable structure |
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| CN101774573A (en) * | 2010-02-08 | 2010-07-14 | 哈尔滨工业大学 | Method for amination of carbon nano tube |
| 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 |
| CN104332597A (en) * | 2014-10-20 | 2015-02-04 | 北京化工大学 | Polyacid/polyaniline/carbon nano tube electrode material as well as preparation method and application thereof |
| CN104362316A (en) * | 2014-10-28 | 2015-02-18 | 华南师范大学 | Lithium-sulfur battery composite cathode material, and preparation method and application thereof |
| CN105129772A (en) * | 2015-09-18 | 2015-12-09 | 同济大学 | Method for preparing amination CNT (carbon nano tube)-graphene aerogel |
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| CN101774573A (en) * | 2010-02-08 | 2010-07-14 | 哈尔滨工业大学 | Method for amination of carbon nano tube |
| 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 |
| CN104332597A (en) * | 2014-10-20 | 2015-02-04 | 北京化工大学 | Polyacid/polyaniline/carbon nano tube electrode material as well as preparation method and application thereof |
| CN104362316A (en) * | 2014-10-28 | 2015-02-18 | 华南师范大学 | Lithium-sulfur battery composite cathode material, and preparation method and application thereof |
| CN105129772A (en) * | 2015-09-18 | 2015-12-09 | 同济大学 | Method for preparing amination CNT (carbon nano tube)-graphene aerogel |
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