CN105390687A - High-performance three-dimensional carbon nanotube composite negative electrode material, preparation method therefor and application thereof - Google Patents
High-performance three-dimensional carbon nanotube composite negative electrode material, preparation method therefor and application thereof Download PDFInfo
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- CN105390687A CN105390687A CN201510738181.2A CN201510738181A CN105390687A CN 105390687 A CN105390687 A CN 105390687A CN 201510738181 A CN201510738181 A CN 201510738181A CN 105390687 A CN105390687 A CN 105390687A
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Abstract
The invention discloses a preparation method for a high-performance three-dimensional carbon nanotube composite negative electrode material. The preparation method comprises: by taking a carboxylated carbon nanotube as a three-dimensional network framework and taking a high-capacity material subjected to layer by layer self-assembly and modification as an active substance, uniformly mixing the carbon nanotube with the active substance under the action of electrostatic attraction; and then performing in-situ coating by taking a mixed element-containing N or S-doped carbon source as a three-dimensional coating layer, and performing high-temperature treatment to obtain the high-performance three-dimensional carbon nanotube composite negative electrode material. The invention furthermore discloses the high-performance three-dimensional carbon nanotube composite negative electrode material and an application thereof. According to the preparation method, the cycle performance of the active substance is remarkably improved, and the capacity of the composite material can be controllably adjusted by controlling a ratio of the carbon nanotube to the active substance. In addition, a solvent used in the method is water, so that the method is environmentally-friendly, good in repeatability and low in cost, and has relatively high potential of large-scale application and good industrialized prospects.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, be specifically related to a kind of high performance three-dimensional carbon nano-tube composite negative pole material and its preparation method and application.
Background technology
Lithium ion battery has that open circuit voltage is high, energy density is large, long service life, memoryless effect, of low pollution and the advantage such as self-discharge rate is little, it is better than other traditional secondary battery on overall performance, is unanimously considered to various portable electric appts and ideal power supply used for electric vehicle.Although conventional lithium ion battery negative material graphite good cycling stability and cost performance higher, but because its charging and discharging capacity is lower, volume and capacity ratio does not have advantage especially, be difficult to meet dynamical system particularly electric motor car and hybrid electric vehicle to the requirement of cell high-capacity.Therefore exploitation have height ratio capacity, high charge-discharge efficiencies, long circulation life Novel cathode material for lithium ion battery have urgency.
In the research of novel non-carbon negative material, the pure metals such as silicon, tin, germanium, metal oxide and composite metal oxide material more and more attract attention because having the embedding lithium capacity of higher theory.If the negative material of these high power capacity can reach degree of being practical, the range of application of lithium ion battery will be made greatly to widen.But the most conductivity of negative material of these high power capacity is lower, and under high level removal lithium embedded condition, there is serious bulk effect, causes the cyclical stability of electrode poor.For the volume efficiency of the negative material of these high power capacity, by it with there is elasticity and the carrier compound of stable performance, the change in volume of buffering silicon, improves the effective way of its cyclical stability while of will being and keeping high power capacity.Carbon is owing to having lighter quality, and good conductivity, lower intercalation potential, in deintercalation process, change in volume is little and cheap etc., and plurality of advantages etc. is widely used in anode material.
Carbon nano-tube, owing to having higher mechanical strength, good conductivity, is once applied in electrode material widely.But due to the limitation that the theoretical capacity of material with carbon element own is lower, the electrode capacity prepared by independent carbon nano-tube is on the low side becomes the major obstacle of its development of restriction.By carbon nano-tube and the negative material phase compound with high theoretical capacity, in conjunction with both advantages, the lithium cell negative pole material with superior performance can be prepared.The people such as Zhou by nano-silicon and carbon nanotube dispersed in the solution of phenolic resins, by preparing electrode material after Pintsch process, the reversible capacity (J.AlloysCompd.2010,493 (1-2): 636-639.) of 711mAh/g can be kept after the circulation of 20, this electrode.The people such as Yue, by mixing nano silica fume and carbon nano-tube, utilize sodium carboxymethylcellulose as adhesive, and the dry after annealing of suction filtration is prepared from extrusion coating paper electrode.Carbonization due to sodium carboxymethylcellulose causes the deflation of structure, makes silicon nanoparticle be compressed in carbon nano tube structure, forms good contact with silicon, the effective expansion suppressing silicon volume.Still can keep the reversible capacity of 942mAh/g after prepared 30, compound electric paper circulation, under the electric current of 500mA/g, average reversible capacity still can reach 650mAh/g(Electrochim.Acta, 76,326 – 332,2012.).But the aspects such as the combination electrode capacity up to this point, utilizing the method for carbon nano-tube and the mixing of high power capacity active material to prepare and the improvement of cycle performance all can't be of great satisfaction.Trace it to its cause, key is: the 1) sex chromosome mosaicism that is uniformly dispersed of carbon nano-tube and high power capacity active material compound.In the method for common mixing, because the electrostatic attraction of composite material both sides is limited, active material can not be scattered in the spacial framework of carbon nano-tube uniformly, causes carbon nano-tube effectively can not improve the bulk effect of high power capacity active material; 2) effectively can not contact between carbon nano-tube and high power capacity active material, cause charge transfer efficiency lower.
Summary of the invention
Goal of the invention: first technical problem to be solved of the present invention there is provided a kind of preparation method of high performance three-dimensional carbon nano-tube composite negative pole material.
Second technical problem to be solved of the present invention there is provided a kind of high performance three-dimensional carbon nano-tube composite negative pole material.
3rd technical problem to be solved of the present invention there is provided a kind of high performance three-dimensional carbon nano-tube composite negative pole material and is preparing the application in combination electrode.
Technical scheme: in order to solve the problems of the technologies described above, the invention provides a kind of preparation method of high performance three-dimensional carbon nano-tube composite negative pole material, by using carboxylic carbon nano-tube as the network skeleton of three-dimensional, with the material of the modified high power capacity of LBL self-assembly for active material, by the effect of electrostatic attraction, carboxylic carbon nano-tube is mixed uniformly with active material, the carbon source of then being adulterated containing assorted element N or S by in-stiu coating prepares high performance three-dimensional carbon nano-tube composite negative pole material as three-dimensional bags coating via high-temperature process.
A preparation method for high performance three-dimensional carbon nano-tube composite negative pole material, specifically comprises the following steps:
1) carbon nano-tube is carried out carboxylated process;
2) be added to the water by carboxylic carbon nano-tube, ultrasonic disperse prepares carboxylic carbon nano-tube solution;
3) be added to the water by the material of high power capacity modified for LBL self-assembly, ultrasonic disperse, stirs and obtains mixed liquor;
4) step 2 poured into by dispersed mixed liquor step 3) obtained) carboxylic carbon nano-tube solution in, after stirring leave standstill, obtain the carboxylic carbon nano-tube/active material suspension-turbid liquid of lower floor after removing upper strata clear aqueous solution;
5) under condition of ice bath, in the carboxylic carbon nano-tube/active material suspension-turbid liquid of step 4), drip conducting polymer monomer, ultrasonic disperse, stir and obtain mixed solution;
6) mixed solution of step 5) is first stirred under ice bath, regulate pH value, then drip the aqueous solution containing oxidant, stir under ice bath and spend the night, obtain carboxylic carbon nano-tube/active material/polymer composites through suction filtration;
7) carboxylic carbon nano-tube/active material/polymer composites of step 6) high-temperature process under protection gas is prepared high performance three-dimensional carbon nano-tube composite negative pole material.
The carboxylated treatment step of described step 1) is: first remaining metal ion is removed in carbon nano-tube 80 DEG C of backflows in concentrated hydrochloric acid, be the concentrated sulfuric acid/salpeter solution 60 DEG C of ultrasonic 3h of 3/1 again by it use volume ratio, after being washed till neutral rear drying with a large amount of deionized water.
The step of described step 3) LBL self-assembly modification is: using anionic polyelectrolyte diallyl dimethyl ammoniumchloride (PDDA) and cationic polyelectrolyte kayexalate (PSS) as raw material, carry out layer assembly at the material surface of high power capacity, change the charge property of active material surface.
The material of described high power capacity is one or more in nano silica fume, germanium powder, glass putty; Or nano-oxide powder comprises one or more in tin ash, tungsten oxide, zinc oxide, indium oxide; Or nano composite metal oxide comprises one or more in zinc manganate, cobalt acid manganese, Manganese Ferrite powder.
Described carboxylic carbon nano-tube is the one in Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes.Be preferably cheap multi-walled carbon nano-tubes.
Described carboxylic carbon nano-tube and the mass ratio of active material are 1:5 ~ 1:10.
In described step 5), conducting polymer monomer is the one in aniline monomer, pyrrole monomer, thiophene monomer, the addition of described conducting polymer monomer is 0.5 ~ 2 times of the quality of active material, in step 6), the addition of oxidant is 2.4 ~ 5 times of the quality of polymer monomer, and oxidant is (NH
4)
2s
2o
8.
High-temperature process in described step 7) is: 500 ~ 800 DEG C are carried out in a vacuum or inert atmosphere, and inert atmosphere is Ar, Ar/H
2gaseous mixture or He.
The high performance three-dimensional carbon nano-tube composite negative pole material that above-mentioned preparation method prepares.
Above-mentioned high performance three-dimensional carbon nano-tube composite negative pole material is preparing the application in combination electrode.
Beneficial effect: the present invention improves obviously the cycle performance of active material, and can according to the capacity of ratio controllable adjustment composite material controlling carbon nano-tube and active material.In addition, solvent used in the present invention is water, environmental friendliness, and reproducible, with low cost, and have good scale application potential, industrial prospect is good.Raw materials of the present invention is cheap, and operating procedure is simple, and yield is high, and the charge-discharge performance of material is excellent, is convenient to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is preparation technology's schematic flow sheet of high performance three-dimensional carbon nano-tube composite negative pole material;
The electromicroscopic photograph of Fig. 2 sample prepared by embodiment 1 ~ 3.The TEM figure of a Si/C composite material that () prepares for carbonization after Si-polyaniline compound; (b/c) for scheming with TEM and SEM of carbon nano-tube compound after Si modified by nano particles; D SEM figure that () is obtained three dimensional carbon nanotubes Si base composite negative pole material; (e-h) be the TEM figure of obtained three dimensional carbon nanotubes Si base composite negative pole material; (i/j) be three dimensional carbon nanotubes SnO
2the TEM figure of base compound; (k/l) be three dimensional carbon nanotubes ZnFe
2o
4the TEM figure of base compound;
Fig. 3 (a) is Si, the cycle performance figure of Si and MWCNTS electrode material after oxidation processes; B cycle performance figure that () is Si/MWCNTS and Si/C combination electrode material; The cycle performance figure under 200mA/g and 400mA/g of c three dimensional carbon nanotubes Si base composite negative pole material that () obtains for embodiment 1; The high rate performance figure of d three dimensional carbon nanotubes Si base composite negative pole material that () obtains for embodiment 1;
Fig. 4 is that embodiment 2 obtains three dimensional carbon nanotubes SnO
2prepared by base composite negative pole material, electrode is at 400mAg
-1charging and discharging currents density under cycle performance test curve;
Fig. 5 is that embodiment 3 obtains three dimensional carbon nanotubes ZnFe
2o
4prepared by base composite negative pole material, electrode is at 400mAg
-1charging and discharging currents density under cycle performance test curve.
Embodiment
Further describe embodiment of the present invention below in conjunction with accompanying drawing, following examples are implemented under premised on technical solution of the present invention, give detailed execution mode and concrete operating process, but protection scope of the present invention are not limited to following embodiment.
Granularity is all adopted to be the active material of below 200nm in following examples, and in advance in concentrated hydrochloric acid 80 DEG C backflow and by volume ratio be subsequently 3/1 the concentrated sulfuric acid/salpeter solution 60 DEG C of ultrasonic 3h, (external diameter is 60-100nm to the carboxylation multi-walled carbon nano-tubes obtained after being washed till neutral rear drying with a large amount of deionized water, Nanjing pioneer's nanosecond science and technology company), the mean molecule quantity of PSS is 70000.And implement in accordance with the technological process shown in Fig. 1.
Embodiment 1
1) aqueous solution 200mL two parts of the NaCl of preparation containing 1wt.%PDDA and 0.2M, ultrasonic disperse makes it dispersed in 10 minutes; The aqueous solution 200mL of preparation 1wt.%PSS is a, and ultrasonic disperse makes it dispersed in 10 minutes; By the Si powder through surface oxidation treatment (particle diameter is 100 ~ 200nm) of 1g, successively through PDDA-PSS-PDDA process modification, filter, 70 DEG C of 2h vacuumizes, grinding after dry, mark is deposited;
2) the Si powder 0.1g getting above-mentioned modification is scattered in 200mL deionized water again, and ultrasonic disperse makes it dispersed in 2 hours;
3) add in 200mL deionized water by 0.02g carboxylic carbon nano-tube, ultrasonic disperse makes carboxylic carbon nano-tube dispersed in 2 hours;
4) when high-speed stirred, the Si powder solution getting above-mentioned modification pours the dispersion liquid of carboxylic carbon nano-tube into, continues stirring and leaves standstill after 2 hours, uses separatory funnel to take out the carboxylic carbon nano-tube/active material suspension-turbid liquid of lower floor, it is settled to 50mL;
5) aniline monomer getting 0.2mL is scattered in the deionized water of 40mL, ultrasonic agitation 1h in frozen water.By above-mentioned steps 4) carboxylic carbon nano-tube/active material Si suspension-turbid liquid add in above-mentioned aniline monomer dispersion liquid, stir 1 hour at condition of ice bath lower magnetic force.Then regulate the pH value of solution to be about 3 with concentrated hydrochloric acid, continue to stir 20min.Preparation 10mL is containing (NH
4)
2s
2o
8the aqueous solution of 0.75g, adds it in above-mentioned solution.Keep condition of ice bath, reaction 24h.By mixture suction filtration, spend deionized water 3 times, dry, grinding, under Ar gas, 800 DEG C of 3h sintering prepare three dimensional carbon nanotubes/Si composite negative pole material.The mass ratio of described carboxylic carbon nano-tube and active material Si is 1:5, and the addition of described aniline monomer is 2 times of the quality of active material Si, described oxidant (NH
4)
2s
2o
8addition be 3.7 times of the quality of aniline monomer.After fully being ground by material after sintering, and carbon black and carboxymethyl cellulose are according to the ratio of 60: 20: 20, and mix, after film, 60 DEG C of vacuumize 4h, prepare combination electrode.By electrode in 2025 battery cases, being to electrode with lithium sheet, take polyethylene film as barrier film, with 1MLiPF
6eC/DEC (v/v=1/1) carries out constant current charge-discharge test for electrolyte assembled battery.Test result is see experimental example.
Embodiment 2
1) aqueous solution 200mL two parts of the NaCl of preparation containing 1wt.%PDDA and 0.2M, ultrasonic disperse makes it dispersed in 10 minutes; The aqueous solution 200mL of preparation 1wt.%PSS is a, and ultrasonic disperse makes it dispersed in 10 minutes; By the sintered SnO of 1g
2nano particle (50nm), successively through PDDA-PSS-PDDA process modification, filters, 70 DEG C of 2h vacuumizes.Grinding after dry, mark is deposited;
2) SnO of above-mentioned modification is got
2nano particle 0.2g is scattered in 200mL deionized water again, and ultrasonic disperse makes it dispersed in 2 hours;
3) add in 200mL deionized water by 0.02g carboxylic carbon nano-tube, ultrasonic disperse makes carboxylic carbon nano-tube dispersed in 2 hours;
4) when high-speed stirred, the SnO of above-mentioned modification is got
2nanoparticles solution pours the dispersion liquid of carboxylation carbon nano-tube into, continues stirring and leaves standstill after 2 hours, uses separatory funnel to take out the carboxylic carbon nano-tube/active material suspension-turbid liquid of lower floor, it is settled to 50mL;
5) pyrrole monomer getting 0.1mL is scattered in the deionized water of 40mL, ultrasonic agitation 1h in frozen water.By above-mentioned steps 4) carboxylic carbon nano-tube/active material SnO
2suspension-turbid liquid adds in above-mentioned pyrrole monomer dispersion liquid, stirs 30 minutes at condition of ice bath lower magnetic force.Then regulate the pH value of solution to be about 3 with concentrated hydrochloric acid, continue to stir 20min.Preparation 10mL is containing (NH
4)
2s
2o
8the aqueous solution of 0.495g, adds it in above-mentioned solution.Keep condition of ice bath, react 24 hours.By mixture suction filtration, spend deionized water 3 times, dry, after grinding, under Ar gas, 600 DEG C of 5h sintering prepare three dimensional carbon nanotubes/SnO
2composite negative pole material.Described carboxylic carbon nano-tube and active material SnO
2mass ratio be 1:10, the addition of described pyrrole monomer is about active material SnO
20.5 times of quality, described oxidant (NH
4)
2s
2o
8addition be 5 times of the quality of pyrrole monomer.After fully being ground by material after sintering, and carbon black and carboxymethyl cellulose are according to the ratio of 60: 20: 20, and mix, after film, 60 DEG C of vacuumize 4h, prepare combination electrode.By electrode in 2025 battery cases, being to electrode with lithium sheet, take polyethylene film as barrier film, with 1MLiPF
6eC/DEC (v/v=1/1) carries out constant current charge-discharge test for electrolyte assembled battery.Test result is see experimental example.
Embodiment 3
1) aqueous solution 200mL two parts of the NaCl of preparation containing 1wt.%PDDA and 0.2M, ultrasonic disperse makes it dispersed in 10 minutes; The aqueous solution 200mL of preparation 1wt.%PSS is a, and ultrasonic disperse makes it dispersed in 10 minutes; By the sintered ZnFe of 1g
2o
4nano particle (about 50nm), successively through PDDA-PSS-PDDA process modification, filters, 70 DEG C of 2h vacuumizes.Grinding after dry, mark is deposited;
2) 0.1gZnFe of above-mentioned modification is got
2o
4nano particle is scattered in 200mL deionized water again, and ultrasonic disperse makes it dispersed in 2 hours;
3) add in 200mL deionized water by 0.01g carboxylic carbon nano-tube, ultrasonic disperse makes carboxylic carbon nano-tube dispersed in 2 hours;
4) when high-speed stirred, the 0.1gZnFe of above-mentioned modification is got
2o
4nanoparticles solution pours the dispersion liquid of carbon nano-tube into, continues stirring and leaves standstill after 2 hours, uses separatory funnel to take out the carbon nano-tube/active material suspension-turbid liquid of lower floor, it is settled to 50mL;
5) thiophene monomer getting 0.1mL is scattered in the deionized water of 40mL, ultrasonic agitation 1h in frozen water.By above-mentioned steps 4) carboxylic carbon nano-tube/active material ZnFe
2o
4suspension-turbid liquid adds in above-mentioned thiophene monomer dispersion liquid, stirs 1 hour at condition of ice bath lower magnetic force.Then regulate the pH value of solution to be about 3 with concentrated hydrochloric acid, continue to stir 20min.Preparation 10mL is containing (NH
4)
2s
2o
8the aqueous solution of 0.322g, adds it in above-mentioned solution.Keep condition of ice bath, react 24 hours.By mixture suction filtration, spend deionized water 3 times, dry, after grinding, under Ar gas, 500 DEG C of 3h sintering prepare three dimensional carbon nanotubes/ZnFe
2o
4composite negative pole material.Described carboxylic carbon nano-tube and active material ZnFe
2o
4mass ratio be 1:10, the addition of described thiophene monomer is active material ZnFe
2o
41.3 times of quality, described oxidant (NH
4)
2s
2o
8addition be 2.4 times of the quality of thiophene monomer.After fully being ground by material after sintering, and carbon black and carboxymethyl cellulose are according to the ratio of 60: 20: 20, and mix, after film, 60 DEG C of vacuumize 4h, prepare combination electrode.By electrode in 2025 battery cases, being to electrode with lithium sheet, take polyethylene film as barrier film, with 1MLiPF
6eC/DEC (v/v=1/1) carries out constant current charge-discharge test for electrolyte assembled battery.Test result is see experimental example.
Experimental example:
To the pattern of composite material and by cycle performance test below by SEM and TEM photo the chemical property of composite material prepared by the present invention is tested and characterized.
1, tem analysis
The TEM photo of Fig. 2 sample and associated sample prepared by the embodiment of the present invention 1 ~ 3.The TEM figure of the Si/C composite material that Fig. 2 (a) prepares for carbonization after Si-polyaniline compound, can find out that nano Si material has a unformed carbon-coating to exist on surface; (b/c) for scheming with TEM and SEM of carboxylic carbon nano-tube compound after Si modified by nano particles, can find out that Si nano particle is dispersed in the middle of carboxylic carbon nano-tube network uniformly; D SEM figure that () is obtained three dimensional carbon nanotubes Si base composite negative pole material, can find out the coated characteristic of carbon network that surface presentation is homogeneous; (e-h) be the TEM figure of obtained three dimensional carbon nanotubes Si base composite negative pole material, can be clear that from figure and be connected by carbon between Si nano particle and carboxylic carbon nano-tube, form three-dimensional network configuration.(i/j) be three dimensional carbon nanotubes SnO
2the TEM figure of base compound, can be clear that SnO from figure
2connected by carbon between nano particle and carboxylic carbon nano-tube, form three-dimensional network configuration; (k/l) be three dimensional carbon nanotubes ZnFe
2o
4the TEM figure of base compound, can be clear that ZnFe from figure
2o
4connected by carbon between nano particle and carboxylic carbon nano-tube, form three-dimensional network configuration.
2, cycle performance test
Fig. 3 (a) is Si, the cycle performance figure of Si and the MWCNTS electrode material of oxidation processes, compare MWCNTS as can be known from Figure, the Si electrode material of Si and oxidation processes all has higher initial capacity, but the cyclical stability of MWCNTS electrode is better, so silicon and carboxylic carbon nano-tube are combined, the high and combination electrode of good cycling stability of the capacity that likely prepares; B cycle performance figure that () is Si/MWCNTS and Si/C combination electrode material, compare the electrode with naked silicon, cyclical stability is improved; The c cycle performance figure of three dimensional carbon nanotubes Si base composite negative pole material under 200mA/g and 400mA/g that () obtains for embodiment 1, preparation-obtained combination electrode demonstrates good cyclical stability, after 100 circulations, still can keep 1141 and 1087mAhg respectively
-1discharge capacity; The high rate performance figure of d three dimensional carbon nanotubes Si base composite negative pole material that () obtains for embodiment 1, at 10000mAg
-1electric current under, still have an appointment 380mAhg
-1discharge capacity, be much better than the battery performance of conventional graphite negative pole.
Fig. 4 is three dimensional carbon nanotubes SnO prepared by embodiment 2
2base composite negative pole material cycle performance test curve, relative to the SnO be not wrapped by
2the electrode of material, the electrode after compound shows larger performance improvement, and after 100 circulations, discharge capacity is from 171mAhg
-1be improved to 971mAhg
-1.
Fig. 5 is three dimensional carbon nanotubes ZnFe prepared by embodiment 3
2o
4the cycle performance test curve of base composite negative pole material, relative to the ZnFe be not wrapped by
2o
4the electrode of material, the electrode after compound shows larger performance improvement equally, and after 100 circulations, discharge capacity is from 73mAhg
-1be improved to 858mAhg
-1.
In sum, in three dimensional carbon nanotubes base composite negative pole material prepared by the present invention, nano particle is successfully coated in material with carbon element, the structure of porous and hollow makes active material particle great volumetric expansion in charge and discharge process effectively be suppressed, three-dimensional network configuration can accelerate electrical conductivity, thus improves the cycle performance of material greatly.
Claims (10)
1. the preparation method of a high performance three-dimensional carbon nano-tube composite negative pole material, it is characterized in that, by using carboxylic carbon nano-tube as the network skeleton of three-dimensional, with the material of the modified high power capacity of LBL self-assembly for active material, by the effect of electrostatic attraction, carboxylic carbon nano-tube is mixed uniformly with active material, the carbon source of then being adulterated containing assorted element N or S by in-stiu coating prepares high performance three-dimensional carbon nano-tube composite negative pole material as three-dimensional bags coating via high-temperature process.
2. the preparation method of a kind of high performance three-dimensional carbon nano-tube composite negative pole material according to claim 1, is characterized in that, specifically comprise the following steps:
1) carbon nano-tube is carried out carboxylated process;
2) be added to the water by carboxylic carbon nano-tube, ultrasonic disperse prepares carboxylic carbon nano-tube solution;
3) be added to the water by the material of high power capacity modified for LBL self-assembly, ultrasonic disperse, stirs and obtains mixed liquor;
4) step 2 poured into by dispersed mixed liquor step 3) obtained) carboxylic carbon nano-tube solution in, after stirring leave standstill, obtain the carboxylic carbon nano-tube/active material suspension-turbid liquid of lower floor after removing upper strata clear aqueous solution;
5) under condition of ice bath, in the carboxylic carbon nano-tube/active material suspension-turbid liquid of step 4), drip conducting polymer monomer, ultrasonic disperse, stir and obtain mixed solution;
6) mixed solution of step 5) is first stirred under ice bath, regulate pH value, then drip the aqueous solution containing oxidant, stir under ice bath and spend the night, obtain carboxylic carbon nano-tube/active material/polymer composites through suction filtration;
7) carboxylic carbon nano-tube/active material/polymer composites of step 6) high-temperature process under protection gas is prepared high performance three-dimensional carbon nano-tube composite negative pole material.
3. the preparation method of a kind of high performance three-dimensional carbon nano-tube composite negative pole material according to claim 1 and 2, it is characterized in that, the carboxylated treatment step of described step 1) is: first remaining metal ion is removed in carbon nano-tube 80 DEG C of backflows in concentrated hydrochloric acid, be the concentrated sulfuric acid/salpeter solution 60 DEG C of ultrasonic 3h of 3/1 again by it use volume ratio, after being washed till neutral rear drying with a large amount of deionized water.
4. the preparation method of a kind of high performance three-dimensional carbon nano-tube composite negative pole material according to claim 1 and 2, it is characterized in that, the step of described step 3) LBL self-assembly modification is: using anionic polyelectrolyte diallyl dimethyl ammoniumchloride and cationic polyelectrolyte kayexalate as raw material, carry out layer assembly at the material surface of high power capacity, change the charge property of active material surface.
5. the preparation method of a kind of high performance three-dimensional carbon nano-tube composite negative pole material according to claim 1 and 2, is characterized in that, the material of described high power capacity is one or more in nano silica fume, germanium powder, glass putty; Or nano-oxide powder comprises one or more in tin ash, tungsten oxide, zinc oxide, indium oxide; Or nano composite metal oxide comprises one or more in zinc manganate, cobalt acid manganese, Manganese Ferrite powder.
6. the preparation method of a kind of high performance three-dimensional carbon nano-tube composite negative pole material according to claim 1 and 2, it is characterized in that, described carboxylic carbon nano-tube is the one in Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes.
7. the preparation method of a kind of high performance three-dimensional carbon nano-tube composite negative pole material according to claim 1 and 2, it is characterized in that, described carboxylic carbon nano-tube and the mass ratio of active material are 1:5 ~ 1:10.
8. the preparation method of a kind of high performance three-dimensional carbon nano-tube composite negative pole material according to claim 1 and 2, it is characterized in that, in described step 5), conducting polymer monomer is the one in aniline monomer, pyrrole monomer, thiophene monomer, the addition of described conducting polymer monomer is 0.5 ~ 2 times of the quality of active material, in step 6), the addition of oxidant is 2.4 ~ 5 times of the quality of polymer monomer, and oxidant is (NH
4)
2s
2o
8.
9. the preparation method of a kind of high performance three-dimensional carbon nano-tube composite negative pole material according to claim 1 and 2, it is characterized in that, the high-temperature process in described step 7) is: 500 ~ 800 DEG C are carried out in a vacuum or inert atmosphere, and inert atmosphere is Ar, Ar/H
2gaseous mixture or He.
10. the high performance three-dimensional carbon nano-tube composite negative pole material that the preparation method described in claim 1 or 2 prepares is preparing the application in combination electrode.
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