CN109817899A - A kind of preparation method and application of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material - Google Patents
A kind of preparation method and application of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material Download PDFInfo
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- CN109817899A CN109817899A CN201811479348.8A CN201811479348A CN109817899A CN 109817899 A CN109817899 A CN 109817899A CN 201811479348 A CN201811479348 A CN 201811479348A CN 109817899 A CN109817899 A CN 109817899A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses the preparation methods and application of a kind of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material.By the way that transition metal salt, fructose, cyano amine etc. are dispersed in solvent by after evenly mixing, it is handled by rotary evaporation, after obtained powder is sufficiently dried, pass through high temperature sintering in an inert atmosphere, powder is using thioacetamide hydro-thermal vulcanizing treatment to get miscellaneous element doping carbon nanotube encapsulation metal sulfide material after being heat-treated.The combination electrode prepared using miscellaneous element doping carbon nanotube encapsulation metal sulfide material, according to the feature in anode material of lithium-ion battery charge and discharge cycles, uniform carbon-coating is coated by the encapsulation in the outside of active material, the one-dimentional structure of its carbon nanotube is conducive to improve electronics conduction, to effectively improve, improve the chemical property of electrode material.Preparation manipulation simple process of the present invention, the charge-discharge performance of high income, material is excellent, is convenient for industrialized production.
Description
Technical field
The present invention relates to anode material of lithium-ion battery technical fields, and in particular to a kind of miscellaneous element doping carbon nanotube envelope
Fill the preparation method and application of metal sulfide composite negative pole material.
Background technique
Sodium-ion battery working principle is similar with lithium ion battery, and using sodium ion, embedding de- process is realized between positive and negative anodes
Charge and discharge.Compared with lithium ion battery, sodium-ion battery has been had the advantage that: (1) sodium salt raw material rich reserves, price are low
It is honest and clean, it is compared ternary cathode material of lithium ion battery using ferrimanganic nickel-base anode material, cost of material reduces half；(2) due to
Sodium salt characteristic allows using low concentration electrolyte (same concentration electrolytic solution, sodium salt conductivity are higher than lithium electrolyte 20% or so) drop
Low cost；(3) sodium ion does not form alloy with aluminium, and cathode can be used aluminium foil as collector, can further reduce the cost 8%
Left and right reduces weight 10% or so；(4) since sodium-ion battery is without over-discharge electrical characteristics, sodium-ion battery is allowed to discharge into zero volt.
Sodium-ion battery energy density is greater than 100Wh/kg, can compare favourably with ferric phosphate lithium cell, but its cost advantage is obvious, is expected to
Replace traditional lead acid batteries in extensive energy storage.
Up to the present, the main foundation of the research of anode material of lithium-ion battery has with intercalation, alloying and conversion
Mechanism etc..The material of intercalation mechanisms such as graphite and Na3V2(PO4)3, show outstanding circulation and rate capability, but their theory
It is low with actual capacity.Alloy mechanism such as the Sn and P or metal oxide of transformation mechanism such as Fe2O3And CuO, there is very high reason
By storage sodium capacity, but due to the disadvantages of its bulk effect is big, structure change is big, so that their cycle life is very poor.Metal sulphur
Compound is to study more active field in recent years, in sodium-ion battery direction due to specific capacity with higher and preferable
Cycle performance shows very big potentiality.In order to further improve the chemical property of metal sulfide, by it and good conductivity
Carbon material combine prepare the mainstream research direction that composite negative pole material is current sode cell.
Carbon nanotube is due to possessing lighter quality, preferable electric conductivity, lower intercalation potential, volume during deintercalation
Changing many advantages, such as small and cheap etc. is widely used in anode material.Transient metal sulfide is encapsulated in
The inserted composite construction of inside-formation of carbon nanotube, can protect sulfide material during deintercalation sodium structure not by
It destroys, and can further improve the conductivity of material, polarization is reduced, so that high degree improves the circulation of electrode material
Performance.But transient metal sulfide up to this point, is encapsulated in this technology of the inside of carbon nanotube, is also rarely had both at home and abroad
Report.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of miscellaneous element doping carbon nanotube encapsulation metals
The preparation method and application of sulfide composite negative pole material, negative electrode material conductivity, preparation process is simple, low in cost,
And used as battery component, improve the cycle performance of electrode.
To solve prior art problem, the technical scheme adopted by the invention is as follows:
A kind of preparation method of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material, first prepares alcohol-water
Mixed solution, sequentially add cyano amine, transition metal salt and fructose into mixed solution, when addition continues stirring until completely molten
Solution, then rotary evaporation remove solvent, vacuum drying black powder；Secondly, black powder is passed through high temperature in an inert atmosphere
Sintering；Finally, powder is sealed using thioacetamide hydro-thermal vulcanizing treatment to get miscellaneous element doping carbon nanotube after being heat-treated
Fill metal sulfide composite negative pole material；The transition metal salt is transition metal sulfate, transition metal villaumite or transition gold
Genus nitrobacter；The transition metal is iron, cobalt or nickel.
The preparation method of above-mentioned miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material, including following step
It is rapid:
Step 1, the volume ratio of the mixed solution of configuration dehydrated alcohol and water, the water and ethyl alcohol is 9-19:1；Step 2, by cyanogen
Base amine is dispersed in above-mentioned mixed solution, and after ultrasonic dissolution is complete, transition metal salt is added, is ultrasonically treated after twenty minutes, then plus
It is complete to enter fructose ultrasonic dissolution, solvent is removed by way of rotary evaporation, then precursor is prepared via vacuum drying
The mass ratio of end, the cyano amine and fructose is 10-20:1, and the mass ratio of transition metal salt and fructose is 0.3-2:1；Step 3,
Precursor powder is transferred in tube furnace, constant heating rates sintering after heat preservation 2 hours, is continuously heating to 600 DEG C under an inert atmosphere
800 DEG C, heat preservation was down to room temperature after 2 hours, obtained black powder；Step 4, black powder is dispersed in the ethyl alcohol of thioacetamide
In solution, ultrasonic agitation uniformly after, go in hydrothermal reaction kettle vulcanizing treatment 5-24h at 150-220 DEG C, stirring is taken out after 24 hours
Filter is cleaned filter residue and is dried to get miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material, the sulphur
It is 3-5:1 for the mass ratio of acetamide and black powder.
It is that inert atmosphere is by Ar, Ar/H described in step 3 as improved2What gaseous mixture or He were formed.
It is that the rate of constant heating rates sintering is 2 DEG C/min in step 4 as improved.
Above-mentioned miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material is on preparing compound negative electrode
Using.
It is that the application is by miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material as improved
Material, carbon black and carboxymethyl cellulose are uniformly mixed, and are dried in vacuo 4 hours at 60 DEG C after film to get combination electrode.
Beneficial effect
The present invention is received according to the feature in sode cell negative electrode material charge and discharge cycles by the way that transient metal sulfide is encapsulated in carbon
The inserted composite construction of inside-formation of mitron can protect sulfide material structure during deintercalation sodium not to be destroyed,
The conductivity of material can further be improved again, polarization is reduced, so that high degree improves the cycle performance of electrode material.
The present invention prepares that raw material is cheap, and operating procedure is simple, and the charge-discharge performance of high income, material is excellent, is convenient for industrialized production.This
Invention improves the cycle performance and high rate performance of active material obvious.In addition, one of raw material used in the present invention is fructose,
Solvent is water, environmental-friendly, and reproducible, low in cost, has preferable scale application potentiality, and industrial prospect is good
It is good.
Detailed description of the invention
Fig. 1 is the SEM figure of the miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material of the present invention, wherein
It (a) is comparative example 1, (b) embodiment 1, (c) embodiment 3, (d) embodiment 5；
Fig. 2 is the XPS map of sample prepared by the comparative example (molysite is not added) of embodiment 1；
Fig. 3 is the XRD spectrum of the miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material of the present invention；
Fig. 4 is that the electrode of the miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material preparation of Examples 1 to 5 exists
1A·g-1Charging and discharging currents density under cycle performance test curve.
Specific embodiment
Further describe below in conjunction with attached drawing to embodiment of the present invention: following embodiment is with technical solution of the present invention
Premised under implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is unlimited
In following embodiments.
Embodiment 1
A kind of preparation method of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material, comprising the following steps:
1) mixed solution of 100 mL dehydrated alcohols and water, the volume ratio 9:1 of water and ethyl alcohol are configured；
2) the cyano amine of 3g is dispersed in above-mentioned mixed solution, after ultrasonic dissolution is complete, ferric sulfate 0.3g, 20 points of ultrasound is added
Zhong Hou, the fructose ultrasonic dissolution for adding 0.3g is complete, solvent is removed by way of rotary evaporation, then make via vacuum drying
It is standby to obtain precursor powder；
3) precursor powder is transferred in tube furnace, rises to 600 DEG C under argon gas with the heating rate of 2 DEG C/min, keep the temperature two
Hour, then 800 DEG C are risen to the heating rate of 2 DEG C/min, it is down to room temperature after keeping the temperature two hours, obtains black powder, as
Carbon nanotube encapsulation iron nano-particle composite material；
4) it disperses carbon nanotube encapsulation iron nano-particle composite material 0.1g in the ethanol solution of thioacetamide (containing thio
Acetamide 0.3g), ultrasonic agitation uniformly after, it is near to be transferred to 180 DEG C of 12 h vulcanization reaction, reaction in hydrothermal reaction kettle and terminate
After filter, compound is dried to obtain after cleaning and obtains miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material
Material；
5) after miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material being fully ground and carbon black and carboxymethyl
Cellulose is uniformly mixed, 60 DEG C of 4 h of vacuum drying after film according to the ratio of weight ratio 70: 15: 15, is prepared multiple
Composite electrode.It is to electrode, using polyethylene film as diaphragm, with 1M NaClO with sodium piece by combination electrode in 2025 battery cases4?
EC:EMC:DMC(volume ratio 1/1/1)+5%FEC be electrolyte assembled battery carry out constant current charge-discharge test.
Embodiment 2
A kind of preparation method of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material, comprising the following steps:
1) ratio of the mixed solution of 200 mL dehydrated alcohols and water of configuration, water and ethyl alcohol is 19:1；
2) the cyano amine of 3g is dispersed in above-mentioned mixed solution, after ultrasonic dissolution is complete, 0.6 g of ferric sulfate, ultrasound 20 is added
After minute, the fructose ultrasonic dissolution for adding 0.3g is complete, solvent is removed by way of rotary evaporation, then via vacuum drying
Precursor powder is prepared；
3) by above-mentioned precursor powder to entering in tube furnace, 600 DEG C are risen to the heating rate of 2 DEG C/min under argon gas, heat preservation
Two hours, then 800 DEG C are risen to the heating rate of 2 DEG C/min, it is down to room temperature after keeping the temperature two hours, obtains black powder,
As carbon nanotube encapsulation iron nano-particle composite material；
4) it disperses carbon nanotube encapsulation iron nano-particle composite material 0.1g in the ethanol solution of thioacetamide (containing thio
Acetamide 0.5g), ultrasonic agitation uniformly after, it is near to be transferred to 200 DEG C of 6 h vulcanization reaction, reaction in hydrothermal reaction kettle and terminate
After filter, compound is dried to obtain after cleaning and obtains miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material
Material；
6) after miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material being fully ground and carbon black and carboxymethyl
Cellulose is uniformly mixed, 60 DEG C of 4 h of vacuum drying after film according to the ratio of weight ratio 70: 15: 15, is prepared multiple
Composite electrode.It is to electrode, using polyethylene film as diaphragm, with 1M NaClO with sodium piece by combination electrode in 2025 battery cases4?
EC:EMC:DMC(volume ratio 1/1/1)+5%FEC be electrolyte assembled battery carry out constant current charge-discharge test.
Embodiment 3
A kind of preparation method of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material, comprising the following steps:
1) ratio of the mixed solution of 200 mL dehydrated alcohols and water of configuration, water and ethyl alcohol is 15:1.
2) the cyano amine of 3g is dispersed in above-mentioned mixed solution, after ultrasonic dissolution is complete, 0.1 g of ferric sulfate is added, surpasses
After twenty minutes, the fructose ultrasonic dissolution for adding 0.3g is complete for sound, solvent is removed by way of rotary evaporation, then via vacuum
Precursor powder is prepared in drying；
3) by above-mentioned precursor powder to entering in tube furnace, 600 DEG C are risen to the heating rate of 2 DEG C/min under argon gas, heat preservation
Two hours, then 800 DEG C are risen to the heating rate of 2 DEG C/min, it is down to room temperature after keeping the temperature two hours, obtains black powder,
As carbon nanotube encapsulation iron nano-particle composite material；
4) it disperses the dusty material 0.1g of step 3) in the ethanol solution of thioacetamide (containing thioacetamide 0.4g), surpasses
Sound is after mixing evenly, near to be transferred to 220 DEG C of 3 h vulcanization reaction in hydrothermal reaction kettle, filters after reaction, does after cleaning
The dry compound that obtains obtains miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material.
6) after miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material being fully ground and carbon black and carboxylic
Methylcellulose is uniformly mixed, 60 DEG C of 4 h of vacuum drying, are prepared into after film according to the ratio of weight ratio 70: 15: 15
To combination electrode.It is to electrode, using polyethylene film as diaphragm, with 1M with sodium piece by combination electrode in 2025 battery cases
NaClO4In EC:EMC:DMC(volume ratio 1/1/1)+5%FEC be electrolyte assembled battery carry out constant current charge-discharge test.
Embodiment 4
A kind of preparation method of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material, comprising the following steps:
1) ratio of the mixed solution of 200 mL dehydrated alcohols and water of configuration, water and ethyl alcohol is 10:1.
2) the cyano amine of 6g is dispersed in above-mentioned mixed solution, after ultrasonic dissolution is complete, 0.5 g of cobalt chloride is added, surpasses
After twenty minutes, the fructose ultrasonic dissolution for adding 0.3g is complete for sound, solvent is removed by way of rotary evaporation, then via vacuum
Precursor powder is prepared in drying；
3) by above-mentioned precursor powder to entering in tube furnace, in Ar/H2Under with the heating rate of 2 DEG C/min rise to 600 DEG C, heat preservation
Two hours, then 800 DEG C are risen to the heating rate of 2 DEG C/min, it is down to room temperature after keeping the temperature two hours, obtains black powder,
As carbon nanotube encapsulation cobalt nano-particle composite material；
4) it disperses carbon nanotube encapsulation cobalt nano-particle composite material 0.1g in the ethanol solution of thioacetamide (containing thio
Acetamide 0.35g), it is near to be transferred to 150 DEG C of 24 h vulcanization reaction in hydrothermal reaction kettle, reaction knot after ultrasonic agitation is uniform
It is filtered after beam, compound is dried to obtain after cleaning and obtains miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material
Material.
6) after being fully ground sintered material and carbon black and carboxymethyl cellulose are according to weight ratio 70: 15: 15
Ratio is uniformly mixed, and 60 DEG C of 4 h of vacuum drying, are prepared combination electrode after film.By electrode in 2025 battery cases,
It is to combination electrode, using polyethylene film as diaphragm, with 1M NaClO with sodium piece4In EC:EMC:DMC(volume ratio 1/1/1)+5%
FEC is that electrolyte assembled battery carries out constant current charge-discharge test.
Embodiment 5
A kind of preparation method of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material, comprising the following steps:
1) ratio of the mixed solution of 200 mL dehydrated alcohols and water of configuration, water and ethyl alcohol is 10:1.
2) the cyano amine of 6g is dispersed in above-mentioned mixed solution, after ultrasonic dissolution is complete, nickel nitrate 0.1g, ultrasound is added
After twenty minutes, the fructose ultrasonic dissolution for adding 0.3g is complete, and solvent is removed by way of rotary evaporation, then dry via vacuum
It is dry that precursor powder is prepared；
3) by above-mentioned precursor powder to entering in tube furnace, 600 DEG C are risen to the heating rate of 2 DEG C/min under He gas, heat preservation
Two hours, then 800 DEG C are risen to the heating rate of 2 DEG C/min, it is down to room temperature after keeping the temperature two hours, obtains black powder,
As carbon nanotube encapsulation nano nickel particles composite material；
4) it disperses carbon nanotube encapsulation nano nickel particles composite material 0.1g in the ethanol solution of thioacetamide (containing thio
Acetamide 0.35g), it is near to be transferred to 180 DEG C of 15 h vulcanization reaction in hydrothermal reaction kettle, reaction knot after ultrasonic agitation is uniform
It is filtered after beam, compound is dried to obtain after cleaning and obtains miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material
Material.
6) after miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material being fully ground and carbon black and carboxylic
Methylcellulose is uniformly mixed, 60 DEG C of 4 h of vacuum drying, are prepared into after film according to the ratio of weight ratio 70: 15: 15
To combination electrode.It is to electrode, using polyethylene film as diaphragm, with 1M with sodium piece by combination electrode in 2025 battery cases
NaClO4In EC:EMC:DMC(volume ratio 1/1/1)+5%FEC be electrolyte assembled battery carry out constant current charge-discharge test.
Below by specific characterization to the structure and morphology of composite material and the electrification of composite material prepared by the present invention
Performance is learned to be tested and characterized.
1, sem analysis
Fig. 1 is the embodiment of the present invention 1, embodiment 3, sample and the TEM photo of associated sample prepared by embodiment 5.Fig. 1 (a) is
The comparative example when being added without molysite of scheme one.It can be seen that in the case where being added without molysite, prepared material
Flaky texture is presented, does not have nano tube structure pattern.Fig. 1 (b), Fig. 1 (c) and Fig. 1 (d) are divided into embodiment 1, embodiment 3, reality
The corresponding SEM of example 5 figure is applied, can be seen from the chart, miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material
Carbon nanotubular structure is presented.In addition, the centre of nanotube can high-visible there are nanoparticle structures.Carbon nanotube
Wall is very thin.This is the structure that common carbon nanotube cannot be presented.
2, XPS and XRD analysis
The XPS map of sample prepared by the comparative example (molysite is not added) of Fig. 2 embodiment 1.As can be seen that sample mainly includes on figure
C, tri- kinds of elements of N, O, wherein atomic ratio shared by carbon is 80%, and nitrogen-atoms accounts for 17%, and oxygen atom accounts for 3%.The doping of nitrogen can be more
The conductivity of the improvement composite material of high level, to reduce polarization of the electrode material under big multiplying power.Fig. 3 is that the present invention is implemented
The XRD diagram of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material prepared by example 1 ~ 3, can from figure
Out, FeS is presented in miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material2Crystal phase structure goes out at 25 ° or so
Existing steamed bun peak is the characteristic peak of amorphous carbon material.
3, cycle performance is tested
Fig. 4 is that embodiment 1 ~ 5 prepares the compound of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material preparation
Electrode is in 1Ag-1Charging and discharging currents density under cycle performance test curve.Even if on figure it can be seen that in very high charge and discharge
Under electric current density, all electrodes prepared by embodiment are able to maintain higher reversible specific capacity, and recycle 100 times or so
Basically no attenuation.
In conclusion a kind of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material prepared by the present invention
Material, sulfide nanoparticle are successfully coated in carbon nanotube, and hollow carbon nano tube structure makes active material particle
Great volume expansion is effectively inhibited in charge and discharge process, to greatly improve the cycle performance of material.This
Outside, the doping of miscellaneous element N can adequately improve the electron conduction of combination electrode material.What special preparation method was prepared
The wall of carbon nanotube is very thin.These features combine, and can make prepared sulfide composite negative pole in sodium-ion battery
Efficiently, stable operation.
Claims (6)
1. a kind of preparation method of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material, which is characterized in that
The mixed solution for first preparing alcohol-water, sequentially adds cyano amine, transition metal salt and fructose into mixed solution, and when addition holds
Continuous stirring is to being completely dissolved, then rotary evaporation removes solvent, vacuum drying black powder；Secondly, by black powder in inertia
Pass through high temperature sintering in atmosphere；Finally, powder is using thioacetamide hydro-thermal vulcanizing treatment to get miscellaneous element after being heat-treated
Doped carbon nanometer pipe package metals sulfide composite negative pole material；The transition metal salt is transition metal sulfate, transition gold
Belong to villaumite or transition metal nitrate；The transition metal is iron, cobalt or nickel.
2. a kind of system of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material according to claim 1
Preparation Method, which comprises the following steps: step 1, configure the mixed solution of dehydrated alcohol and water, the water and ethyl alcohol
Volume ratio be 9-19:1；Step 2, cyano amine is dispersed in above-mentioned mixed solution, after ultrasonic dissolution is complete, transition gold is added
Belong to salt, after twenty minutes, it is complete to add fructose ultrasonic dissolution for ultrasonic treatment, solvent is removed by way of rotary evaporation, then pass through
Precursor powder is prepared by vacuum drying, the mass ratio of the cyano amine and fructose is 10-20:1, transition metal salt and fruit
The mass ratio of sugar is 0.3-2:1；Step 3, precursor powder is transferred in tube furnace, under an inert atmosphere constant heating rates sintering to 600
DEG C, after heat preservation 2 hours, 800 DEG C are continuously heating to, heat preservation was down to room temperature after 2 hours, obtained black powder；Step 4, by black
Powder is scattered in the ethanol solution of thioacetamide, ultrasonic agitation uniformly after, go in hydrothermal reaction kettle sulphur at 150-220 DEG C
Change processing 5-24h, stirring filters after 24 hours, cleans filter residue and is dried to get miscellaneous element doping carbon nanotube encapsulation gold
The mass ratio of category sulfide composite negative pole material, the thioacetamide and black powder is 3-5:1.
3. a kind of system of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material according to claim 2
Preparation Method, which is characterized in that inert atmosphere is by Ar, Ar/H described in step 32What gaseous mixture or He were formed.
4. a kind of system of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material according to claim 2
Preparation Method, which is characterized in that the rate of constant heating rates sintering is 2 DEG C/min in step 4.
5. multiple in preparation based on miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material prepared by claim 1
Close the application on negative electrode.
6. application according to claim 5, which is characterized in that miscellaneous element doping carbon nanotube encapsulation metal sulfide will be contained
Composite negative pole material, carbon black and carboxymethyl cellulose are uniformly mixed, and are dried in vacuo 4 hours at 60 DEG C after film to get compound electric
Pole.
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