CN103500820A - Sulfur/porous carbon-coated carbon nano tube compound positive material for lithium-sulfur battery and preparation method thereof - Google Patents
Sulfur/porous carbon-coated carbon nano tube compound positive material for lithium-sulfur battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a sulfur/porous carbon-coated carbon nano tube compound positive material for a lithium-sulfur battery and a preparation method thereof. The lithium-sulfur battery compound positive material is formed by compounding a carbon nano tube compound carbon material coated with porous carbon with a micro-nano structure and elemental sulfur. The preparation method comprises the following steps of: firstly coating poly-dopamine on the surface of a carbon nano tube; then carrying out high temperature carbonization, and compounding with the elemental sulfur to obtain the compound positive material. The preparation method disclosed by the invention has the advantages of easiness for operation and low cost. The prepared lithium-sulfur battery compound positive material is high in sulfur utilization ratio and greatly enhances the cycle property of the lithium-sulfur battery.
Description
Technical field
The present invention relates to a kind of sulphur for lithium-sulfur cell/porous carbon enveloped carbon nanometer tube composite positive pole and preparation method thereof, belong to new energy field.
Background technology
Along with the extensive use of lithium ion battery in portable type electronic product, electric automobile and instant-plugging hybrid electric vehicle, in the urgent need to developing the more battery of high-energy-density.Because the anode material for lithium-ion batteries specific capacity improves, be restricted, the energy density of lithium ion battery is difficult to further increase considerably.Improve energy density by the voltage platform that increases positive electrode simultaneously and can bring safety issue again.Forward positive electrode to " conversion reaction chemism " from " de-embedding mechanism ", be expected to obtain the material of height ratio capacity and specific energy.Elemental sulfur is one of the most promising positive electrode, and sulphur generates Li with the lithium metal complete reaction
2s, cell reaction is S+2Li=Li
2s, be the bielectron course of reaction, do not relate to the de-embedding reaction of lithium ion.Because the molecular weight of sulphur is low, the theoretical specific capacity of sulphur is up to 1675mAhg
-1(be almost LiFePO
410 times), theoretical specific energy is up to 2600WhKg
-1.In addition, elemental sulfur is abundant at the nature reserves, low toxicity, cheap, so elemental sulfur is a kind of positive electrode had a great attraction.
Yet there are the problems such as active material utilization is low, cycle performance is poor, the further raising of high rate performance needs in lithium-sulfur cell.And active material sulfur materials itself and final discharging product Li in lithium-sulfur cell
2s is the insulator of electronics and ion, and the intermediate product polysulfide in discharge process is soluble in electrolyte, and these can cause irreversible loss and the capacity attenuation of active material.For this reason, the conductivity how suppressed in the diffusion of polysulfide, the distribution of improving sulphur and the anodal cyclic process of raising sulphur is the research emphasis of sulfenyl positive electrode.
For solving these problems of lithium-sulfur cell, at present normally by elemental sulfur load (load, adhere to, mixing, epitaxial growth, coating etc.) in the carbon element class material with high-specific surface area, high porosity and excellent conductive performance feature, form composite positive pole, with the various negative effects that in the restriction cyclic process, polysulfide dissolves in electrolyte and causes thus.Wherein, carbon nano-tube has the advantages such as good conductivity, draw ratio be large, between them, can be barricaded as natural conductive network by bridge, is conducive to the diffusion of electrical conductivity and lithium ion.In addition, the draw ratio that carbon nano-tube is large can strengthen collector, bonding agent and the intergranular engaging force of active material, the positive meaning to the stabilized electrodes structure generation.But the general specific area of traditional carbon nano-tube material is less, sulfur loaded limited in one's ability, cause that sulfur content in the composite positive pole of preparation is low, skewness, be assembled into circulating battery after a few, still there is a large amount of active material sulphur can be from the surface dissolution of carbon nano-tube, cause the loss of active material, the lithium-sulfur cell energy density is difficult to further improve.If in composite positive pole, sulfur content further promotes, a large amount of sulphur are distributed in the outer surface of carbon nano-tube, cause on the one hand the conductive capability of electrode to descend; The polysulfide that this part sulphur generates after electrode reaction on the other hand easily diffusion shuttles back and forth, and causes the irreversible loss of active material, and the chemical property of material can not get bringing into play preferably.
Through retrieval pertinent literature and patent, carbon nano-tube and elemental sulfur 300 ℃ of heat under vacuum condition are compound, the sulfur content of the carbon nano-tube obtained/sulphur composite positive pole is 40wt.%, the sulfur electrode that composite positive pole, conductive carbon black, bonding agent are made according to the mass ratio of 8:1:1, be assembled into lithium-sulfur cell and carry out constant current charge-discharge test discovery, after 100 circles circulations, capability retention also has 53.3%, and enclosed pasture efficiency has reached 89%, embodied excellent chemical property, but sulfur content is on the low side.（Juchen?Guo,Yunhua?Xu,and?Chunsheng?Wang.Sulfur-Impregnated?Disordered?Carbon?Nanotubes?Cathode?for?Lithium-Sulfur?Batteries.Nano?Lett.2011,11,4288–4294）。In addition, about the carbon nano-tube of high sulfur content/sulphur composite positive pole, report is also arranged, after multi-walled carbon nano-tubes mixes than ball milling by the quality of 1:3 with elemental sulfur, 155 ℃ of compound 24h of melting under inert atmosphere, obtain the multi-walled carbon nano-tubes of sulfur content 72.6wt.%-sulphur composite positive pole, by composite positive pole, conductive carbon black, the sulfur electrode that bonding agent is made according to the mass ratio of 8:1:1, be assembled into lithium-sulfur cell and carry out the constant current charge-discharge test under the current density of 100mA/g, discharge capacity has 1180mAh/g first, after 100 circle circulations, capacity only remains 380mAh/g, the chemical property that shows the carbon nano-tube of high sulfur content/sulphur composite positive pole is unsatisfactory.(Min?He,Li-Xia?Yuan,Wu?Xing?Zhang,Yun?Hui?Huang.Porous?carbon?nanotubes?improved?sulfur?composite?cathode?for?lithium-sulfur?battery.J?Solid?State?Electrochem,201317:1641–1647)。Carbon nano-tube described above/sulphur composite positive pole has all improved some chemical properties of lithium-sulfur cell, take full advantage of conductivity and the network configuration of carbon nano-tube, the restrictions such as but the character that is limited to carbon nano-tube itself is as less as specific area, pore volume is low, carbon nano-tube/sulphur composite positive pole ubiquity sulphur load capacity problem on the low side, this causes the specific capacity of sulfur electrode integral body less than normal, the problems such as energy density is low, be unfavorable for suitability for industrialized production.
Summary of the invention
The present invention is directed to that carbon nano-tube of the prior art/sulphur composite positive pole ubiquity sulphur load capacity is on the low side, and cause the sulfur electrode specific capacity less than normal, the problems such as energy density is low, purpose is to be to provide a kind of high positive active material utilization efficiency that has, and can improve the sulphur of lithium-sulfur cell cycle performance/porous carbon enveloped carbon nanometer tube composite positive pole.
Another object of the present invention is the preparation method who is to provide the described sulphur of a kind of preparation simple to operate, that cost is low/porous carbon enveloped carbon nanometer tube composite positive pole, and the method is suitable for suitability for industrialized production.
The invention provides a kind of sulphur for lithium-sulfur cell/porous carbon enveloped carbon nanometer tube composite positive pole, this composite positive pole is composited by porous carbon enveloped carbon nanometer tube complex carbon material and elemental sulfur with micro-nano structure; Described porous carbon enveloped carbon nanometer tube complex carbon material is that poly-dopamine is coated on to carbon nano tube surface by 500～1200 ℃ of high temperature carbonizations, and the nanoporous carbon structure of being constructed by poly-dopamine obtained is grown in the surperficial carbon-to-carbon organic combination formed of carbon skeleton that carbon nano-tube is constructed.
It is by carbon nano-tube being joined containing the polymerization reaction of dopamine occurs in the solution of dopamine, generating poly-dopamine rete in carbon nano tube surface and realize that described poly-dopamine is coated on carbon nano tube surface.
Described poly-dopamine thicknesses of layers is 5nm～100nm, and thickness is controlled by polymerization reaction time.
The specific area of described porous carbon enveloped carbon nanometer tube complex carbon material is 200～2000m
2/ g.
Described elemental sulfur spread loads is in the duct of porous carbon enveloped carbon nanometer tube complex carbon material inside and in the pore structure of the nanoporous carbon structure on surface; Described nanoporous carbon structure has take micropore as main pore structure, and mutually connects between pore structure; Aperture≤the 2nm of described micropore, wherein, the ratio that micropore accounts for whole pore structure is 50～80%.
Described carbon nano-tube is one or both of Single Walled Carbon Nanotube, multi-walled carbon nano-tubes; The diameter of described carbon nano-tube is 10nm～200nm, and length is 500nm～10 μ m.
The present invention also provides a kind of preparation method of described composite positive pole, this preparation method is by the ultrasonic solution be distributed to containing dopamine of carbon nano-tube, under the condition stirred, toward slowly splashing into the alkaline solution that pH is 8～10 in solution, carry out polymerization reaction; After having reacted, the carbon nano tube products that the surface of gained is coated with to poly-dopamine is placed in stove, under inert atmosphere, with the heating rate of 5～15 ℃/min, temperature is risen to 500～1200 ℃ from room temperature, after being incubated 5～20h; The porous carbon enveloped carbon nanometer tube complex carbon material and the elemental sulfur that obtain are compound, obtain.
The concentration range of described dopamine solution is 0.5～10mg/mL.
Described alkaline solution is KOH, NaOH, ammoniacal liquor, K
2cO
3, Na
2cO
3, K
3pO
4, Na
3pO
4one or more in solution.
Describedly be complex as a kind of in ball-milling method, high temperature heat fusing, liquid phase in-situ deposition, liquid infiltration method.
Described dopamine is the analog of 3,4-dihydroxy-L-Phe.
The preparation process of sulphur for lithium-sulfur cell of the present invention/porous carbon enveloped carbon nanometer tube composite positive pole: the carbon mano-tube composite presoma of the poly-dopamine clad surface of (1) preparation: carbon nano-tube is joined in the dopamine solution that concentration is 0.5～10mg/mL, after ultrasonic dispersion treatment 1～5h, obtain suspension-turbid liquid; Continuing under the condition stirred, slowly splash into the dilute alkaline soln that PH is 8～10 in solution, stirring reaction 1～20h at room temperature, the product of gained with deionized water and each washing of ethanolic solution for several times, obtains the carbon mano-tube composite presoma of poly-dopamine clad surface; (2) the charing preparation has the porous carbon enveloped carbon nanometer tube complex carbon material of micro-nano structure: the carbon mano-tube composite presoma of poly-dopamine clad surface is transferred in tube furnace, under argon gas atmosphere, heating rate with 5～15 ℃/min, temperature is risen to 500～1200 ℃ from room temperature, insulation 5～20h, obtain porous carbon enveloped carbon nanometer tube complex carbon material; (3) the compound sulphur/porous carbon enveloped carbon nanometer tube composite positive pole for preparing, the porous carbon enveloped carbon nanometer tube complex carbon material of (2) gained is compound by a kind of and elemental sulfur in ball-milling method, high temperature heat fusing, liquid phase in-situ deposition, liquid infiltration method, obtain.
Beneficial effect of the present invention: the present invention is devoted to the study on the modification of carbon nano-tube/sulphur positive electrode, make first the carbon nano-tube of poly-dopamine clad surface, method in conjunction with high temperature carbonization obtains the porous carbon structure enveloped carbon nanometer tube complex carbon material with micro-nano structure again, it is large that this complex carbon material carries sulfur content, and can effectively suppress the dissolving of polysulfide in electrolyte, make its utilance with higher active material sulphur, greatly improved the cyclical stability of lithium-sulfur cell.The present invention slowly generates poly-dopamine by polymerization by dopamine and evenly is coated on carbon nano tube surface, in conjunction with the method for high temperature carbonization, the nanoporous carbon structure that obtains being constructed by poly-dopamine is grown in the surperficial carbon-to-carbon organic combination formed of carbon skeleton that carbon nano-tube is constructed again; This carbon-to-carbon organic combination has that poly-dopamine charing constructs simultaneously, and to take micropore be the nano level hollow duct that main porous carbon structure and carbon nano-tube itself exist, these pore structures have all kept physicochemical characteristic separately, and mutually connect again between pore structure, make to obtain porous carbon enveloped carbon nanometer tube complex carbon material and there is higher porosity and larger specific area, greatly increase the load capacity (weight content reaches 55～85%) of elemental sulfur and the contact area of elemental sulfur, improved electric transmission speed and response area; Whole porous carbon enveloped carbon nanometer tube complex carbon material is perfect carbon-to-carbon organic combination simultaneously, has kept carbon nano-tube good ion transfer ability and conductivity, for whole positive pole provides effective conductive network and lithium ion migrating channels; The nanoporous carbon that dopamine is constructed simultaneously, the micropore of Nano grade reaches 50～80% of pore structure, the network duct of nanoscale has effectively suppressed the dissolving diffusion loss of many lithium sulfides, greatly improve the utilization ratio of active substances in cathode materials sulphur, be conducive to the raising of lithium-sulfur cell cyclical stability; In addition, the raw material sources that the present invention adopts are wide, cheapness, and the preparation method is simple to operate, cost is low, is applicable to suitability for industrialized production.
The accompanying drawing explanation
The SEM figure of the sulphur that [Fig. 1] obtains for embodiment 1/porous carbon enveloped carbon nanometer tube composite positive pole.
The discharge curve first of the sulphur that [Fig. 2] obtains for embodiment 1/porous carbon enveloped carbon nanometer tube composite positive pole and carbon nano-tube/sulphur composite positive pole.
The sulphur that [Fig. 3] obtains for embodiment 1/porous carbon enveloped carbon nanometer tube composite positive pole and carbon nano-tube/sulphur composite positive pole 100 circle cycle performance figure under the 0.2C current density.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not restricted to the protection range of invention.Embodiment 1
By the Single Walled Carbon Nanotube of 1.0g, (diameter is 20nm, length is 1 μ m) join in the dopamine aqueous solution that 200mL concentration is 5mg/mL, under room temperature, ultrasonic processing 2h obtains finely dispersed carbon nanotube suspension, then under lasting magnetic agitation, toward the NaOH solution that slowly splashes into pH=9 in suspension-turbid liquid, after at room temperature mechanical agitation reaction 10h, products therefrom is washed respectively three times with deionized water and ethanol, remove impurity and the dopamine monomer on product surface, obtain poly-dopamine coated carbon nano-tube composite material.A certain amount of poly-dopamine coated carbon nano-tube composite material is transferred in tube furnace; under the protection of inert nitrogen gas, with the heating rate of 10 ℃/min, temperature is risen to 800 ℃ from room temperature; insulation 10h, obtain porous carbon enveloped carbon nanometer tube complex carbon material after charing.Through the BET test, find, the specific area of porous carbon enveloped carbon nanometer tube complex carbon material is by the 160m of original carbon nano-tube
2/ g is elevated to 802m
2/ g, the aperture≤2nm of micropore, the ratio that micropore accounts for whole pore structure is 70%.By porous carbon enveloped carbon nanometer tube complex carbon material and sulphur powder; mass ratio high speed ball milling mixing 2h with 2:8; then transfer in tube furnace; under the protection of inert gas argon gas; be warming up to 155 ℃; insulation 24h, obtain sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, by thermogravimetric, tests to such an extent that its actual sulfur content is 72.5wt.%.As a comparison, original carbon nano-tube is prepared according to the method described above to (71.8wt.%) carbon nano-tube that sulfur content is close/sulphur composite positive pole.Sulphur/porous carbon enveloped carbon nanometer tube composite positive pole preparation flow as schematic diagram as shown in Figure 1.The SEM figure that Fig. 2 is sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, as can be seen from Fig., sulphur is evenly distributed in whole composite positive pole.
The composite positive pole of embodiment 1 gained, conductive black, Kynoar (PVDF) are evenly mixed according to the mass ratio of 8:1:1, and be dispersed in the NMP of certain mass and do form slurry (solid content is 80wt%), then be coated on aluminum foil current collector, obtain a kind of lithium-sulphur cell positive electrode sheet after 60 ℃ of lower vacuumize.
The battery assembling with test is: positive plate is struck out to the electrode slice that diameter is 10mm, take metal lithium sheet as negative pole, electrolyte is 1M LiTFSI/DOL:DME (1:1), is assembled into the CR2025 button cell in being full of the glove box of argon gas.Under room temperature, (25 ℃) are with 0.2C(335mA/g) current density carry out the constant current charge-discharge test, discharging and recharging cut-ff voltage is 1.5～3.0V.Relatively the chemical property of sulphur/porous carbon enveloped carbon nanometer tube composite positive pole and carbon nano-tube/sulphur composite positive pole, find that they have all demonstrated the typical discharge platform of lithium-sulfur cell, as shown in Figure 3.The former first discharge specific capacity is 1360mAh/g, and after 100 circulations, specific capacity keeps 700mAh/g, and latter's first discharge specific capacity is 1200mAh/g, and after 100 circulations, specific discharge capacity is 400mAh/g, has maintained respectively 51.5% and 33.3% capability retention.Sulphur/porous carbon enveloped carbon nanometer tube composite positive pole is compared to carbon nano-tube/sulphur composite positive pole, has improved cyclical stability and the active material utilization of lithium-sulfur cell.
Embodiment 2
By the multi-walled carbon nano-tubes of 0.8g, (diameter is 100nm, length is 5 μ m) join in the dopamine aqueous solution that 200mL concentration is 0.5mg/mL, under room temperature, ultrasonic processing 1h obtains finely dispersed carbon nanotube suspension, then under lasting magnetic agitation, toward the NaOH solution that slowly splashes into pH=8 in suspension-turbid liquid, after at room temperature mechanical agitation reaction 8h, products therefrom is washed respectively three times with deionized water and ethanol, remove impurity and the dopamine monomer on product surface, obtain poly-dopamine coated carbon nano-tube composite material.A certain amount of poly-dopamine coated carbon nano-tube composite material is transferred in tube furnace; under the protection of inert nitrogen gas, with the heating rate of 5 ℃/min, temperature is risen to 1000 ℃ from room temperature; insulation 5h, obtain porous carbon enveloped carbon nanometer tube complex carbon material after charing.Through the BET test, find, the specific area of porous carbon enveloped carbon nanometer tube complex carbon material is by the 195m of original carbon nano-tube
2/ g is elevated to 1030m
2/ g, the aperture≤2nm of micropore, the ratio that micropore accounts for whole pore structure is 60%.By porous carbon enveloped carbon nanometer tube complex carbon material and sulphur powder; mass ratio high speed ball milling mixing 5h with 1:9; then transfer in tube furnace; under the protection of inert gas argon gas; be warming up to 155 ℃; insulation 20h, obtain sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, by thermogravimetric, tests to such an extent that its actual sulfur content is 84.8wt.%.
Embodiment 3
By the Single Walled Carbon Nanotube of 1.5g, (diameter is 10nm, length is 500nm) join in the dopamine aqueous solution that 100mL concentration is 10mg/mL, under room temperature, ultrasonic processing 3h obtains finely dispersed carbon nanotube suspension, then under lasting magnetic agitation, toward the KOH solution that slowly splashes into pH=8 in suspension-turbid liquid, after at room temperature mechanical agitation reaction 5h, products therefrom is washed respectively three times with deionized water and ethanol, remove impurity and the dopamine monomer on product surface, obtain poly-dopamine coated carbon nano-tube composite material.A certain amount of poly-dopamine coated carbon nano-tube composite material is transferred in tube furnace; under the protection of inert nitrogen gas, with the heating rate of 15 ℃/min, temperature is risen to 1200 ℃ from room temperature; insulation 8h, obtain porous carbon enveloped carbon nanometer tube complex carbon material after charing.Through the BET test, find, the specific area of porous carbon enveloped carbon nanometer tube complex carbon material is by the 120m of original carbon nano-tube
2/ g is elevated to 612m
2/ g, the aperture≤2nm of micropore, the ratio that micropore accounts for whole pore structure is 55%.By porous carbon enveloped carbon nanometer tube complex carbon material and sulphur powder; mass ratio high speed ball milling mixing 3h with 4:6; then transfer in tube furnace; under the protection of inert gas argon gas; be warming up to 155 ℃; insulation 16h, obtain sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, by thermogravimetric, tests to such an extent that its actual sulfur content is 55.6wt.%.
Embodiment 4
By the multi-walled carbon nano-tubes of 2.0g, (diameter is 50nm, length is 10 μ m) join in the dopamine aqueous solution that 200mL concentration is 8mg/mL, under room temperature, ultrasonic processing 4h obtains finely dispersed carbon nanotube suspension, then under lasting magnetic agitation, toward the Na that slowly splashes into pH=9 in suspension-turbid liquid
2cO
3solution, after at room temperature mechanical agitation reaction 12h, wash products therefrom respectively three times with deionized water and ethanol, removes impurity and the dopamine monomer on product surface, obtains poly-dopamine coated carbon nano-tube composite material.A certain amount of poly-dopamine coated carbon nano-tube composite material is transferred in tube furnace; under the protection of inert nitrogen gas, with the heating rate of 6 ℃/min, temperature is risen to 850 ℃ from room temperature; insulation 2h, obtain porous carbon enveloped carbon nanometer tube complex carbon material after charing.Through the BET test, find, the specific area of porous carbon enveloped carbon nanometer tube complex carbon material is by the 180m of original carbon nano-tube
2/ g is elevated to 1980m
2/ g, the aperture≤2nm of micropore, the ratio that micropore accounts for whole pore structure is 80%.By porous carbon enveloped carbon nanometer tube complex carbon material and sulphur powder; mass ratio high speed ball milling mixing 4h with 3:7; then transfer in tube furnace; under the protection of inert gas argon gas; be warming up to 155 ℃; insulation 12h, obtain sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, by thermogravimetric, tests to such an extent that its actual sulfur content is 68.5wt.%.
Embodiment 5
By the Single Walled Carbon Nanotube of 1.2g, (diameter is 15nm, length is 2 μ m) join in the dopamine aqueous solution that 500mL concentration is 1mg/mL, under room temperature, ultrasonic processing 5h obtains finely dispersed carbon nanotube suspension, then under lasting magnetic agitation, toward the KHCO that slowly splashes into pH=10 in suspension-turbid liquid
3solution, after at room temperature mechanical agitation reaction 6h, wash products therefrom respectively three times with deionized water and ethanol, removes impurity and the dopamine monomer on product surface, obtains poly-dopamine coated carbon nano-tube composite material.A certain amount of poly-dopamine coated carbon nano-tube composite material is transferred in tube furnace; under the protection of inert nitrogen gas, with the heating rate of 8 ℃/min, temperature is risen to 500 ℃ from room temperature; insulation 12h, obtain porous carbon enveloped carbon nanometer tube complex carbon material after charing.Through the BET test, find, the specific area of porous carbon enveloped carbon nanometer tube complex carbon material is by the 120m of original carbon nano-tube
2/ g is elevated to 320m
2/ g, the aperture≤2nm of micropore, the ratio that micropore accounts for whole pore structure is 50%, specific area and pore volume have all obtained significant raising.By porous carbon enveloped carbon nanometer tube complex carbon material and sulphur powder; mass ratio high speed ball milling mixing 6h with 2:8; then transfer in tube furnace; under the protection of inert gas argon gas; be warming up to 155 ℃; insulation 48h, obtain sulphur/porous carbon enveloped carbon nanometer tube composite positive pole, by thermogravimetric, tests to obtain its actual sulphur sulfur-bearing 70.8wt.%.
Claims (10)
1. the sulphur for lithium-sulfur cell/porous carbon enveloped carbon nanometer tube composite positive pole, is characterized in that, by porous carbon enveloped carbon nanometer tube complex carbon material and elemental sulfur with micro-nano structure, is composited; Described porous carbon enveloped carbon nanometer tube complex carbon material is that poly-dopamine is coated on to carbon nano tube surface by 500～1200 ℃ of high temperature carbonizations, and the nanoporous carbon structure of being constructed by poly-dopamine obtained is grown in the surperficial carbon-to-carbon organic combination formed of carbon skeleton that carbon nano-tube is constructed.
2. composite positive pole according to claim 1, it is characterized in that, it is by carbon nano-tube being joined containing the polymerization reaction of dopamine occurs in the solution of dopamine, generating poly-dopamine rete in carbon nano tube surface and realize that described poly-dopamine is coated on carbon nano tube surface.
3. composite positive pole according to claim 2, is characterized in that, described poly-dopamine thicknesses of layers is 5nm～100nm, and thickness is controlled by polymerization reaction time.
4. composite positive pole according to claim 1, is characterized in that, the specific area of described porous carbon enveloped carbon nanometer tube complex carbon material is 200～2000m
2/ g.
5. composite positive pole according to claim 1, is characterized in that, described elemental sulfur spread loads is in the duct of porous carbon enveloped carbon nanometer tube complex carbon material inside and in the pore structure of the nanoporous carbon structure on surface; Described nanoporous carbon structure has take micropore as main pore structure, and mutually connects between pore structure; Aperture≤the 2nm of described micropore, wherein, the ratio that micropore accounts for whole pore structure is 50～80%.
6. composite positive pole according to claim 1, is characterized in that, described carbon nano-tube is one or both of Single Walled Carbon Nanotube, multi-walled carbon nano-tubes; The diameter of described carbon nano-tube is 10nm～200nm, and length is 500nm～10 μ m.
7. the preparation method according to the described composite positive pole of claim 1～6 any one, it is characterized in that, by in the ultrasonic solution be distributed to containing dopamine of carbon nano-tube, under the condition stirred, toward slowly splashing into the alkaline solution that pH is 8～10 in solution, carry out polymerization reaction; After having reacted, the carbon nano tube products that the surface of gained is coated with to poly-dopamine is placed in stove, under inert atmosphere, with the heating rate of 5～15 ℃/min, temperature is risen to 500～1200 ℃ from room temperature, after being incubated 5～20h; The porous carbon enveloped carbon nanometer tube complex carbon material and the elemental sulfur that obtain are compound, obtain.
8. preparation method according to claim 7, is characterized in that, the concentration range of described dopamine solution is 0.5～10mg/mL.
9. preparation method according to claim 7, is characterized in that, described alkaline solution is KOH, NaOH, ammoniacal liquor, K
2cO
3, Na
2cO
3, K
3pO
4, Na
3pO
4one or more in solution.
10. preparation method according to claim 7, is characterized in that, describedly is complex as a kind of in ball-milling method, high temperature heat fusing, liquid phase in-situ deposition, liquid infiltration method.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855363A (en) * | 2014-02-28 | 2014-06-11 | 广州市香港科大霍英东研究院 | Long-service-life and high-specific-capacity poly-dopamine-coated hollow sulfur microsphere composite positive electrode material and preparation method thereof |
| CN104362290A (en) * | 2014-10-09 | 2015-02-18 | 南京中储新能源有限公司 | Preparation and application of porous carbon coated orientation carbon nano tube/sulfur composite anode |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142554A (en) * | 2011-02-16 | 2011-08-03 | 中国人民解放军63971部队 | Nano carbon sulfur composite material with network structure and preparation method of nano carbon composite material |
| CN102447113A (en) * | 2011-12-12 | 2012-05-09 | 南开大学 | Lithium battery with polymer-coated sulfur/carbon composite material as anode |
| CN103151524A (en) * | 2013-03-04 | 2013-06-12 | 北京化工大学常州先进材料研究院 | Positive pole material for high-performance lithium-sulfur battery and preparation method thereof |
| CN103258990A (en) * | 2013-04-24 | 2013-08-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Lithium sulfur battery cathode material and preparation method thereof |
-
2013
- 2013-09-18 CN CN201310428298.1A patent/CN103500820B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142554A (en) * | 2011-02-16 | 2011-08-03 | 中国人民解放军63971部队 | Nano carbon sulfur composite material with network structure and preparation method of nano carbon composite material |
| CN102447113A (en) * | 2011-12-12 | 2012-05-09 | 南开大学 | Lithium battery with polymer-coated sulfur/carbon composite material as anode |
| CN103151524A (en) * | 2013-03-04 | 2013-06-12 | 北京化工大学常州先进材料研究院 | Positive pole material for high-performance lithium-sulfur battery and preparation method thereof |
| CN103258990A (en) * | 2013-04-24 | 2013-08-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Lithium sulfur battery cathode material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| YONGGUANG ZHANG ET AL.: "A novel sulfur/polypyrrole/multi-walled carbon nanotube nanocomposite cathode with core–shell tubular structure for lithium rechargeable batteries", 《SOLID STATE IONICS》, vol. 238, 1 May 2013 (2013-05-01), pages 30 - 35, XP028545134, DOI: 10.1016/j.ssi.2013.03.006 * |
| ZHAOFENG DENG ET AL.: "A sulfur-carbon composite for lithium/sulfur battery based on activated vapor-grown carbon fiber", 《SOLID STATE IONICS》 * |
| ZHAOFENG DENG ET AL.: "A sulfur-carbon composite for lithium/sulfur battery based on activated vapor-grown carbon fiber", 《SOLID STATE IONICS》, vol. 238, 1 May 2013 (2013-05-01), pages 44 - 49 * |
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