CN104218230A - Carbon nano tube sponge conducting polymer composite cathode for secondary battery - Google Patents
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a carbon nano tube sponge conducting polymer composite cathode, a preparation method and application. Carbon nano tube sponge is used as a substrate of the composite cathode, and loading of sulfur active substances can be achieved by means of in-situ polymerization polypyrrole and hot melting diffusion. A conductive network formed by composition of the carbon nano tube sponge and polypyrrole has features of a range limiting function, a surface adsorption function, high electrical conductivity and the like, sulfur active substances can be adsorbed, dissolution of sulfur reduction products can be inhibited, and electrical conductivity and cycle performance of the composite cathode can be further improved. Addition of conductive agents and bonder to the composite cathode is not required, the preparing process is simple, costs are low, and the energy density is high.
Description
Technical field
The invention belongs to battery material and new energy field, relate to a kind of carbon nano-tube sponge conducting polymer, preparation method and apply secondary aluminium cell prepared by this electrode.
Background technology
The develop rapidly of the new energy technologies such as regenerative resource is grid-connected, electric automobile and intelligent grid is in the urgent need to developing the more energy storage system of high-energy-density.Secondary aluminium-sulfur battery, as emerging battery system, is to take metallic aluminium as negative pole, and sulphur or sulfur-based compound are anodal battery system, have the features such as aboundresources, pollution-free, cheap, energy density is high, use is safe.The volume and capacity ratio of aluminium is 8050mAh/cm
3, be 4 times of lithium, and chemical activity is stable, is desirable negative material; And the theoretical volume specific capacity of sulphur is 3467mAh/cm
3, be one of positive electrode that known energy density is the highest.Yet the dissolving in electrolyte due to the nonconducting attribute of elemental sulfur and discharging product, easily causes the utilance of active material low, electrode passivation, the problems such as battery capacity declines, and cycle performance is poor, solution is that sulfur-bearing active material and carbon-based material and conducting polymer is compound.
Wherein, carbon nano-tube has and conducts electricity very well, and the advantage such as draw ratio is large, can be barricaded as natural conductive network by bridge between them, is conducive to the conduction of electronics and the diffusion of ion, is widely used in battery electrode material.Traditional carbon nano-tube mostly is unordered reunion shape, main by the suction-operated sulfur loaded on carbon nano-tube sponge surface, be subject to the restriction of carbon-based material loose structure and surface chemistry simultaneously, a little less than the interaction very on sulphur and carbon matrix surface, cause that sulphur content in carbon matrix is low, skewness, while discharging and recharging, a large amount of sulphur can directly dissolve in electrolyte from the surface of carbon nano-tube, cause the loss of active material, energy content of battery density is difficult to improve.Therefore, only depend on the confinement effect of material with carbon element hole and the loss by dissolution that adsorption effect is difficult to thoroughly suppress poly sulfide, cycle performance can't reach practical degree.
Polypyrrole has good conductivity and stability, high energy storage capacity and high electrochemical redox characteristic, and ion can freely transmit in film, is a kind of desirable electrode material.But relative carbon electrode, cycle life is unstable, and expansion and the contraction of volume easily occur in charge and discharge process, easily from electrode, comes off.
Summary of the invention
(1) goal of the invention
For the problems referred to above and deficiency, the object of the present invention is to provide a kind of carbon nano-tube sponge conducting polymer composite anode, described anode composite is to take carbon nano-tube sponge as conducting matrix grain, as matrix load polypyrrole and sulphur active material, forms.
Carbon nano-tube sponge has huge specific area, and more load byte can be provided, thus the more sulphur of load; The three-dimensional conductive network simultaneously forming due to space between its ordered structure and pipe is nanoscale, can make sulphur active material dispersed with nano shape, closely compound with conducting matrix grain, improves better the reactivity of sulphur; Simultaneously, to being filled in the sulphur in space in nanotube and between pipe, the orderly hole of these nanoscales and the major diameter of network channel and nanotube can produce than more confinement effect and the suction-operated of " long-range " of common carbon-based material, can suppress dissolving of sulfur-bearing reduzate in electrolyte, thereby slow down the loss of sulphur.
In addition, because described electrode is without adding conductive agent and binding agent, can significantly improve the specific capacity of electrode, the energy density of electrode is higher.
The present invention also aims to provide a kind of preparation method of carbon nano-tube sponge conducting polymer composite anode.
The present invention also aims to provide a kind of secondary aluminium cell of applying this anodal preparation.
(2) technical scheme
For achieving the above object, the invention provides following technical scheme:
A carbon nano-tube sponge conducting polymer composite anode, comprising:
(a) carbon nano-tube sponge;
(b) polypyrrole; With
(c) elemental sulfur.
Carbon nano-tube sponge described in scheme has dimensional network structure and bigger serface.
Carbon nano-tube sponge conducting polymer composite anode described in scheme, is characterized in that, polypyrrole is by the mode enveloped carbon nanometer tube sponge of in-situ polymerization.
Carbon nano-tube sponge conducting polymer composite anode described in scheme, is characterized in that, described elemental sulfur infiltrates in carbon nano-tube sponge/polypyrrole material by hot melt diffusion way.
Carbon nano-tube sponge conducting polymer composite anode described in scheme, is characterized in that, the ratio of carbon nano-tube sponge, polypyrrole and sulphur is 1:50 ~ 100:250 ~ 1500.
A preparation method for carbon nano-tube sponge conducting polymer composite anode described in scheme, is characterized in that comprising the steps:
The preparation of step 1 carbon nano-tube sponge: add carbon nano-tube and surfactant dodecyl sodium sulfate in container, make gluey carbon nano-tube by sol-gal process, then by making carbon nano-tube sponge with liquid carbon dioxide exchange of solvent;
The preparation of step 2 carbon nano-tube sponge/Pt/Polypyrrole composite material: by the carbon nano-tube sponge after vacuumize and pyrroles in mass ratio 1:50 ~ 1:100 be placed in round-bottomed flask, the ammonium persulfate solution that preparation mass fraction is 2% ~ 10%, with separatory funnel, solution is dripped in round-bottomed flask, the mass ratio that makes ammonium persulfate and pyrroles is 1:2 ~ 1:6, ice bath dipping 12 ~ 30h, shift out liquid, with deionized water and ethanol, compound is washed 6 ~ 20 times, be finally placed in vacuumize 6 ~ 18h under 30 ~ 60 ℃ of conditions;
The preparation of step 3 carbon nano-tube sponge conducting polymer composite anode: by the carbon nano-tube sponge/polypyrrole preparing and elemental sulfur in mass ratio 1:5 ~ 1:15 put into the reactor of the airtight polytetrafluoroethylene that contains nitrogen, be placed in baking oven and be heated to 120 ~ 300 ℃ and sulphur fully melted and be diffused into carbon nano-tube sponge/Pt/Polypyrrole composite material hole, be cooled to room temperature and obtain carbon nano-tube sponge conducting polymer composite anode.
In step 3, the mode of described heating sulphur fusing, is characterized in that, adopts the mode that is once heated to uniform temperature or heating-cooling-heating to carry out.
Scheme also provides a kind of secondary aluminium cell, comprising:
(a) positive pole, is characterized in that, described just very above-mentioned carbon nano-tube sponge conducting polymer composite anode;
(b) containing aluminium negative pole;
(c) non-water is containing aluminium electrolyte.
Secondary aluminium cell described in scheme also can comprise the barrier film between positive pole and negative pole.Suitable solid porous diaphragm material includes but not limited to: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.
Described in scheme containing aluminium negative active core-shell material, include but not limited to: aluminum metal, for example aluminium foil and be deposited on the aluminium on base material; Aluminium alloy, comprises and contains at least one element of being selected from Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Mn, Sn, Pb, Ma, Ga, In, Cr, Ge and the alloy of Al.
Non-water described in scheme is organic salt-aluminum halide system ionic liquid containing aluminium electrolyte, and wherein, the mol ratio of organic salt and aluminum halide is 1:1.1 ~ 3.0.
In organic salt-aluminum halide system described in scheme, the cation of organic salt comprises imidazol ion, pyridinium ion, pyrroles's ion, piperidines ion, morpholine ion, quaternary ammonium salt ion ， quaternary alkylphosphonium salt ion and tertiary sulfosalt ion; The anion of organic salt comprises Cl
-, Br
-, I
-, PF
6 -, BF
4 -, CN
-, SCN
-, [N (CF
3sO
2)
2]
-, [N (CN)
2]
-plasma.
Organic salt-aluminum halide system described in scheme, is characterized in that, described aluminum halide is a kind of in aluminium chloride, aluminium bromide or silver iodide.
Described in scheme, the preparation method of secondary aluminium cell is as follows: after the carbon sulphur anode composite of above-mentioned preparation is dry, be cut into 40mm wide * pole piece that the long 0.33mm of 15mm is thick, be wound into battery core with the thick non-negative pole of knitting barrier film and making as negative active core-shell material with aluminium flake of glass fibre of 0.16mm and pack nickel plating box hat into, the non-water that reinjects is containing aluminium electrolyte, and AA type secondary aluminium cell is made in sealing.
(3) beneficial effect
1) the present invention adopts situ aggregation method to prepare carbon nano-tube sponge conducting polymer composite anode, this anode composite has the advantages such as specific area that carbon nano-tube sponge is large and polypyrrole satisfactory electrical conductivity on the one hand, has also made up on the other hand the electrode material unsteadiness causing due to volumetric expansion in polypyrrole charge and discharge process.
2) the carbon nano-tube sponge conducting polymer composite anode that prepared by the present invention has three-dimensional three-dimensional conductive network structure, can transmit better ion and electronics, thereby improves electric conductivity and the specific discharge capacity of material; Its stereochemical structure and large specific area can also be adsorbed the reduzate in sulphur active material and discharge process well simultaneously, improve the cycle performance of anode composite.
3) preparation of this positive pole, without additional conductive agent and binding agent, can further promote the specific capacity of electrode, and method is simple to operate, cost is low.
4) apply that secondary aluminium cell energy density of this anodal preparation is high, capacity large, good cycle, price economy, Environmental Safety and application prospect extensive.
(4) embodiment
Below with reference to embodiment, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.The following examples have been described several execution mode of the present invention, and they are only illustrative, and nonrestrictive.
embodiment 1:
1) preparation of carbon nano-tube sponge: carbon nano-tube and dodecyl sodium sulfate surfactant are placed in to container, be put in ultrasonic disperser and form suspension, in suspension, the mass fraction of carbon nano-tube is 10mg/ml, the mass ratio of surfactant and carbon nano-tube is 5:1, then places 12h and forms gel; Exchange of solvent is carried out in the water-bath that gel is placed in to 90 ℃ of polyvinyl alcohol that contain 5% mass fraction, and exchange of solvent 3 days is changed polyvinyl alcohol water solution every day one time; Gel is first put in to quick-frozen in liquid nitrogen, is placed in freeze-dryer and keeps 12h; Finally gel is placed in to liquid carbon dioxide and keeps 10min, obtain carbon nano-tube sponge.
2) preparation of carbon nano-tube sponge/Pt/Polypyrrole composite material: by the carbon nano-tube sponge after vacuumize and pyrroles in mass ratio 1:50 be placed in round-bottomed flask, the ammonium persulfate solution that preparation mass fraction is 6%, with separatory funnel, solution is dripped in round-bottomed flask, the mass ratio that makes ammonium persulfate and pyrroles is 1:2, ice bath, dipping 18h, shifts out liquid, with deionized water and ethanol, compound is washed 15 times, be finally placed in vacuumize 10h under 45 ℃ of conditions.
3) preparation of carbon nano-tube sponge conducting polymer composite anode: by the carbon nano-tube sponge/polypyrrole preparing and sulphur in mass ratio 1:5 put into the reactor of the airtight polytetrafluoroethylene that contains nitrogen, be placed in baking oven and be heated to 160 ℃ and sulphur fully melted and be diffused into carbon nano-tube sponge/Pt/Polypyrrole composite material hole, be cooled to room temperature and obtain carbon nano-tube sponge conducting polymer composite anode.
4) preparation of secondary aluminium cell: after the carbon sulphur anode composite of above-mentioned preparation is dry, be cut into 40mm wide * pole piece that the long 0.33mm of 15mm is thick, be wound into battery core with the thick non-negative pole of knitting barrier film and making as negative active core-shell material with aluminium flake of glass fibre of 0.16mm and pack nickel plating box hat into, aluminium chloride-triethylamine hydrochloride ionic liquid electrolyte that reinjects, AA type secondary aluminium cell is made in sealing.
embodiment 2:
1) preparation of carbon nano-tube sponge/Pt/Polypyrrole composite material: by the carbon nano-tube sponge after vacuumize and pyrroles in mass ratio 1:80 be placed in round-bottomed flask, the ammonium persulfate solution that preparation mass fraction is 8%, with separatory funnel, solution is dripped in round-bottomed flask, the mass ratio that makes ammonium persulfate and pyrroles is 1:2, ice bath, dipping 16h, shifts out liquid, with deionized water and ethanol, compound is washed 15 times, be finally placed in vacuumize 10h under 45 ℃ of conditions.
2) other are with embodiment 1.
embodiment 3:
1) preparation of carbon nano-tube sponge conducting polymer composite anode: under argon atmosphere, carbon nano-tube sponge and elemental sulfur are put into the air that polytetrafluoroethylene reactor then continues to pass into nitrogen 30min discharge reactor by 1:5 mass ratio; Under the argon gas atmosphere that flows, carbon nano-tube sponge and elemental sulfur mixture are heated to 120 ℃ of left and right, at this temperature, keep 2h, after be heated to about 150 ℃ insulation 1h, after cooling to again 120 ℃, be heated to 150 ℃, at this temperature, be incubated 1h, repeated multiple timesly sulphur is fully melted and be diffused in carbon nano-tube sponge/polypyrrole, naturally cooling, obtain the carbon sulphur anode composite based on carbon nano-tube sponge.
2) other are with embodiment 2.
embodiment 4
Made battery is carried out to charge and discharge cycles test, with 1C, charge to 2.2V, 0.5C electric discharge, discharge cut-off voltage is 1.2V, test result is as follows:
1) the made battery of embodiment mono-material, open circuit voltage 1.82V, discharge capacity 920mAh, circulates after 50 times first, and capacity attenuation rate is 21.2%.
2) the made battery of embodiment bis-material, open circuit voltage 1.85V, discharge capacity 936mAh, circulates after 50 times first, and capacity attenuation rate is 22.7%.
3) the made battery of embodiment tri-material, open circuit voltage 1.83V, discharge capacity 925mAh, circulates after 50 times first, and capacity attenuation rate is 20.2%.
Although the present invention is described in detail with reference to embodiment, but those skilled in the art is to be understood that, in the situation that do not depart from the spirit and scope of the present invention described in appended claims and equivalent thereof, can make various modifications and replacement to it.
Claims (6)
1. a carbon nano-tube sponge conducting polymer composite anode, comprising:
(a) carbon nano-tube sponge;
(b) polypyrrole; With
(c) elemental sulfur.
2. carbon nano-tube sponge conducting polymer composite anode as claimed in claim 1, is characterized in that, polypyrrole is by the mode enveloped carbon nanometer tube sponge of in-situ polymerization.
3. carbon nano-tube sponge conducting polymer composite anode as claimed in claim 1, is characterized in that, the mode that elemental sulfur spreads by hot melt is infiltrated in carbon nano-tube sponge conducting polymer composite anode.
4. carbon nano-tube sponge conducting polymer composite anode as claimed in claim 1, is characterized in that, the ratio of carbon nano-tube sponge, polypyrrole and sulphur is 1:50 ~ 100:250 ~ 1500.
5. a preparation method for carbon nano-tube sponge conducting polymer composite anode as claimed in claim 1, is characterized in that comprising the following steps:
The preparation of step 1 carbon nano-tube sponge: add carbon nano-tube and surfactant dodecyl sodium sulfate in container, make gluey carbon nano-tube by sol-gal process, then by obtaining carbon nano-tube sponge with liquid carbon dioxide exchange of solvent;
The preparation of step 2 carbon nano-tube sponge/Pt/Polypyrrole composite material: by the carbon nano-tube sponge after vacuumize and pyrroles in mass ratio 1:50 ~ 1:100 be placed in round-bottomed flask, the ammonium persulfate solution that preparation mass fraction is 2% ~ 10%, with separatory funnel, solution is dripped in round-bottomed flask, the mass ratio that makes ammonium persulfate and pyrroles is 1:2 ~ 1:6, ice bath dipping 12 ~ 30h, shift out liquid, with deionized water and ethanol, compound is washed 6 ~ 20 times, be finally placed in vacuumize 6 ~ 18h under 30 ~ 60 ℃ of conditions;
The preparation of step 3 carbon nano-tube sponge conducting polymer composite anode: by the carbon nano-tube sponge/polypyrrole preparing and elemental sulfur in mass ratio 1:5 ~ 1:15 put into the reactor of the airtight polytetrafluoroethylene that contains nitrogen, be placed in baking oven and be heated to 120 ~ 300 ℃ and sulphur fully melted and be diffused into carbon nano-tube sponge/Pt/Polypyrrole composite material hole, be cooled to room temperature and obtain carbon nano-tube sponge conducting polymer composite anode.
6. a secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that:
(a) positive pole, is characterized in that, carbon nano-tube sponge conducting polymer composite anode just very as claimed in claim 1;
(b) containing aluminium negative pole;
(c) non-water is containing aluminium electrolyte.
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| CN114940778A (en) * | 2022-06-30 | 2022-08-26 | 江苏集萃脑机融合智能技术研究所有限公司 | Sponge gel composite electrode and preparation method and application thereof |
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| CN114940778A (en) * | 2022-06-30 | 2022-08-26 | 江苏集萃脑机融合智能技术研究所有限公司 | Sponge gel composite electrode and preparation method and application thereof |
| CN114940778B (en) * | 2022-06-30 | 2023-08-15 | 江苏集萃脑机融合智能技术研究所有限公司 | Sponge gel composite electrode and preparation method and application thereof |
| CN116885196A (en) * | 2023-09-06 | 2023-10-13 | 潍坊科技学院 | Polypyrrole@three-dimensional cavity carbon skeleton composite electrode material and preparation and application thereof |
| CN116885196B (en) * | 2023-09-06 | 2023-12-22 | 潍坊科技学院 | Polypyrrole@three-dimensional cavity carbon skeleton composite electrode material and preparation and application thereof |
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|---|---|
| CN104218230B (en) | 2016-09-07 |
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