CN104218230B - A kind of CNT sponge conducting polymer composite anode for secondary cell - Google Patents
A kind of CNT sponge conducting polymer composite anode for secondary cell Download PDFInfo
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- CN104218230B CN104218230B CN201410493605.9A CN201410493605A CN104218230B CN 104218230 B CN104218230 B CN 104218230B CN 201410493605 A CN201410493605 A CN 201410493605A CN 104218230 B CN104218230 B CN 104218230B
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- H01M4/00—Electrodes
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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Abstract
The invention discloses a kind of CNT sponge conducting polymer composite anode, preparation method and application.This anode composite is with CNT sponge as substrate, spreads sulfur loaded active material by in-situ polymerization polypyrrole and hot melt.The conductive network that CNT sponge and polypyrrole are formed after being combined has confinement effect, adsorption effect and electric conductivity high, can adsorb sulphur active material and suppress the dissolving of sulphur reduzate, improves electric conductivity and the cycle performance of positive pole further.This anode composite is without adding conductive agent and binding agent, and preparation section is simple, with low cost, and energy density is high.
Description
Technical field
The invention belongs to battery material and new energy field, relate to a kind of CNT sponge conducting polymer, secondary aluminium cell prepared by this electrode of preparation method and application.
Background technology
The energy storage system developed rapidly in the urgent need to developing higher energy density of the new energy technologies such as regenerative resource is grid-connected, electric automobile and intelligent grid.Secondary aluminium-sulfur battery, as emerging battery system, is with metallic aluminium as negative pole, and sulphur or sulfur-based compound are the battery system of positive pole, 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/cm3, it is 4 times of lithium, and chemical activity is stable, is preferable negative material；And the theoretical volume specific capacity of sulphur is 3467mAh/cm3, it is one of positive electrode that known energy density is the highest.But, due to the nonconducting attribute of elemental sulfur and discharging product dissolving in the electrolytic solution, the utilization rate being easily caused active material is low, electrode passivation, the problems such as battery capacity declines, cycle performance difference, solution is that sulfur-bearing active material and carbon-based material and conducting polymer are combined.
Wherein, CNT has and conducts electricity very well, and the advantages such as draw ratio is big can be barricaded as natural conductive network with bridge between them, and beneficially the conduction of electronics and the diffusion of ion, be widely used in battery electrode material.Traditional CNT mostly is unordered reunion shape, the main suction-operated sulfur loaded by CNT sponge surface, limited by carbon-based material loose structure and surface chemistry simultaneously, sulphur is the most weak with the interaction on carbon matrix surface, causing that sulphur content in carbon matrix is low, skewness, during discharge and recharge, a large amount of sulphur can directly dissolve in electrolyte from the surface of CNT, causing the loss of active material, battery energy density is difficult to improve.Therefore, only it is difficult to thoroughly to suppress the loss by dissolution of many polysulfides, cycle performance can't reach practical degree by the confinement effect of material with carbon element hole and adsorption effect.
Polypyrrole has good electrical conductivity and stability, high energy storage capacity and high electrochemical redox characteristic, and ion freely can transmit in film, is a kind of preferably electrode material.But relative carbon electrode, cycle life is unstable, expansion and the contraction of volume easily occurs in charge and discharge process, easily comes off from electrode.
Summary of the invention
(1) goal of the invention
For the problems referred to above and deficiency, it is an object of the invention to provide a kind of CNT sponge conducting polymer composite anode, described anode composite is with CNT sponge as conducting matrix grain, forms as matrix load polypyrrole and sulphur active material.
CNT sponge has huge specific surface area, it is possible to provide more load byte, thus loads more sulphur；Simultaneously because the three-dimensional conductive network that between its ordered structure and pipe, space is constituted is nanoscale, sulphur active material can be made dispersed with nano shape, be closely combined with conducting matrix grain, preferably improve the reactivity of sulphur；Simultaneously, to the sulphur in space in being filled in nanotube and between pipe, the major diameter of the orderly hole of these nanoscales and network channel and nanotube can produce the confinement effect than common carbon-based material more " long-range " and suction-operated, the dissolving in the electrolytic solution of sulfur-bearing reduzate can be suppressed, thus slow down the loss of sulphur.
Additionally, due to 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 the preparation method of a kind of CNT sponge conducting polymer composite anode.
The present invention also aims to provide a kind of secondary aluminium cell applying this positive pole to prepare.
(2) technical scheme
For achieving the above object, the technical scheme is that
A kind of CNT sponge conducting polymer composite anode, including:
(a) CNT sponge；
(b) polypyrrole；With
(c) elemental sulfur.
CNT sponge described in scheme has dimensional network structure and bigger serface.
Polypyrrole described in scheme enveloped carbon nanometer tube sponge by the way of in-situ polymerization.
Elemental sulfur described in scheme is penetrated in CNT sponge/polypyrrole material by hot melt diffusion way.
The ratio of CNT sponge, polypyrrole and sulphur described in scheme is 1:50 ~ 100:250 ~ 1500.
The preparation method of the CNT sponge conducting polymer composite anode described in a kind of scheme, comprises the steps:
The preparation of step 1 CNT sponge: add CNT and surfactant sodium dodecyl base sodium sulfonate in a reservoir, prepares gluey CNT by sol-gal process, then by preparing CNT sponge with liquid carbon dioxide exchange of solvent；
The preparation of step 2 CNT sponge/Pt/Polypyrrole composite material: by the CNT sponge after vacuum drying and pyrroles during 1:50 ~ 1:100 is placed in round-bottomed flask in mass ratio, preparation mass fraction is the ammonium persulfate solution of 2% ~ 10%, with separatory funnel, solution is dripped in round-bottomed flask, making ammonium persulfate is 1:2 ~ 1:6 with the mass ratio of pyrroles, ice bath dipping 12 ~ 30h, removal liquid, with deionized water and ethanol, compound is washed 6 ~ 20 times, under the conditions of being finally placed in 30 ~ 60 DEG C, be vacuum dried 6 ~ 18h；
The preparation of step 3 CNT sponge conducting polymer composite anode: the CNT prepared sponge/polypyrrole and elemental sulfur 1:5 ~ 1:15 in mass ratio are put into containing in the reactor of the airtight polytetrafluoroethylene (PTFE) of nitrogen, it is placed in baking oven and is heated to 120 ~ 300 DEG C and makes sulphur fully melt and be diffused in CNT sponge/Pt/Polypyrrole composite material hole, be cooled to room temperature and obtain CNT sponge conducting polymer composite anode.
In step 3, the mode of described heating sulphur fusing, it is characterised in that use the mode being once heated to uniform temperature or heating-cooling-heating to carry out.
Scheme also provides for a kind of secondary aluminium cell, including:
(a) above-mentioned CNT sponge conducting polymer composite anode；
B () contains aluminum honeycomb；
C () is non-aqueous containing aluminium electrolyte.
Secondary aluminium cell described in scheme may also include the barrier film between positive pole and negative pole.Suitably solid porous separator material includes but not limited to: polyolefin such as polyethylene and polypropylene, glass fiber filter paper and ceramic material.
Described in scheme containing aluminum honeycomb active material, include but not limited to: aluminum metal, such as aluminium foil and the aluminium that is deposited on base material；Aluminium alloy, including the alloy containing at least one element in Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Mn, Sn, Pb, Ma, Ga, In, Cr, Ge with Al.
Non-aqueous described in scheme is organic salt-aluminum halide system ionic liquid containing aluminium electrolyte, and wherein, organic salt is 1:1.1 ~ 3.0 with the mol ratio of aluminum halide.
In organic salt described in scheme-aluminum halide system, the cation of organic salt includes imidazol ion, pyridinium ion, pyrrolidinium ion, piperidines ion, morpholinium ion, quaternary ammonium salt ion, quaternary salt ion and tertiary salt ion；The anion of organic salt includes Cl-, Br-, I-, PF6 -, BF4 -, CN-, SCN-, [N (CF3SO2)2]-, [N (CN)2]-Plasma.
Organic salt described in scheme-aluminum halide system, it is characterised in that described aluminum halide is the one in aluminium chloride, aluminium bromide or silver iodide.
The preparation method of secondary aluminium cell described in scheme is as follows: the carbon sulphur anode composite of above-mentioned preparation is cut into 40mm width × long 0.33mm of 15mm thick pole piece after drying, the glass fibre thick with 0.16mm is non-to be knitted barrier film and is wound into battery core loading nickel plating box hat with aluminium flake as the negative pole that negative active core-shell material is made, reinjecting non-aqueous containing aluminium electrolyte, AA type secondary aluminium cell is made in sealing.
(3) beneficial effect
1) present invention uses situ aggregation method to be prepared for CNT sponge conducting polymer composite anode, on the one hand this anode composite has the advantages such as the big specific surface area of CNT sponge and polypyrrole satisfactory electrical conductivity, on the other hand also compensate for the electrode material unstability caused in polypyrrole charge and discharge process due to volumetric expansion.
2) the CNT sponge conducting polymer composite anode that prepared by the present invention has the three-dimensional conductive network structure of solid, can preferably transmit ion and electronics, thus improve electric conductivity and the specific discharge capacity of material；Its stereochemical structure and big specific surface area can also adsorb the reduzate in sulphur active material and discharge process well simultaneously, improve the cycle performance of anode composite.
3) preparation of this positive pole is without additional conductive agent and binding agent, can promote the specific capacity of electrode further, and method is simple to operate, low cost.
4) apply that secondary aluminium cell energy density prepared by this positive pole is high, capacity is big, good cycle, price economy, Environmental Safety and application prospect extensive.
(4) detailed description of the invention
Below with reference to embodiment, the technique effect of design, concrete structure and the generation of the present invention is described further, to be fully understood from the purpose of the present invention, feature and effect.The following examples describe the several embodiments of the present invention, and they are merely illustrative, and nonrestrictive.
Embodiment 1:
1) preparation of CNT sponge: CNT and dodecyl sodium sulfate surfactant are placed in container, it is put in ultrasonic dispersers formation suspension, in suspension, the mass fraction of CNT is 10mg/ml, the mass ratio of surfactant and CNT is 5:1, then places 12h and forms gel；Gel is placed in 90 DEG C and carries out exchange of solvent, exchange of solvent 3 days containing in the water-bath of the polyvinyl alcohol of 5% mass fraction, change a polyvinyl alcohol water solution every day；Gel is first put in quick-frozen in liquid nitrogen, is placed in freeze-dryer holding 12h；Finally gel is placed in liquid carbon dioxide holding 10min, obtains CNT sponge.
2) preparation of CNT sponge/Pt/Polypyrrole composite material: by the CNT sponge after vacuum drying and pyrroles during 1:50 is placed in round-bottomed flask in mass ratio, preparation mass fraction is the ammonium persulfate solution of 6%, with separatory funnel, solution is dripped in round-bottomed flask, the mass ratio making ammonium persulfate and pyrroles is 1:2, ice bath, impregnates 18h, removes liquid, with deionized water and ethanol, compound is washed 15 times, under the conditions of being finally placed in 45 DEG C, be vacuum dried 10h.
3) preparation of CNT sponge conducting polymer composite anode: the CNT prepared sponge/polypyrrole and sulphur 1:5 in mass ratio are put into containing in the reactor of the airtight polytetrafluoroethylene (PTFE) of nitrogen, it is placed in baking oven and is heated to 160 DEG C and makes sulphur fully melt and be diffused in CNT sponge/Pt/Polypyrrole composite material hole, be cooled to room temperature and obtain CNT sponge conducting polymer composite anode.
4) preparation of secondary aluminium cell: the carbon sulphur anode composite of above-mentioned preparation is cut into after drying the thick pole piece of 40mm width × long 0.33mm of 15mm, the glass fibre thick with 0.16mm is non-to be knitted barrier film and is wound into battery core loading nickel plating box hat with aluminium flake as the negative pole that negative active core-shell material is made, reinjecting aluminium chloride-triethylamine hydrochloride ionic liquid electrolyte, AA type secondary aluminium cell is made in sealing.
Embodiment
2
:
1) preparation of CNT sponge/Pt/Polypyrrole composite material: by the CNT sponge after vacuum drying and pyrroles during 1:80 is placed in round-bottomed flask in mass ratio, preparation mass fraction is the ammonium persulfate solution of 8%, with separatory funnel, solution is dripped in round-bottomed flask, the mass ratio making ammonium persulfate and pyrroles is 1:2, ice bath, impregnates 16h, removes liquid, with deionized water and ethanol, compound is washed 15 times, under the conditions of being finally placed in 45 DEG C, be vacuum dried 10h.
2) other are with embodiment 1.
Embodiment
3
:
1) preparation of CNT sponge conducting polymer composite anode: under argon atmosphere, is put into, by CNT sponge and elemental sulfur, the air being then continually fed in polytetrafluoroethylene (PTFE) reactor in nitrogen 30min discharge reactor by 1:5 mass ratio；Under flowing argon gas atmosphere, CNT sponge and elemental sulfur mixture are heated to about 120 DEG C, keep 2h at this temperature, after be heated to about 150 DEG C insulation 1h, it is heated to 150 DEG C after cooling to 120 DEG C again, is incubated 1h at this temperature, repeated multiple times make sulphur fully melt and be diffused in CNT sponge/polypyrrole, naturally cooling, obtains carbon sulphur anode composite based on CNT sponge.
2) other are with embodiment 2.
Embodiment
4
Made battery being carried out charge and discharge cycles test, charges to 2.2V, 0.5C electric discharge with 1C, discharge cut-off voltage is 1.2V, and test result is as follows:
1) the made battery of embodiment one material, open-circuit voltage 1.82V, first discharge capacity 920mAh, after circulating 50 times, capacity attenuation rate is 21.2%.
2) the made battery of embodiment two material, open-circuit voltage 1.85V, first discharge capacity 936mAh, after circulating 50 times, capacity attenuation rate is 22.7%.
3) the made battery of embodiment three material, open-circuit voltage 1.83V, first discharge capacity 925mAh, after circulating 50 times, capacity attenuation rate is 20.2%.
Although the present invention being described in detail with reference to embodiment, but those skilled in the art is to be understood that, in the case of without departing from the spirit and scope of the present invention described in appended claims and equivalent thereof, it can be made various amendment and replacement.
Claims (2)
1. a preparation method for CNT sponge conducting polymer composite anode, comprises the following steps:
The preparation of step 1 CNT sponge: add CNT and surfactant sodium dodecyl base sodium sulfonate in a reservoir, prepares gluey CNT by sol-gal process, then by obtaining CNT sponge with liquid carbon dioxide exchange of solvent；
The preparation of step 2 CNT sponge/Pt/Polypyrrole composite material: by the CNT sponge after vacuum drying and pyrroles during 1:50 ~ 1:100 is placed in round-bottomed flask in mass ratio, preparation mass fraction is the ammonium persulfate solution of 2% ~ 10%, with separatory funnel, solution is dripped in round-bottomed flask, making ammonium persulfate is 1:2 ~ 1:6 with the mass ratio of pyrroles, ice bath dipping 12 ~ 30h, removal liquid, with deionized water and ethanol, compound is washed 6 ~ 20 times, under the conditions of being finally placed in 30 ~ 60 DEG C, be vacuum dried 6 ~ 18h；
The preparation of step 3 CNT sponge conducting polymer composite anode: the CNT prepared sponge/polypyrrole and elemental sulfur 1:5 ~ 1:15 in mass ratio are put into containing in the reactor of the airtight polytetrafluoroethylene (PTFE) of nitrogen, it is placed in baking oven and is heated to 120 ~ 300 DEG C and makes sulphur fully melt and be diffused in CNT sponge/Pt/Polypyrrole composite material hole, be cooled to room temperature and obtain CNT sponge conducting polymer composite anode.
2. the preparation method of CNT sponge conducting polymer composite anode as claimed in claim 1, it is characterised in that: this anode composite can be used for secondary aluminium cell.
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| CN106147226B (en) * | 2015-03-25 | 2018-09-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Elastic conduction hybrid inorganic-organic aeroge and its preparation method and application |
| CN106159221A (en) * | 2015-04-27 | 2016-11-23 | 中国人民解放军63971部队 | A kind of nano-sized carbon sulfur composite for lithium-sulfur cell |
| 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 |
| 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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| CN102593433B (en) * | 2012-02-27 | 2014-08-13 | 清华大学 | Directional carbon nano-tube composite cathode material for lithium-sulfur secondary battery |
| CN103682353A (en) * | 2012-09-12 | 2014-03-26 | 苏州宝时得电动工具有限公司 | Electrode composite material as well as preparation method thereof, positive electrode and battery with same |
| JP2014175246A (en) * | 2013-03-12 | 2014-09-22 | Sony Corp | Secondary battery, method for manufacturing secondary battery, positive electrode for secondary battery, method for manufacturing positive electrode for secondary battery, battery pack, electronic apparatus and electric vehicle |
| CN103450682B (en) * | 2013-08-23 | 2016-01-13 | 清华大学 | A kind of Carbon nanotube/polypyrrolecomposite composite sponge and preparation method thereof |
| CN103840167B (en) * | 2014-03-03 | 2016-03-02 | 东南大学 | Based on selenium/sulphur carbon electrode and preparation method thereof and the application of graphene sponge |
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