CN204289602U - A kind of combination electrode based on copolymer nano fiber array and the secondary aluminium-sulfur battery comprising this combination electrode - Google Patents
A kind of combination electrode based on copolymer nano fiber array and the secondary aluminium-sulfur battery comprising this combination electrode Download PDFInfo
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- CN204289602U CN204289602U CN201420664852.6U CN201420664852U CN204289602U CN 204289602 U CN204289602 U CN 204289602U CN 201420664852 U CN201420664852 U CN 201420664852U CN 204289602 U CN204289602 U CN 204289602U
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- combination electrode
- fiber array
- nano fiber
- copolymer nano
- aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The utility model discloses a kind of combination electrode based on copolymer nano fiber array and the secondary aluminium-sulfur battery comprising this combination electrode.Described combination electrode comprises collector and coat, and coat is positioned at collector upper and lower surface, and coat comprises active material and binding agent, and wherein, active material is copolymer nano fiber array/sulphur composite material.Described combination electrode eliminates conductive agent, has excellent conductivity and stability, and the secondary aluminium-sulfur battery capacity prepared thus is high, cyclicity good.
Description
Technical field
The utility model belongs to electrochemistry and new forms of energy product scope, relates to a kind of combination electrode based on copolymer nano fiber array and the application in secondary aluminium-sulfur battery thereof.
Background technology
Along with the fast development of the new powers such as electronics and communication apparatus, electric automobile, wind power generation and photovoltaic generation, the battery performance demand of the mankind to supporting power supply is more and more higher, in the urgent need to exploitation electrokinetic cell and energy-storage battery.The secondary cell formed with aluminium and sulphur is a kind of aboundresources, pollution-free, cheap, energy density is high, the energy storage system of use safety, is representative and the direction of secondary cell.
The electrical insulating property of sulphur causes the utilance of sulphur positive active material low, and the discharge and recharge of secondary aluminium-sulfur battery to react the Small molecular sulfur-based compound intermediate product produced soluble in electrolyte, thus cause irreversible loss and the capacity attenuation of active material, cause the self-discharge rate of battery high, cycle life is short, have impact on its large-scale application.
In order to overcome the defect that elemental sulfur exists, being loaded to by elemental sulfur in the conducting polymer materials with high-specific surface area, satisfactory electrical conductivity and stability is one of conventional solution, conventional conducting polymer comprises polyaniline, polypyrrole, polythiophene, polyacrylonitrile etc., usual and material with carbon element, sulphur are compounded to form positive electrode, the mode of in-situ polymerization is adopted to prepare, play the effect improving positive electrode stability, conductivity, specific capacity, also can suppress the molten mistake of sulphur simultaneously, improve cycle performance.Conductive copolymer is compared to single polymers, and in monomer, conjugatedπbond increases, and conductivity and stability are more excellent.
Summary of the invention
(1) goal of the invention
The purpose of this utility model is that the sulphur load capacity improving the existence of existing electrode is on the low side, specific capacity is less than normal, energy density is low, the problems such as capacity attenuation is fast, provide a kind of combination electrode based on copolymer nano fiber array, described electrode active material is copolymer nano fiber array/sulphur composite material, there is ordered three-dimensional structure, carry sulfur content large, energy density be high, conductivity and excellent in stability, prepared secondary aluminium-sulfur battery stability is high, good cycle.
The purpose of this utility model is also to provide a kind of and adopts above-mentioned combination electrode to be the secondary aluminium-sulfur battery of positive pole.
(2) technical scheme
For realizing above-mentioned utility model object, the utility model provides following technical scheme:
Based on a combination electrode for copolymer nano fiber array, comprise collector and coat, it is characterized in that, coat is positioned at collector upper and lower surface, and in coat, active material is copolymer nano fiber array/sulphur composite material.
The combination electrode based on copolymer nano fiber array described in scheme, is characterized in that, described copolymer nano fiber array comprise in polyaniline/polypyrrole, polypyrrole/polythiophene, polyaniline/polythiophene any one.
The combination electrode based on copolymer nano fiber array described in scheme, is characterized in that, described combination electrode is without the need to adding conductive agent.
A kind of secondary aluminium-sulfur battery, comprises positive pole, contains aluminium electrolyte containing aluminum honeycomb and non-water, it is characterized in that, described just very based on the combination electrode of copolymer nano fiber array.
Here is the description of the preferred positive pole of secondary aluminium-sulfur battery of the present invention, negative pole, electrolyte and barrier film.
(1) positive pole
The positive pole of secondary aluminium-sulfur battery described in the utility model comprises positive active material, binding agent and collector.
Positive active material described in the utility model is copolymer nano fiber array/sulphur composite material.
Adhesive described in the utility model be aqueous binder LA132(Chengdu mattress happy), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), Kynoar (PVDF), polystyrenebutadienes copolymer (SBR), Viton and polyurethane, PVP, polyethyl acrylate, polyvinyl chloride, polyacrylonitrile, polycaprolactam, polybutadiene, polyisoprene, polyacrylic acid, and derivative, mixture or copolymer.
Collector described in the utility model comprises stainless steel, copper, nickel, titanium, aluminium.More preferably the aluminium collector of carbon coating, more easily covers the coating comprising positive active material, has lower contact resistance, and can suppress the corrosion of sulfide.
(2) negative pole
Described in the utility model containing aluminum honeycomb active material, comprising: aluminum metal, such as aluminium foil and the aluminium that is deposited on base material; Aluminium alloy, comprises the alloy containing at least one element be selected from Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Mn, Sn, Pb, Ma, Ga, In, Cr, Ge and Al.
(3) electrolyte
Non-water described in the utility model 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 described in the utility model-aluminum halide system, the cation of organic salt comprises imidazol ion, pyridinium ion, pyrrolidinium ion, piperidines ion, morpholinium 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]
-ion.
Organic salt of the present invention-aluminum halide system, is characterized in that, described aluminum halide is the one in aluminium chloride, aluminium bromide or silver iodide.
Organic salt described in the utility model-aluminum halide system comprises aluminium chloride-triethylamine hydrochloride, aluminium chloride-chlorination 1-butyl-3-methylimidazole, aluminium chloride-phenyl trimethicone ammonium chloride, aluminium bromide-1-ethyl-3-methyllimidazolium bromide ionic liquid.
(4) barrier film
Secondary aluminium cell described in the utility model also can comprise the barrier film between positive pole and negative pole.Suitable solid porous separator material comprises polyolefin as the one in polyethylene and polypropylene, glass fiber filter paper and ceramic material.
Being prepared as follows of the combination electrode based on pyrroles/thiophene nanofiber array described in scheme: adopt template synthesis conductive copolymer nanofiber array, heat treated mode is adopted by sulphur to be carried in fiber array surface and space again, then coat 1 is mixed into binding agent, be coated on collector 2, oven dry rolls to 0.3mm thickness, is cut into applicable size and namely obtains compound electric pole piece.
Described in scheme, the preparation method of secondary aluminium-sulfur battery is as follows: with the compound electric pole piece of above-mentioned preparation for positive pole, the barrier film thick with 0.16mm and be wound into battery core with aluminium flake as the negative pole that negative active core-shell material is made and load nickel plating box hat, reinject electrolyte, and secondary aluminium cell is made in sealing.
(3) beneficial effect
The utility model provides a kind of combination electrode based on copolymer nano fiber array, and with the secondary aluminium-sulfur battery that this electrode is positive pole.Above-mentioned combination electrode has ordered three-dimensional structure, and carry sulfur content large, energy density is high.Compare single conducting polymer, copolymer is due to conjugatedπbond increase in monomer, and conductivity and stability are more excellent, and the secondary aluminium-sulfur battery stability prepared thus is high, good cycle.
(4) accompanying drawing explanation
Fig. 1 is anode composite structural representation described in the utility model.
Fig. 2 is secondary aluminium-sulfur battery structural representation described in the utility model.
Fig. 3 is winding-structure schematic diagram described in the utility model.
Wherein, 1-coat, 2-collector, 4-upper cover, 5-insulated enclosure circle, 6-housing, 7-winding-structure, 8-anode pole piece, 9-barrier film, 10-cathode pole piece.
(5) embodiment
Be described further below with reference to embodiment and the accompanying drawing technique effect to design of the present utility model, concrete structure and generation, to understand the purpose of this utility model, characteristic sum effect fully.The following examples describe several execution mode of the present utility model, and they are only illustrative, and nonrestrictive.
As shown in Figure 1, the combination electrode based on copolymer nano fiber array described in this embodiment, comprise collector 2 and coat 1, coat 1 is positioned at collector 2 upper and lower surface, coat 1 comprises active material and binding agent, wherein, active material is copolymer nano fiber array/sulphur composite material.
As shown in Fig. 2 ~ 3, the secondary aluminium cell described in this embodiment, it comprises battery container 6, be positioned over winding-structure 7 in battery container 6 and cell cover 4; Wherein said winding-structure comprises the repetitive structure be made up of anode pole piece 8, barrier film 9 and cathode pole piece 10 successively; Insulated enclosure circle 5 is had between described winding-structure 7 and battery container.
The secondary aluminium cell carbon sulphur anode composite that the utility model provides, wherein in active material, sulphur adopts heat treated mode uniform load in copolymer fibre array surface, combined temp is preferably 300-450 DEG C, and the mass ratio of copolymer fibre and sulphur is preferably 10:1-15:1.
Embodiment 1
Based on a combination electrode for copolymer nano fiber array, comprise collector 2 and coat 1.Wherein, collector 2 is the nickel foam that 0.15mm is thick, and coat 1 is made up of active material polyaniline/polythiophene nanofiber array/sulphur composite material and binding agent, and thickness is 0.2mm, and coat is positioned at collector 2 upper and lower surface.In active material, the mass ratio of polyaniline/polythiophene nanofiber array and sulphur is 15:1, and the temperature of composite sulfur is 450 DEG C.
Be positive plate with above-mentioned, be assembled into secondary aluminium-sulfur battery together with barrier film, electrolyte, aluminum honeycomb, shell.
Embodiment 2
Based on a combination electrode for copolymer nano fiber array, comprise collector 2 and coat 1.Wherein, collector 2 is the aluminium foil that 0.1mm is thick, and coat 1 is made up of active material polyaniline/polypyrrole nanofiber array/sulphur composite material and binding agent, and thickness is 0.2mm, and coat is positioned at collector 2 upper and lower surface.In active material, the mass ratio of polyaniline/polypyrrole nanofiber array and sulphur is 10:1, and the temperature of composite sulfur is 400 DEG C.
Be positive plate with above-mentioned, be assembled into secondary aluminium-sulfur battery together with barrier film, electrolyte, aluminum honeycomb, shell.
Embodiment 3
Based on a combination electrode for copolymer nano fiber array, comprise collector 2 and coat 1.Wherein, collector 2 is the aluminium foil that 0.1mm is thick, and coat 1 is made up of active material polypyrrole/polythiophene nanofiber array/sulphur composite material and binding agent, and thickness is 0.2mm, and coat is positioned at collector 2 upper and lower surface.In active material, the mass ratio of polypyrrole/polythiophene nanofiber array and sulphur is 15:1, and the temperature of composite sulfur is 400 DEG C.
Be positive plate with above-mentioned, be assembled into secondary aluminium-sulfur battery together with barrier film, electrolyte, aluminum honeycomb, shell.
Embodiment 4
Based on a combination electrode for copolymer nano fiber array, comprise collector 2 and coat 1.Wherein, collector 2 is the nickel foam that 0.15mm is thick, and coat 1 is made up of active material polypyrrole/polythiophene nanofiber array/sulphur composite material and binding agent, and thickness is 0.2mm, and coat is positioned at collector 2 upper and lower surface.In active material, the mass ratio of polypyrrole/polythiophene nanofiber array and sulphur is 13:1, and the temperature of composite sulfur is 300 DEG C.
Be positive plate with above-mentioned, be assembled into secondary aluminium-sulfur battery together with barrier film, electrolyte, aluminum honeycomb, shell.
Embodiment 5
Carry out charge and discharge cycles test to secondary aluminium-sulfur battery prepared in embodiment 1-4, carry out charging to 2.5V with 1C, 0.1C discharges, and discharge cut-off voltage is 1.2V.Test result is as following table.
Table 1 secondary aluminium cell
Although be described in detail the utility model with reference to embodiment, but those skilled in the art is to be understood that, when the design of the present utility model do not departed from described in appended claims and equivalent thereof and scope, various amendment and replacement can be made to it.
Claims (6)
1. based on a combination electrode for copolymer nano fiber array, comprise collector and coat, it is characterized in that, coat is positioned at collector upper and lower surface, and in coat, active material is copolymer nano fiber array/sulphur composite material.
2., as claimed in claim 1 based on the combination electrode of copolymer nano fiber array, it is characterized in that, described copolymer nano fiber array comprise in polyaniline/polypyrrole, polypyrrole/polythiophene, polyaniline/polythiophene any one.
3., as claimed in claim 1 based on the combination electrode of copolymer nano fiber array, it is characterized in that, described combination electrode is without the need to adding conductive agent.
4. a secondary aluminium-sulfur battery, comprises positive pole, contains aluminium electrolyte containing aluminum honeycomb and non-water, it is characterized in that, the combination electrode based on copolymer nano fiber array in described just very claim 1.
5. secondary aluminium-sulfur battery as claimed in claim 4, is characterized in that, the described aluminum honeycomb that contains comprises aluminum metal or aluminium alloy.
6. secondary aluminium-sulfur battery as claimed in claim 4, is characterized in that, described non-water comprises organic salt-aluminum halide system ionic liquid containing aluminium electrolyte.
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|---|---|---|---|
| CN201420664852.6U CN204289602U (en) | 2014-11-07 | 2014-11-07 | A kind of combination electrode based on copolymer nano fiber array and the secondary aluminium-sulfur battery comprising this combination electrode |
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|---|---|---|---|
| CN201420664852.6U CN204289602U (en) | 2014-11-07 | 2014-11-07 | A kind of combination electrode based on copolymer nano fiber array and the secondary aluminium-sulfur battery comprising this combination electrode |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106653394A (en) * | 2016-12-30 | 2017-05-10 | 吉林大学 | Pyrrole and 3,4-ethylenedioxythiophene copolymerization nanowire array and preparation method |
-
2014
- 2014-11-07 CN CN201420664852.6U patent/CN204289602U/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106653394A (en) * | 2016-12-30 | 2017-05-10 | 吉林大学 | Pyrrole and 3,4-ethylenedioxythiophene copolymerization nanowire array and preparation method |
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Granted publication date: 20150422 Termination date: 20191107 |
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| CF01 | Termination of patent right due to non-payment of annual fee |