CN204189873U - A kind of polypyrrole sulphur positive pole based on graphene array and secondary aluminium cell - Google Patents
A kind of polypyrrole sulphur positive pole based on graphene array and secondary aluminium cell Download PDFInfo
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- CN204189873U CN204189873U CN201420583433.XU CN201420583433U CN204189873U CN 204189873 U CN204189873 U CN 204189873U CN 201420583433 U CN201420583433 U CN 201420583433U CN 204189873 U CN204189873 U CN 204189873U
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- polypyrrole
- positive pole
- graphene array
- sulphur
- graphene
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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 polypyrrole sulphur positive pole based on graphene array and secondary aluminium cell.Described positive pole is to have the graphene array of conductive substrates for three-dimensional conductive skeleton, sulfur-bearing active material is uniformly distributed in conducting matrix grain, the coated polypyrrole of outermost layer, without the need to adding conductive agent and binding agent in preparation process, operation is simple, with low cost, energy density is high, effectively can improve the specific capacity of secondary aluminium cell, stability and cyclicity.
Description
Technical field
The invention belongs to battery and new energy field, relate to a kind of polypyrrole sulphur positive pole based on graphene array.The invention still further relates to a kind of secondary aluminium cell of this anode composite of application.
Background technology
Regenerative resource is grid-connected, the develop rapidly of the new energy technology such as electric automobile and intelligent grid is in the urgent need to developing the energy storage system of more high-energy-density.Secondary aluminium-sulfur battery is as emerging battery system, and be take metallic aluminium as negative pole, sulphur or sulfur-based compound are the battery system of positive pole, has aboundresources, pollution-free, cheap, energy density is high, the feature such as use safety.The theoretical volume specific capacity of aluminium is 8050mAh/cm
3, be 4 times of lithium, and chemical activity is stablized, and be 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.But, the dissolving in organic electrolyte due to the nonconducting natural quality of elemental sulfur and electric discharge intermediate product, easily cause the utilance of active material low, electrode passivation, the capacity of battery declines, the problems such as cycle performance difference, one of approach of solution is by sulfur-bearing active material and has the high carbon-based material of confinement effect, adsorption effect and conductivity and conducting polymer materials compound.
Graphene is a kind of carbon element class material of accurate Colloidal particles, the great specific area had, and the conductivity of superelevation and outstanding heat conductivility are one of desirable energy storage materials.But, because Graphene is very easily reunited, this greatly reduces its surface area as electrode material, seriously reduce its actual specific area and the performance as active ingredient carriers, electrolyte is not only made to be difficult to fully contact with graphenic surface, and the adsorbance of active material is few, utilance is low.
Polypyrrole has higher conductivity, high energy storage capacity, good stability, high electrochemical redox characteristic, and ion freely can transmit in film, is a kind of ideal electrode material.But charcoal base electrode cycle life is unstable relatively, expansion and the contraction of volume can occur in charge and discharge process, easily come off from electrode.
Summary of the invention
(1) goal of the invention
For the deficiency that prior art exists, the object of the present invention is to provide a kind of graphene array-polypyrrole-sulphur anode composite, wherein Graphene vertical oriented growth is in conductive substrates, in three-dimensional net structure, form the conducting matrix grain of electrode, the sulfur-bearing active material of supporting nanostructures on it, then by polypyrrole is coated.
Graphene array is orderly laminated structure and open bore structure, form the three-dimensional network conducting matrix grain of nano-scale, there is the advantages such as specific surface is huge, absorption affinity strong, good stability, electro transfer and charge transfer are fast, the excellent specific property of Graphene itself can be given full play to.The network configuration of its nano-scale has strong absorption confinement effect, with sulphur compound tense, more active material load byte not only can be provided, sulphur is fixed in further absorption, sulphur is connected with conducting matrix grain on nanoscale, greatly promote activity and the utilance of sulphur, but also can fetter and suppress the dissolving of the intermediate products such as Small molecular sulfide, thus slow down the loss of sulphur.The coating function of polypyrrole can fix sulphur further, suppresses it to run off.Simultaneously polypyrrole can also supplementing as active material, promotes electrode capacity further, and then promote cell integrated efficiency for charge-discharge and cycle performance.In addition, owing to eliminating the interpolation of binding agent and conductive agent in electrode production process, can further improve the specific capacity of electrode.
The present invention also aims to provide a kind of secondary aluminium cell comprising above-mentioned anode composite.
(2) technical scheme
For achieving the above object, the present invention takes following technical scheme:
Based on a polypyrrole sulphur positive pole for graphene array, it is characterized in that, described positive pole, to have the graphene array of conductive substrates for three-dimensional conductive skeleton, is uniformly distributed sulfur-bearing active material in conducting matrix grain, the coated polypyrrole of outermost layer.
The polypyrrole sulphur positive pole based on graphene array described in scheme, is characterized in that, Graphene vertically grows on conductive substrates surface.
The polypyrrole sulphur positive pole based on graphene array described in scheme, it is characterized in that, described conductive substrates comprise in carbon fiber, vitrescence carbon, titanium, nickel, stainless steel, iron, copper, zinc, lead, manganese, cadmium, gold, silver, platinum, tantalum, tungsten, conductive plastics, conductive rubber or highly doped silicon any one.
The polypyrrole sulphur positive pole based on graphene array described in scheme, is characterized in that, described sulfur-bearing active material comprises elemental sulfur or the organic compound containing S-S key.
The polypyrrole sulphur positive pole based on graphene array described in scheme, it is characterized in that, described sulfur-bearing active material and polypyrrole are nano-scale.
This section is deleted
The polypyrrole sulphur positive pole based on graphene array described in scheme, is characterized in that, comprise the sulphur of 60 ~ 80%, the polypyrrole of 15 ~ 30% and the graphene array of 5 ~ 15%, described is mass percentage content.
The preparation method of the polypyrrole sulphur positive pole based on graphene array described in scheme, is characterized in that, comprise the following steps:
Step 1, preparation graphene array: by plasma enhanced chemical vapor deposition in conductive substrates superficial growth graphene array;
Step 2, composite sulfur: adopt heat treated mode or adopt the mode of electrochemical deposition to be carried on by sulphur in the graphene array prepared by step 1, form graphene array-sulphur composite material.
Step 3, compound polypyrrole: the graphene array of mode prepared by the step 2-sulphur composite material surface loaded with nano yardstick polypyrrole adopting situ aggregation method or electrochemical deposition, forms the anode composite based on graphene array.
Present invention also offers a kind of secondary aluminium cell, it is characterized in that:
(a) polypyrrole sulphur positive pole based on graphene array according to claim 1;
B () is containing aluminum honeycomb;
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 separator material comprises: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.
Described in scheme 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.
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 described in scheme-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]
-plasma.
Organic salt described in scheme-aluminum halide system, is characterized in that, described aluminum halide is the one in aluminium chloride, aluminium bromide or silver iodide.
Described in scheme, the preparation method of secondary aluminium cell is as follows: described anode composite is cut into 40mm wide × pole piece that 15mm length × 0.33mm is thick, 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 invention provides a kind of polypyrrole sulphur positive pole based on graphene array and comprise the secondary aluminium cell of this positive pole.Described positive pole specific area is huge, substantially increases the load capacity of sulphur, and the strong absorption confinement effect of nano pore and the coated of polypyrrole realize fixing sulphur, suppress the loss of positive active material; Graphene array has three-dimensional network conducting matrix grain simultaneously, and polypyrrole has adhesive effect and has electro-chemical activity, and prepared by electrode eliminate conductive agent and binding agent, preparation section is easy, with low cost, also improves capacity further.The secondary aluminium cell applying this anode composite is doubly forthright good, and energy density is high, and specific capacity, stability and cyclicity are all improved.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, utility model is further illustrated.
Fig. 1 is combined electrode structure schematic diagram described in the utility model.Fig. 2 is the structural representation of secondary aluminium cell described in the utility model.Fig. 3 is the structural representation of winding-structure described in the utility model.Wherein, 1-graphene array, 2-polypyrrole, 3-sulphur, 4-conductive substrates, 5-upper cover, 6-insulated enclosure circle, 7-housing, 8-winding-structure, 9-positive plate, 10-barrier film, 11-negative plate.
(5) embodiment
Below in conjunction with accompanying drawing, utility model is further illustrated.
See accompanying drawing 1, in the present embodiment, anode composite structure chart comprises graphene array 1, polypyrrole 2, sulphur 3.Conductive substrates 4 surface orientation growing graphene array 1, after sulphur 3 compound, at material surface load polypyrrole 2.
See accompanying drawing 2 ~ 3, the utility model also provides a kind of secondary aluminium cell applying this anode composite.Comprise battery container 7, be positioned over winding-structure 8 in battery container 7 and cell cover 5; Wherein said winding-structure comprises the repetitive structure be made up of positive plate 9, barrier film 10 and negative plate 11 successively; Insulated enclosure circle 6 is had between described winding-structure 8 and battery container 7.
Be described further below with reference to the technique effect of embodiment to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.The following examples describe several execution mode of the present invention, and they are only illustrative, and nonrestrictive.
embodiment 1:
(1) graphene array is prepared: be placed in the quartz glass tube of tube type resistance furnace using 30 μm of thick nickel collectors as substrate, pass into argon gas and the hydrogen mixed gas of 1000sccm, wherein hydrogen volume ratio is 1%, is warming up to 650 DEG C simultaneously; Regulation voltage is to 10kV, produce stable glow plasma, remove substrate surface impurity, after 10min, pass into 150sccm methane and 1350sccm argon gas, pass into steam simultaneously, control relative humidity 40%, then stop passing into argon gas and hydrogen mixed gas, reaction 20min, after end at reducing atmosphere borehole cooling to room temperature, take out for subsequent use.
(2) composite sulfur: first configure 0.05mol/LNa
2s
2o
3the aqueous solution, drips below hydrochloric acid to pH value to 4 in this solution, be then work electrode with graphene array, saturated calomel electrode be reference electrode, platinum electrode for electrode, adopt cyclic voltammetry composite sulfur, deposition voltage is 0.6V, reaction time 1h; Finally take out product, through distilled water flushing, dry obtained graphene array-sulphur composite material.
(3) compound polypyrrole: configuration 0.2mol/L Klorvess Liquid, the pyrrole monomer of 0.1mol/L is added in this solution, by the acidity of hydrochloric acid conditioning solution to pH=3.0, graphene array-sulphur composite material is placed in this mixed solution and soaks 20min, then be work electrode with graphene array, saturated calomel electrode is reference electrode, platinum electrode is for electrode, adopt cyclic voltammetry to prepare polypyrrole, electro-deposition voltage is 0.7V, reaction time 0.5h; Finally take out product, through distilled water flushing, dry obtained combination electrode.
(4) secondary aluminium cell preparation method: above-mentioned anode composite is cut into 40mm wide × pole piece that 15mm length × 0.33mm is thick, 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, reinject aluminium chloride-triethylamine hydrochloride ionic liquid, and AA type cylinder secondary aluminium cell is made in sealing.
During battery charging and discharging loop test, carry out charging to 2.5V with 1C, 0.1C discharges, and discharge cut-off voltage is 1.2V.Battery open circuit voltage is 1.76V, and discharge capacity is 861mAh first, and after 50 charge and discharge cycles, capability retention is 82.9%.
embodiment 2:
(1) graphene array method is prepared with embodiment 1.
(2) composite sulfur: by the graphene array prepared and elemental sulfur in mass ratio 1:10 put into tube furnace, be heated to 155 DEG C under nitrogen atmosphere and form graphene array-sulphur composite materials.
(3) compound polypyrrole: by the graphene array prepared-sulphur composite material and pyrrole monomer in mass ratio 5:2 be dissolved in absolute ethyl alcohol after mixing, add dispersant PEG-4000, dopant p-methyl benzenesulfonic acid, initator ferric trichloride, wherein the mol ratio of p-methyl benzenesulfonic acid/pyrroles/ferric trichloride is 0.75:1:0.5, after then reacting 5h at 0 ~ 5 DEG C, take out and at room temperature stir 24h, after filtration, wash, vacuum drying, obtains graphene array-Pt/Polypyrrole composite material.
Secondary aluminium cell preparation method and method of testing are with embodiment 1.
Battery open circuit voltage is 1.75V, and discharge capacity is 854mAh first, and after 50 charge and discharge cycles, capability retention is 83.7%.
embodiment 3:
Preparation graphene array: adopt the stainless steel-based end, enclose iron powder on its surface, be positioned in CVD (Chemical Vapor Deposition) chamber, sealing; In applying magnetic field, substrate transverse direction; magnetic field intensity is 0.01T, passes into 50sccm argon gas 30min to get rid of reaction indoor oxygen, heated substrate to 700 DEG C; then 100sccm methane is passed into; keep 1h, after reaction terminates, stop heating; close methane; under argon shield, be cooled to room temperature, take out product and adopt 1mol/L hydrochloric acid cleaning, dry for standby.
Composite sulfur and composite conductive polymer method are with embodiment 1, and secondary aluminium cell preparation method and method of testing are with embodiment 1.
Battery open circuit voltage is 1.77V, and discharge capacity is 869mAh first, and after 50 charge and discharge cycles, capability retention is 84.1%.
Although reference embodiment is to invention has been detailed description, but those skilled in the art is to be understood that, when not departing from the spirit and scope of the present invention described in appended claims and equivalent thereof, various amendment and replacement can be made to it.
Claims (6)
1. based on a polypyrrole sulphur positive pole for graphene array, it is characterized in that, described positive pole, to have the graphene array of conductive substrates for three-dimensional conductive skeleton, is uniformly distributed sulfur-bearing active material in conducting matrix grain, the coated polypyrrole of outermost layer.
2. as claimed in claim 1 based on the polypyrrole sulphur positive pole of graphene array, it is characterized in that, Graphene vertically grows on conductive substrates surface.
3. as claimed in claim 1 based on the polypyrrole sulphur positive pole of graphene array, it is characterized in that, described conductive substrates comprise in carbon fiber, vitrescence carbon, titanium, nickel, stainless steel, iron, copper, zinc, lead, manganese, cadmium, gold, silver, platinum, tantalum, tungsten, conductive plastics, conductive rubber or highly doped silicon any one.
4. as claimed in claim 1 based on the polypyrrole sulphur positive pole of graphene array, it is characterized in that, described sulfur-bearing active material comprises elemental sulfur or the organic compound containing S-S key.
5., as claimed in claim 1 based on the polypyrrole sulphur positive pole of graphene array, it is characterized in that, described sulfur-bearing active material and polypyrrole are nano-scale.
6. a secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that:
(a) polypyrrole sulphur positive pole based on graphene array according to claim 1;
B () is containing aluminum honeycomb;
C () non-water is containing aluminium electrolyte.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935916A (en) * | 2017-03-01 | 2017-07-07 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of high-performance zinc Polyaniline Secondary Battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935916A (en) * | 2017-03-01 | 2017-07-07 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of high-performance zinc Polyaniline Secondary Battery |
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| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150304 Termination date: 20191010 |
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| CF01 | Termination of patent right due to non-payment of annual fee |