CN204243148U - A kind of secondary cell combination electrode and secondary aluminium cell - Google Patents
A kind of secondary cell combination electrode and secondary aluminium cell Download PDFInfo
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- CN204243148U CN204243148U CN201420582444.6U CN201420582444U CN204243148U CN 204243148 U CN204243148 U CN 204243148U CN 201420582444 U CN201420582444 U CN 201420582444U CN 204243148 U CN204243148 U CN 204243148U
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- sulphur
- conducting polymer
- titanium dioxide
- ion
- 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
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Abstract
The utility model discloses a kind of secondary cell combination electrode and secondary aluminium cell.Secondary cell combination electrode comprises electrode active material, binding agent and collector, electrode active material is made up of titanium dioxide, conducting polymer and sulphur, described electrode active material has nucleocapsid structure, its center is sulphur, outside sulphur, be coated with titanium dioxide and conducting polymer, structure is followed successively by sulphur, conducting polymer, titanium dioxide from inside to outside; Or, sulphur, titanium dioxide, conducting polymer.Described secondary aluminium cell, comprises positive pole, negative pole and electrolyte, particularly, and described just very above-mentioned secondary cell combination electrode; Described negative pole, for containing aluminum honeycomb, comprises aluminum metal or aluminium alloy; Described electrolyte is that non-water is containing aluminium electrolyte.Prepared secondary aluminium cell excellent conductivity, specific capacity are high, good cycling stability.
Description
Technical field
The utility model belongs to electrochemistry and new forms of energy product scope, relates to a kind of secondary cell combination electrode, and a kind of secondary aluminium cell that is positive pole with this combination electrode.
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, have that energy is high, cost is low, the life-span is long in the urgent need to exploitation, environmental protection, the electrokinetic cell of battery material aboundresources and reusable edible and energy-storage battery.The theoretical specific capacity of metallic aluminium is only second to lithium, but its volume and capacity ratio is four times of lithium, and higher than other any metal materials, therefore secondary aluminium cell has very high application potential and commercial value.
The positive electrode research of current two secondary aluminium electrodes is more is sulphur class, but sulfur-bearing intermediate product easily dissolves in the electrolytic solution in the process of discharge and recharge, the coulombic efficiency of battery charging and discharging is caused to reduce, and sulfur-bearing intermediate product can form deposition along with electrolyte is diffused into negative terminal surface or reacts formation passivating film with negative pole, reduce negative reaction active, cause irreversible capacitance loss.Therefore, how to improve the conductivity of material, and solve the problems of dissolution of discharge and recharge intermediate product, improving the cycle performance of battery, is the research emphasis of sulfur-based positive electrode material.
Normally elemental sulfur is loaded in the carbon element class material and conducting polymer with high-specific surface area, high porosity and excellent conductive performance at present, form composite positive pole, to limit the various negative effects that sulfur-based compound in cyclic process dissolves in electrolyte and causes thus.Wherein, conducting polymer have store the ability of electric charge high, to oxygen and the advantage such as water stability is good, chemical property is good, density is little, and there is reversible oxidation/reduction characteristic, in composite electrode, not only can be used as conductive matrices but also can be used as active material, be used to the electrode material of high-polymer lithium battery and solar cell etc.
There is at Surface coating one deck of sulphurous materials transient metal sulfide or the oxide of ion selectivity, also can prevent electrode material from contacting with the direct of electrolyte, suppress phase in version, improve composite structure stability, reduce polysulfide and reduzate dissolving in the electrolytic solution thereof with this, reach the cyclic reversibility the object suppressing self discharge that improve battery.
Summary of the invention
(1) goal of the invention
The purpose of this utility model is to solve the problem existing for sulphur positive pole, provide a kind of secondary cell combination electrode, described electrode active material comprises the conducting polymer of nano-scale, titanium dioxide and sulphur, both there is the conductivity that conducting polymer is excellent, there is again the physical and chemical performance of inorganic nano-particle uniqueness simultaneously, excellent electrochemical performance.
Described electrode active material has nucleocapsid structure, is followed successively by sulphur-conducting polymer-titanium dioxide from the inside to surface, or sulphur-titanium dioxide-conducting polymer.The physical and chemical performance such as bulk effect, skin effect specific to the titanium dioxide of nano-scale and conducting polymer, effectively can improve the defect of elemental sulfur and electrochemical reaction product electric conductivity difference thereof, increase substantially the conductive capability of positive active material; Meanwhile, there is certain suction-operated to the intermediate product of exoelectrical reaction, effectively can suppress the molten mistake of sulphur in charge and discharge process; In addition, can cushioning effect be played to the change in volume of sulphur in charge and discharge process thus avoid the destruction of electrode to a certain extent.In addition, without the need to adding conductive agent in addition in electrode production process, the two can also as active material supplement, promote electrode capacity further, and then promote cell integrated efficiency for charge-discharge and cycle performance.
The purpose of this utility model is also to provide a kind of secondary aluminium cell being positive pole with described combination electrode.
(2) technical scheme
For realizing above-mentioned utility model object, the utility model provides following technical scheme:
A kind of secondary cell combination electrode, comprise electrode active material, binding agent and collector, it is characterized in that, electrode active material is made up of titanium dioxide, conducting polymer and sulphur, described electrode active material has nucleocapsid structure, its center is sulphur, is coated with titanium dioxide and conducting polymer outside sulphur, and structure is followed successively by sulphur, conducting polymer, titanium dioxide from inside to outside; Or, sulphur, titanium dioxide, conducting polymer.
Secondary cell combination electrode described in the utility model, is characterized in that, described titanium dioxide, conducting polymer and sulphur are nano-scale.
Secondary cell combination electrode described in the utility model, is characterized in that, described composite material comprises titanium dioxide 5 ~ 15wt%, 10 ~ 25wt% conducting polymer, 60 ~ 75wt% sulphur.
Secondary cell combination electrode described in the utility model, is characterized in that, described conducting polymer comprise in polyaniline, polypyrrole, polythiophene, polyacrylonitrile any one.
The preparation of electrode active material described in the utility model, comprises the steps:
The magister of sulfur of (a) nanometer
Added by a certain amount of concentrated sulfuric acid in the sodium thiosulfate solution containing a small amount of polyvinylpyrrolidone, reaction 2 ~ 3h, forms nano-sulfur particles aaerosol solution, centrifugal filtration, the dry obtained nano-sulfur of washing;
(b) composite conductive polymer
Adopt situ aggregation method, the nano-sulfur prepared is added in the solution containing above-mentioned polymer monomer, adds corresponding dispersant and initator, at nano-sulfur in situ Polymerization conducting polymer;
(c) composite titanium dioxide
Adopt chemical deposition, preparation contains the solution of metal ion corresponding to above-mentioned metal oxide, add elemental sulfur wherein, mixed liquor is placed in about 60 DEG C waters bath with thermostatic control, stirs sonic oscillation simultaneously, after reaction 2 ~ 10h, centrifugation precipitates, clean with deionized water and ethanol purge, about 40 DEG C vacuumizes, obtain composite material;
Wherein, step (b) and (c) can exchange order.
A kind of secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that, just very above-mentioned secondary cell combination electrode, and negative pole is for containing aluminum honeycomb, and electrolyte is that non-water is containing aluminium electrolyte.
Here is the description of the preferred positive pole of secondary aluminium cell described in the utility model, negative pole, electrolyte and barrier film.
(1) positive pole
The positive pole of secondary aluminium cell described in the utility model comprises positive active material, binding agent and collector.
Positive active material described in the utility model comprises titanium dioxide, conducting polymer and sulphur.
Binding agent described in the utility model is aqueous binder LA132, 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 described in the utility model-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 is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.
The preparation method of secondary aluminium cell described in the utility model is as follows: positive electrode active materials, binding agent (ratio is 9:1) are made active material slurry and be applied on the thick collector of 0.6mm, oven dry rolls to about 0.33mm, be cut into 40mm wide × the long pole piece of 15mm is as positive plate, the barrier film thick with 0.16mm and negative pole are wound into battery core 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 anode composite and the application in secondary aluminium-sulfur battery thereof, compared with the existing technology there is following advantage: the physical and chemical performance such as bulk effect, skin effect specific to the titanium dioxide of nano-scale and conducting polymer, effectively can improve the defect of elemental sulfur and electrochemical reaction product electric conductivity difference thereof, increase substantially the conductive capability of positive active material; Meanwhile, there is certain suction-operated to the intermediate product of exoelectrical reaction, effectively can suppress the molten mistake of sulphur in charge and discharge process; In addition, can cushioning effect be played to the change in volume of sulphur in charge and discharge process thus avoid the destruction of electrode to a certain extent.In addition, without the need to adding conductive agent in addition in electrode production process, the two can also as active material supplement, promote electrode capacity further, and then promote cell integrated efficiency for charge-discharge and cycle performance.
Accompanying drawing explanation
Fig. 1 is the anode structure schematic diagram of secondary aluminium cell described in the utility model.
Fig. 2 is positive active material structural representation described in the utility model.
Fig. 3 is the another kind of structural representation of positive active material described in the utility model.
Fig. 4 is the structural representation of secondary aluminium cell described in the utility model.
Fig. 5 is the schematic diagram of winding-structure described in the utility model.
Wherein, 1-collector, 2-material layer, 4-upper cover, 5-insulated enclosure circle, 6-housing, 7-winding-structure, 8-positive plate, 9-barrier film, 11-negative plate, 10-sulphur, 20-conducting polymer, 30-titanium dioxide.
Embodiment
Be described further below with reference to the technique effect of drawings and Examples 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 anode structure of the secondary aluminium cell described in this embodiment, comprises collector 1 and material layer 2; Wherein, material layer 2 includes binding agent and active material; Material layer 2 is coated on collector 1.
As shown in Figure 2, the positive active material structure described in this embodiment, comprises sulphur 10, conducting polymer 20 and titanium dioxide 30, wherein, three is nano-scale, and conducting polymer 20 adopts in-situ polymerization to be coated on sulphur 10 surface, then at outer cladding titanium dioxide 30.
Be illustrated in figure 3 the another kind of structure of positive active material, sulphur 10 in innermost layer, outer first cladding titanium dioxide 30, then at outer coated with conductive polymer 20.
As shown in Fig. 4 ~ 5, 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 positive plate 8, barrier film 9 and negative plate 11 successively; Insulated enclosure circle 5 is had between described winding-structure 7 and battery container.
Embodiment 1
(1) nanometer magister of sulfur: added by a certain amount of concentrated sulfuric acid in the sodium thiosulfate solution containing a small amount of polyvinylpyrrolidone, reaction 2 ~ 3h, forms nano-sulfur particles aaerosol solution, centrifugal filtration, the dry obtained nano-sulfur of washing.
(2) compound polypyrrole: by nano-sulfur and pyrrole monomer in mass ratio 3:1 be dissolved in absolute ethyl alcohol after mixing, ultrasonic disperse 30min, then proceed to and stir under ice-water bath condition, in mixture, add dopant p-methyl benzenesulfonic acid and initator ferric trichloride after temperature stabilization, the mol ratio of p-methyl benzenesulfonic acid/pyrroles/ferric trichloride is 0.75:1:0.5.After reaction 3h, be placed in the ultrasonic 3h of supersonic wave cleaning machine, more at room temperature stir 24h, after filtration, wash, vacuum drying is for subsequent use.
(3) composite titanium dioxide: step (2) described composite material is scattered in 50ml water, the mixed liquor instillation of configuration 8ml butyl titanate and 5ml ethanol wherein, then mixed liquor is placed in about 60 DEG C waters bath with thermostatic control, stir sonic oscillation simultaneously, reaction 5h after, centrifugation precipitate, with deionized water and ethanol purge clean, about 40 DEG C vacuumizes, obtain trielement composite material.
(4) secondary aluminium cell is prepared: be 9:1 by above-mentioned composite material, binding agent PVDF(ratio) make active material slurry and be applied on the aluminium collector of the thick carbon coating of 0.6mm, oven dry rolls to about 0.33mm, be cut into 40mm wide × the long pole piece of 15mm is as positive plate, the glass fibre thick with 0.16mm be non-to be knitted barrier film and negative pole and is wound into battery core and loads nickel plating box hat, reinject aluminium chloride-triethylamine hydrochloride ionic liquid, and AA type cylinder secondary aluminium cell 1# is made in sealing.
Embodiment 2
(1) nanometer magister of sulfur is with embodiment 1.
(2) composite polyphenylene amine: the hydrochloric acid solution containing aniline monomer of configuration 0.15mol/L, add nano-sulfur particle, wherein aniline monomer and nano-sulfur mass ratio are 3:1, and ultrasonic disperse 3h, is then placed in there-necked flask by mixed liquor, cool in ice-water bath, after temperature stabilization, slowly drip 0.02mol/L ammonium persulfate solution wherein, stirring reaction 8h, products therefrom through filtering and washing, drying for standby at 60 DEG C.
(3) method of composite titanium dioxide is with embodiment 1.
(4) secondary aluminium cell is prepared: be 7:2:1 by above-mentioned composite material, conductive agent, binding agent PVDF(ratio) make active material slurry and be applied on the thick nickel foam substrate of 0.6mm, oven dry rolls to about 0.33mm, be cut into 40mm wide × the long pole piece of 15mm is as positive plate, the glass fibre thick with 0.16mm be non-to be knitted barrier film and negative pole and is wound into battery core and loads nickel plating box hat, reinject aluminium bromide-triethylamine hydrochloride ionic liquid, and AA type cylinder secondary aluminium cell 2# is made in sealing.
Embodiment 3
(1) nanometer magister of sulfur is with embodiment 1.
(2) compound polythiophene: add in chloroform by the nano-sulfur particle prepared, ultrasonic disperse 4h, then adds thiophene monomer, continue to stir 2h after being uniformly dispersed, add initator anhydrous ferric trichloride, stirred at ambient temperature reaction 6h, filter, washing, 50 DEG C of vacuumize 24h are for subsequent use.
(3) method of the preparation of composite titanium dioxide and secondary aluminium cell is with embodiment 1, obtained secondary aluminium cell 3#.
Embodiment 4
(1) nanometer magister of sulfur is with embodiment 1.
(2) composite polypropylene nitrile: the mixed solution of configuration dimethyl sulfoxide (DMSO) and water (mass ratio is 1:1); add 20wt% acrylonitrile; initiator ammonium persulfate; be placed in one the nano-sulfur particle prepared ultrasonic disperse 5h; Keep agitation be warming up to 50 DEG C under nitrogen protection; product is taken out, washing and drying trielement composite material after insulation 8h.
(3) method of the preparation of composite titanium dioxide and secondary aluminium cell is with embodiment 2, obtained secondary aluminium cell 4#.
Embodiment 5
(2) in embodiment 1 ~ 4 and (3) step are exchanged, prepares secondary aluminium cell 5 ~ 8# respectively.
Carry out charge and discharge cycles test to prepared secondary aluminium cell 1-8#, 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 1.
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 (7)
1. a secondary cell combination electrode, comprise electrode active material, binding agent and collector, it is characterized in that, electrode active material is made up of titanium dioxide, conducting polymer and sulphur, described electrode active material has nucleocapsid structure, its center is sulphur, is coated with titanium dioxide and conducting polymer outside sulphur, and structure is followed successively by sulphur, conducting polymer, titanium dioxide from inside to outside; Or, sulphur, titanium dioxide, conducting polymer.
2. secondary cell combination electrode according to claim 1, is characterized in that, described titanium dioxide, conducting polymer and sulphur are nano-scale.
3. secondary cell combination electrode according to claim 1, is characterized in that, described conducting polymer comprise in polyaniline, polypyrrole, polythiophene, polyacrylonitrile any one.
4. a secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that, combination electrode just very according to claim 1, and negative pole is for containing aluminum honeycomb, and electrolyte is that non-water is containing aluminium electrolyte.
5. secondary aluminium cell according to claim 4, is characterized in that, the described aluminum honeycomb that contains comprises aluminum metal or aluminium alloy.
6. secondary aluminium cell according to claim 4, is characterized in that, described non-water comprises organic salt-aluminum halide system ionic liquid containing aluminium electrolyte.
7. secondary aluminium cell according to claim 6, is characterized in that, the cation of described 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.
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| CN201420582444.6U CN204243148U (en) | 2014-10-10 | 2014-10-10 | A kind of secondary cell combination electrode and secondary aluminium cell |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835948A (en) * | 2015-06-01 | 2015-08-12 | 江西师范大学 | Composite material for lithium-sulfur battery positive electrode, preparation method of composite material, positive electrode made of composite material and battery |
| CN106953074A (en) * | 2015-12-31 | 2017-07-14 | 黄炳照 | Electrode structure |
| CN107665990A (en) * | 2016-07-29 | 2018-02-06 | 横店集团东磁股份有限公司 | A kind of chloride battery positive plate and preparation method thereof |
| CN109560250A (en) * | 2017-09-27 | 2019-04-02 | 财团法人工业技术研究院 | Electrode, method of manufacturing the same, and device including the same |
| WO2019173549A1 (en) * | 2018-03-08 | 2019-09-12 | Sabic Global Technologies B.V. | Double-shell encapsulated sulfur composites for lithium-sulfur cathode |
-
2014
- 2014-10-10 CN CN201420582444.6U patent/CN204243148U/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835948A (en) * | 2015-06-01 | 2015-08-12 | 江西师范大学 | Composite material for lithium-sulfur battery positive electrode, preparation method of composite material, positive electrode made of composite material and battery |
| CN106953074A (en) * | 2015-12-31 | 2017-07-14 | 黄炳照 | Electrode structure |
| CN107665990A (en) * | 2016-07-29 | 2018-02-06 | 横店集团东磁股份有限公司 | A kind of chloride battery positive plate and preparation method thereof |
| CN107665990B (en) * | 2016-07-29 | 2021-02-26 | 横店集团东磁股份有限公司 | Chloride battery positive plate and preparation method thereof |
| CN109560250A (en) * | 2017-09-27 | 2019-04-02 | 财团法人工业技术研究院 | Electrode, method of manufacturing the same, and device including the same |
| WO2019173549A1 (en) * | 2018-03-08 | 2019-09-12 | Sabic Global Technologies B.V. | Double-shell encapsulated sulfur composites for lithium-sulfur cathode |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150401 Termination date: 20191010 |