CN101794907B - Aluminium polymer secondary battery and preparation method thereof - Google Patents
Aluminium polymer secondary battery and preparation method thereof Download PDFInfo
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- CN101794907B CN101794907B CN200910234920A CN200910234920A CN101794907B CN 101794907 B CN101794907 B CN 101794907B CN 200910234920 A CN200910234920 A CN 200910234920A CN 200910234920 A CN200910234920 A CN 200910234920A CN 101794907 B CN101794907 B CN 101794907B
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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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- 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
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Abstract
The invention discloses an aluminium polymer secondary battery and a preparation method thereof. The aluminium polymer secondary battery is prepared by taking metallic aluminium or aluminium alloy, preferably foamed aluminium as the negative pole, vulcanized polyvinyl chloride or carbon-sulfur composite materials as the positive active materials, and halogen aluminic acid ionic liquid formed by aluminum subhalide and one of hyamine, phosphonium actericideor, or sulfur actericide as the electrolyte solution. The battery has the advantages of high energy density, good cycle performance, environment protection, no pollution during the preparation, low cost, simple process and favorable application prospect.
Description
Technical field
The present invention relates to a kind of two secondary aluminiums-polymer battery.More specifically, relating to a kind of is that electrolyte, polymer are the rechargeable aluminum battery of positive active material with the ionic liquid.The technical field that belongs to electrochemistry and chemical power source product.
Background technology
Development of modern science and technology, energy scarcity and the pay attention to day by day of environmental protection required high-energy-density, cheap and aboundresources, safe in utilization, eco-friendly chargeable battery.Aluminum cell is one of the highest battery of energy density, and environment is not polluted, and raw materials used aboundresources, cheap, safe in utilization meets the direction that battery develops.Metallic aluminium is a kind of high-energy carrier as GND, and theoretical specific capacity is 2980mAh/g, is only second to lithium (3870mAh/g); And its volume and capacity ratio is 8050mAh/cm
3, be 4 times of lithium, be higher than other all metal materials, its oxidation-reduction potential is also very low to be-2.35V (vs SHE), is desirable cell negative electrode material.
An aluminum cell that with the aqueous electrolyte is electrolyte is once by extensive concern.The theoretical energy density of aluminium-air cell can reach 8100Wh/Kg, but actual energy density has only 350Wh/kg.This is because a lot of problems that the aluminium electrode can produce in aqueous electrolyte: very strong affinity is arranged between (1) aluminium alloy and the oxygen; In the air and the aqueous solution; The surface generates the fine and close passive oxidation film of one deck; Make the electrode potential of aluminium in neutral solution not reach due theoretical electrode potential, the real work current potential of aluminium is more much lower than theoretical value, the voltage delay phenomenon when also causing discharge simultaneously.(2) aluminium is typical amphoteric metal, and activity is higher, is prone to and acid, alkali effect, oxide-film is destroyed, and in a single day oxide-film is destroyed and will be corroded rapidly, makes the utilance of electrode low, and wet poor storage performance.(3) aluminium is bigger from corrosion in alkaline solution, and serious evolving hydrogen reaction takes place easy and medium, has reduced the utilance of electrode, influences the operate as normal of battery.(4) in the alkaline medium, aluminium anodes becomes stream reaction and corrosion reaction product to be gluey Al (OH)
3, not only reduce electrolytic conductivity but also increase the aluminium anodes polarization, make the aluminum cell mis-behave.(5) need heat-exchange system to get rid of the dissolving of aluminium in alkaline solution and a large amount of heat of corrosion generation.
In addition, because the reduction potential of aluminium is more negative than hydrogen, can not be at aqueous solution electrodeposition aluminium.Therefore, using the reduction of can't charging of the aluminum cell of aqueous electrolyte, can only be primary cell.
As the positive electrode of secondary cell, conducting polymers such as the polymer of main chain conjugation such as polyaniline, polythiophene, polypyrrole, polyphenyl once received extensive studies and exploitation.Conducting polymer is used as positive electrode active materials and makes positive pole with the assembling lithium secondary battery, utilizes anionic doping/dedoping process to realize energy storage.Wherein, the theoretical specific capacity of polythiophene can reach 280Ah/Kg, the about 60-100Ah/Kg of actual discharge specific capacity.Polythiophene is that specific capacity is low excessively as the shortcoming of positive electrode, and traditional lithium one polythiophene chargeable battery commercialization once because of its energy density is too low, is withdrawn from the market after the lithium ion battery listing.
Summary of the invention
For overcome that the energy density that existing electrolytic aluminium battery exists is low, OCP is little and have be the shortcoming of primary cell; The present invention provides a kind of aluminium polymer secondary battery and preparation method thereof, for nonaqueous electrolyte secondary aluminium-sulfur battery has big, the rechargeable advantage of open circuit voltage.
Technical scheme of the present invention is: a kind of aluminium polymer secondary battery, by positive pole, negative pole, electrolyte, barrier film, anodal constitute by positive electrode active materials, conductive agent, binding agent, organic solvent and the collector that is used to conduct electricity,
Negative pole:
Negative pole adopts the metal aluminum or aluminum alloy; Aluminium alloy be selected from aluminium and lithium, sodium, potassium, gallium, indium, thallium, iron, cobalt, nickel, copper, zinc, manganese, tin, lead, magnesium, calcium, chromium, the germanium any or appoint several kinds; In the powder that form is, silk, net, sheet, paper tinsel, the foam any is preferably foamed aluminium; Compare lithium anode, both cheap, material source is extensive, again safety.Handle the aluminum or aluminum alloy sheet through chemical activation, increased the effecting reaction area of negative pole, improve activity, be difficult for producing dendrite simultaneously, the secondary aluminium cell capacity that modification combines is high, good cycle.
The preparation method of foamed aluminium negative material is: select for use styrofoam as base material; Through degreasing, deoil, remove the preliminary treatment of stress after, again through ionize process, be placed on chemical plating last layer copper conductive surface layer or nickel conductive surface layer in chemical bronze plating liquid or the nickel-plating liquid; Or after base material carried out preliminary treatment;, put into the organic electrolyte that contains aluminium salt or contain aluminum ions ion liquid electroplating bath as negative electrode in advance to handle with the method for coating electrically conductive glue through the base material after the above-mentioned conduction processing, with the metal aluminium flake as anode; With direct current, pulsive electroplating electric deposition aluminum, electrolyte temperature is controlled at 20～150 ℃; Electrodeposition time 30～200 minutes, electroplating current density is chosen as 0.001A～0.1A/cm
2, more preferably 30～120 ℃; Electrodeposition time 1～3 hour, electroplating current density is chosen as 0.005A～0.05A/cm
2, most preferably be 50～95 ℃; Electrodeposition time 1～2 hour, electroplating current density is chosen as 0.005A～0.01A/cm
2, constantly stir electrolyte in the electroplating process, electroplate with the dispersibility that improves electrolyte, after plating obtains foamed aluminium, also need under vacuum, heat-treat.
Heat treated process comprises the following two continuous steps: the first step is in air atmosphere; Combustion decomposition, remove the organic foam as matrix, about 200～800 ℃ of heat treatment temperatures, 5～120 minutes time; More preferably about 300～600 ℃; 10～90 minutes time most preferably was about 400～500 ℃, 10～60 minutes time; Second step was eliminated coating stress to the foamed aluminium of pyrolysis, fusion crystalline particle gap under protecting as reducing atmosphere at hydrogen; Eliminate and reduce remaining organic principle and some objectionable impurities, reduction surfaces oxide layer simultaneously, heat treatment temperature 300～800 degree; 10～120 minutes time, more preferably 400～700 spend 15～90 minutes time; Most preferably be 500～600 degree, 20～60 minutes time, promptly get required foamed aluminium negative material after the cooling.
Electrolyte:
Electrolyte is selected from aluminum halide with any formed halogen aluminic acid ionic liquid in quaternary ammonium salt or quaternary alkylphosphonium salt or the season sulfosalt., be preferably the chlorine aluminic acid ionic liquid that aluminium chloride forms with quaternary ammonium salt, more preferably aluminium chloride-phenyl trimethyl ammonium chloride ionic liquid.Electrolyte is that non-water contains the aluminium ion liquid electrolyte, can make the aluminium negative terminal surface not generate oxide-film in assemble under the anaerobic water-less environment and after sealing, no wasteness burn into does not have the colloid accessory substance, has reduced the capacity of negative plates loss.Ionic liquid can also solve the dissolving losing issue of active material to suppress the dissolubility of intermediate product polysulfide in electrolyte of electrode reaction, thereby improves the capacity characteristic and the cycle life of battery.The redox reaction of aluminium electrode in this electrolyte is reversible, and battery is chargeable.In addition, il electrolyte does not have vapour pressure, does not burn, and has strengthened the security performance of battery greatly.
Anodal:
Anodal anodal polymer active material wherein is any in polyacetylene, polyphenyl, polypyrrole, polyaniline, the polythiophene.
Described conductive agent be selected from active carbon, carbon black, acetylene carbon black, super carbon black (Super-P), graphite, polyaniline, polyacetylene, polypyrrole, the polythiophene any or appoint several kinds combination to use;
Described binding agent is selected from polyvinyl acetate, polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone, polyvinylether, polymethyl methacrylate, Kynoar, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinyl pyridine, polystyrene, perhaps their derivative, in the copolymer any or appoint several kinds mixture;
Described organic solvent is selected from any in acetonitrile, methyl alcohol, ethanol, acetone, oxolane, the isopropyl alcohol;
Described collector is selected from any in the electric conducting material of stainless steel, carbon, copper, aluminium, nickel, and form is selected from a kind of or carbon cloth in the foam, net, paper tinsel, sheet form of metal.
The preparation of above-mentioned secondary aluminium cell has following steps:
1) preparation of polymer positive electrode active materials slurry: with the polymer active material is positive electrode; Add a kind or multiple and binding agent in conductive agent such as super conductive carbon black (SUPER-P), conductive black, acetylene black and the graphite powder: Kynoar (PVDF), gather in oxireme (PEO), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), the ethylene-propylene rubber one or more; Mass ratio is 7: 2: 1, adds organic solvent and processes the positive electrode active materials slurry.
2) the above-mentioned polymer positive electrode active materials slurry of processing is coated on the nickel foam substrate; Oven dry is rolled into positive plate; Be wound into the electric stamen nickel plating box hat of packing into the non-barrier film and aluminium or foamed aluminium negative plate knitted of glass fiber; Add aluminium chloride and the phenyl trimethyl ammonium chloride electrolyte of reaction formation in 2: 1 in proportion again, seal and process cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell.
Described secondary aluminium cell also can be processed square etc. the common various ways of individual layer button, multilaminate coiled cylindrical, multilayer folding and in the specification any.
Beneficial effect:
1. the negative pole of aluminium polymer secondary battery of the present invention adopts the metal aluminum or aluminum alloy.Compare lithium anode, both cheap, material source is extensive, again safety.Through the aluminum or aluminum alloy sheet that chemical activation is handled, increased the effecting reaction area of negative pole, improved activity, be difficult for simultaneously producing dendrite, having solved with metal aluminium flake or aluminium powder is that the secondary aluminium cell of negative pole exists problems such as specific area is little, cyclicity difference.The secondary aluminium-sulfur battery capacity that modification combines is high, good cycle.
2. electrolyte system of the present invention adopts non-water to contain the aluminium ion liquid electrolyte, assemble and sealing under the anaerobic water-less environment.Make the aluminium negative terminal surface not generate oxide-film like this, no wasteness burn into does not have the colloid accessory substance, has reduced the capacity of negative plates loss.Secondary aluminium cell of the present invention; With the aluminum or aluminum alloy is negative electrode active material, and polymer is a positive active material, and its basic principle does; In battery system; Reversible dissolving and deposition can take place in the aluminium negative pole, and as the polymer of positive active material can be reversible doping and the anion in the dedoping electrolyte, thereby realize the reversible charge and discharge process of battery.In addition, il electrolyte does not have vapour pressure, does not burn, and has strengthened the security performance of battery greatly.
3. positive electrode active materials of the present invention selects polyacetylene, polyphenyl, polypyrrole, polyaniline, polythiophene and active sulfur polymer and their composite material.Its essential characteristic is that it inserts polymer for anion, and it is reversible each other with the dedoping process to mix, and available electrochemical method is realized.。
4. the invention provides the new-type secondary aluminum cell of a kind of high energy, environmental protection; The preparation process of positive electrode active material material of the present invention, negative pole and electrolyte is pollution-free, and preparation cost is low, and technology is simple; High with this secondary aluminium cell energy density for preparing; Good cycle, and have the excellent safety ability, have a good application prospect.
Embodiment
Below with reference to the present invention of certain embodiments illustrated in detail, yet these certain embodiments should be not the qualifications to the scope of the invention and coordinate thereof from being interpreted as in all senses.
Embodiment 1
The preparation of polyacetylene active material: (PVC) places in the tube type resistance furnace with polyvinyl chloride; Under the argon shield condition; 100 ℃-500 ℃ heating 3-8h; More preferably 200 ℃-400 ℃ heating 4-6h most preferably are 300 ℃ of heating 5h, so that the complete dehydrochlorination of pvc material and obtain polyacetylene.
Embodiment 2
The preparation of polypyrrole active material: in reaction bulb, add 1.0 * 10
-5The surfactant sodium dodecyl benzene sulfonate aqueous solution 30mL of mol/L, pyrroles 0.06mL, vigorous stirring 10min; Cooling; Under 0 ℃ of-5 ℃ of vigorous stirring, drip the 138mmol/L ammonium persulfate solution 6.5mL of cooling in advance, after being added dropwise to complete, deposit 24h in the refrigerator.Filter then, filter cake is used distilled water, absolute ethanol washing successively, obtains the black powder polypyrrole in 80 ℃ of following vacuumize 12h.
Embodiment 3
The preparation of polyaniline active material: in reaction bulb, add 20.27g n-butanol, 10.2g DBSA and 11.42g deionized water successively, stir and make its even dispersion, in above-mentioned solution, add the 2.33g aniline solution; Continue to stir 2h, in above-mentioned solution, slowly drip the aqueous solution that comprises the 7.13g ammonium persulfate, 1h is added dropwise to complete; Stir polymerization 5h; Filter then, fully wash with ethanol and deionized water successively, obtain polyaniline powder in 80 ℃ of following vacuumize 12h.
Embodiment 4
With the polyacetylene is positive active material; Add conductive agent SUPER-P and adhesive PVDF, ratio is 7: 2: 1, processes the positive electrode active materials slurry and is coated on the nickel foam substrate; Oven dry is rolled into positive plate; Knit negative pole that barrier film and aluminium flake process as negative active core-shell material and be wound into the electric stamen nickel plating box hat of packing into glass fiber is non-, add aluminium chloride and the phenyl trimethyl ammonium chloride il electrolyte that forms of reaction in 2: 1 in proportion again, seal and process AA type cylindrical aluminium secondary cell.During the battery charging and discharging loop test, charge to 2.4V with 1C, 0.5C is discharged to 1.2V, and battery open circuit voltage is 1.62V, and high discharge capacity is 752mAh, and discharge capacity is 609mAh after 50 charge and discharge cycles.
Embodiment 5
With the polypyrrole is positive active material, by carrying out the assembling of battery with embodiment 4 identical methods.During the battery charging and discharging loop test, charge to 2.4V with 1C, 0.5C is discharged to 1.2V, and battery open circuit voltage is 1.66V, and high discharge capacity is 693mAh, and discharge capacity is 547mAh after 50 charge and discharge cycles.
Embodiment 6
With the polyaniline is positive active material, by carrying out the assembling of battery with embodiment 4 identical methods.During the battery charging and discharging loop test, charge to 2.4V with 1C, 0.5C is discharged to 1.2V, and battery open circuit voltage is 1.68V, and high discharge capacity is 867mAh, and discharge capacity is 746mAh after 50 charge and discharge cycles.
Embodiment 7
1) preparation of polymer positive electrode active materials slurry: with the polymer active material is positive electrode; Add conductive agent and binding agent respectively; Part by weight is 7: 2: 1, and adding organic solvent such as acetonitrile, methyl alcohol, ethanol, acetone, oxolane, isopropyl alcohol are processed the positive electrode active materials slurry.Described conductive agent be selected from active carbon, carbon black, acetylene carbon black, super carbon black (Super-P), graphite, polyaniline, polyacetylene, polypyrrole, the polythiophene any or appoint several kinds combination to use; Described binding agent is selected from polyvinyl acetate, polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone, polyvinylether, polymethyl methacrylate, Kynoar, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinyl pyridine, polystyrene, perhaps their derivative, in the copolymer any or appoint several kinds mixture;
2) the above-mentioned polymer positive electrode active materials slurry of processing is coated on the nickel foam substrate; Oven dry is rolled into positive plate; Be wound into the electric stamen nickel plating box hat of packing into the non-barrier film and aluminium or foamed aluminium negative plate knitted of glass fiber; Add aluminium chloride and the phenyl trimethyl ammonium chloride electrolyte of reaction formation in 2: 1 in proportion again, seal and process cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell.
Embodiment 8
The preparation method of foamed aluminium negative material is: select for use styrofoam as base material; Through degreasing, deoil, remove the preliminary treatment of stress after, again through ionize process, be placed on chemical plating last layer copper conductive surface layer or nickel conductive surface layer in chemical bronze plating liquid or the nickel-plating liquid; Or after base material carried out preliminary treatment;, put into the organic electrolyte that contains aluminium salt or contain aluminum ions ion liquid electroplating bath as negative electrode in advance to handle with the method for coating electrically conductive glue through the base material after the above-mentioned conduction processing, with the metal aluminium flake as anode; With direct current, pulsive electroplating electric deposition aluminum, electrolyte temperature is controlled at 20～150 ℃; Electrodeposition time 30～200 minutes, electroplating current density is chosen as 0.001A～0.1A/cm
2, more preferably 30～120 ℃; Electrodeposition time 1～3 hour, electroplating current density is chosen as 0.005A～0.05A/cm
2, most preferably be 50～95 ℃; Electrodeposition time 1～2 hour, electroplating current density is chosen as 0.005A～0.01A/cm
2, constantly stir electrolyte in the electroplating process, electroplate with the dispersibility that improves electrolyte, after plating obtains foamed aluminium, also need under vacuum, heat-treat.
Heat treated process comprises the following two continuous steps: the first step is in air atmosphere; Combustion decomposition, remove the organic foam as matrix, about 200～800 ℃ of heat treatment temperatures, 5～120 minutes time; More preferably about 300～600 ℃; 10～90 minutes time most preferably was about 400～500 ℃, 10～60 minutes time; Second step was eliminated coating stress to the foamed aluminium of pyrolysis, fusion crystalline particle gap under protecting as reducing atmosphere at hydrogen; Eliminate and reduce remaining organic principle and some objectionable impurities, reduction surfaces oxide layer simultaneously, heat treatment temperature 300～800 degree; 10～120 minutes time, more preferably 400～700 spend 15～90 minutes time; Most preferably be 500～600 degree, 20～60 minutes time, promptly get required foamed aluminium negative material after the cooling.
Claims (5)
1. aluminium polymer secondary battery is made up of positive pole, negative pole, electrolyte, barrier film, battery case and lead-in wire, and positive pole is made up of positive electrode active materials, conductive agent, binding agent, organic solvent and the collector that is used to conduct electricity, it is characterized in that,
Negative pole adopts the metal aluminum or aluminum alloy, and form is that in powder, silk, net, sheet, the foam any is as negative material;
Electrolyte is aluminium chloride-phenyl trimethyl ammonium chloride ionic liquid;
Anodal positive electrode active materials wherein is a polymer, and other material is conventional anodal materials used.
2. aluminium polymer secondary battery as claimed in claim 1 is characterized in that, described positive electrode active materials polymer is any in polyacetylene, polyphenyl, polypyrrole, polyaniline, the polythiophene.
3. aluminium polymer secondary battery as claimed in claim 1 is characterized in that, described negative material is a foamed aluminium, is made by following method:
Select for use organic foam material as base material; Through degreasing, deoil, remove the preliminary treatment of stress after, again through ionize process, be placed on chemical plating last layer copper conductive surface layer or nickel conductive surface layer in chemical bronze plating liquid or the nickel-plating liquid; Or after base material carried out preliminary treatment; Method with coating electrically conductive glue is handled, put into the organic electrolyte that contains aluminium salt or contain aluminum ions ion liquid electroplating bath as negative electrode through the base material after the above-mentioned conduction processing, with the metal aluminium flake as anode; With direct current or pulsive electroplating electric deposition aluminum, electrolyte temperature is controlled at 20～150 ℃; Electrodeposition time 30～200 minutes, electroplating current density is chosen as 0.001A～0.1A/cm
2Constantly stir electrolyte in the electroplating process, after plating obtains foamed aluminium, heat treatment in a vacuum;
Heat treated process comprises the following two continuous steps: the first step is in air atmosphere, combustion decomposition, removes the organic foam as matrix, 200～800 ℃ of heat treatment temperatures, 5～120 minutes time; Second step, foamed aluminium heat treatment temperature 300～800 degree to pyrolysis, promptly got required foamed aluminium negative material at 10～120 minutes time after the cooling under protecting as reducing atmosphere at hydrogen.
4. aluminium polymer secondary battery as claimed in claim 1; It is characterized in that, described conductive agent be selected from active carbon, acetylene carbon black, super conductive carbon black, graphite, polyaniline, polyacetylene, polypyrrole, the polythiophene any or appoint several kinds combination to use;
Described binding agent is selected from polyvinyl acetate, polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone, polyvinylether, polymethyl methacrylate, Kynoar, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinyl pyridine, polystyrene, perhaps their derivative, in the copolymer any or appoint several kinds mixture;
Described organic solvent is selected from any in acetonitrile, methyl alcohol, ethanol, acetone, oxolane, the isopropyl alcohol;
Described collector is selected from any in the electric conducting material of stainless steel, copper, aluminium, nickel, and form is selected from a kind of or carbon cloth in the foam, net, sheet form of metal.
5. the preparation method of aluminium polymer secondary battery as claimed in claim 1 is characterized in that, step is:
The first step; The preparation of positive electrode active materials slurry: according to the weight ratio positive electrode active materials: conductive agent: binding agent is the ratio of 6-8: 1-3: 0.5-1.5; With the polymer is positive electrode active materials, adds conductive agent and binding agent, processes anodal polymer active material paste after mixing;
Second step; The polymer active material paste that the first step is processed is coated on the nickel foam substrate; Oven dry is rolled into positive plate; Knit negative plate that barrier film and metal aluminum or aluminum alloy make and be wound into electric core and pack in the nickel plating box hat with glass fiber is non-, add aluminium chloride-phenyl trimethyl ammonium chloride ionic liquid again, seal and process the cylinder secondary aluminium cell as electrolyte.
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| US9831044B2 (en) | 2012-04-13 | 2017-11-28 | PolyJoule, Inc. | Devices and methods including polyacetylenes |
| CN104078679B (en) * | 2014-05-23 | 2015-08-12 | 南京中储新能源有限公司 | A kind of carbon nanotube conducting sulfide polymer positive pole and secondary aluminium cell |
| CN104078704B (en) * | 2014-07-03 | 2016-03-23 | 南京中储新能源有限公司 | A kind of secondary aluminium cell and nonaqueous electrolyte thereof |
| CN104377374B (en) * | 2014-09-11 | 2017-07-07 | 中山大学 | One kind is without additional electrolytic cell |
| CN106887636A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Aluminium ion battery based on conducting polymer positive pole and preparation method thereof |
| CN105826543A (en) * | 2016-05-10 | 2016-08-03 | 哈尔滨工业大学（威海） | Aluminum-polyaniline secondary battery |
| CN107394260B (en) | 2016-05-17 | 2020-06-09 | 财团法人工业技术研究院 | Metal ion battery |
| CN105977526A (en) * | 2016-06-15 | 2016-09-28 | 昆明理工大学 | Rechargeable aluminum carbon battery and preparation method thereof |
| TWI611618B (en) | 2016-12-16 | 2018-01-11 | 財團法人工業技術研究院 | Metal-ion battery |
| CN108134093A (en) * | 2017-12-28 | 2018-06-08 | 上海应用技术大学 | A kind of carbon nanotube paper-metal or alloy composite current collector and preparation method thereof |
| CN109244361B (en) * | 2018-10-12 | 2020-10-27 | 深圳中科瑞能实业有限公司 | Coated aluminum cathode, preparation method and application thereof, lithium secondary battery and application thereof |
| CN110767878B (en) * | 2019-09-23 | 2022-06-14 | 合肥国轩高科动力能源有限公司 | Conductive polymer coated silicon-based negative electrode plate and preparation method and application thereof |
| CN111668481B (en) * | 2020-05-27 | 2021-12-03 | 北京科技大学 | Preparation method of metal aluminum secondary battery with multi-group organic micromolecules as positive electrode |
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| CN1311538A (en) * | 2000-03-01 | 2001-09-05 | 东芝株式会社 | Aluminum battery |
| CN1487122A (en) * | 2003-07-03 | 2004-04-07 | 孙伟成 | Preparation method of foamed aluminum |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1311538A (en) * | 2000-03-01 | 2001-09-05 | 东芝株式会社 | Aluminum battery |
| CN1487122A (en) * | 2003-07-03 | 2004-04-07 | 孙伟成 | Preparation method of foamed aluminum |
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