CN101764258A - Secondary aluminium cell and preparation method thereof - Google Patents
Secondary aluminium cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a secondary aluminium cell and a preparation method thereof. Foamed aluminium serves as a cathode. A carbon and sulfur composite material or sulfurized polyacrylonitrile serves as an anode active material. A halogen aluminate ionic liquid formed from halogen aluminium acid and any one of halogenated quaternary ammonium salt, quaternary alkylphosphonium salt or quaternary sulfosalt is obtained by preparing electrolyte. The cell has the advantages of high energy density, good cycle performance, safety, environmental protection, no pollution in the preparation process, low cost and simple process.
Description
Technical field
The present invention relates to a kind of secondary aluminium-sulfur battery that uses il electrolyte.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 battery cathode, 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.Sulphur has the theoretical energy density of 1675mAhg, is the highest positive electrode of known energy density.No matter be elemental sulfur directly as electrode, or sulfur-based compound, comparing in the following aspects with traditional positive electrode all has great advantage: (1) theoretical specific capacity is big; (2) the occurring in nature reserves are abundant, obtain easily, and are cheap; (3) safety non-toxic, environmental pollution is little; (4) synthesis technique is simple, can synthesize with multiple material.Sulphur is as a kind of desirable cell positive material, but cooperates the aluminium-sulfur battery of the cheap and aboundresources of constructed price, pollution-free, safe in utilization, high-energy-density with the aluminium negative pole.
Licht equals the nineties in 20th century exploitation a kind of high specific energy alkaline aqueous solution of the novel S of containing aluminium-sulfur battery (US Pat:5431881,4828492,5648183) that at normal temperatures can repid discharge.This battery is anode with the aluminium alloy, is negative electrode with the polysulfide that is dissolved in the alkaline electrolyte.But because the imperfection of aluminium anodes polarization and electrolyte system, the aluminium-sulfur battery of developing in the reality has only the battery Open Circuit Potential of 1.3V and the energy density of 110Wh/kg.(Investigation?of?a?novel?aqueous?aluminum/sulfurbattery.Journal?of?Power?Sources，1993，3(45)：311-323)
Though the theoretical energy density of aluminium-air cell can reach 8100Wh/Kg, 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 passive oxidation film of one deck densification, 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, easily with acid, alkali effect, oxide-film is destroyed, and will be corroded rapidly and oxide-film is in a single day destroyed, 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.
With elemental sulfur (S
8) for the redox reaction of positive active material is a multistep electron exchange process, this redox reaction has certain electrochemical reversibility.During discharge (electrochemical reduction), the fracture of sulphur sulfide linkage, the oxidation number of sulphur reduces; When recharging (electrochemical oxidation), the sulphur sulfide linkage forms, and the oxidation number of sulphur raises.By this redox reaction, the sulphur in the sulfur-based compound can store and produce power.This provides theoretical foundation for elemental sulfur as the electrode for secondary battery active material.
Yet, because being wrapped in the active material particle surface, the product of the dissolving of the product of elemental sulfur, electrode conductivuty difference and electronic isolation cause the granule interior active material to lose efficacy, cause the utilance of active material low poor, restricted the commercialization process of metal/sulfur rechargeable battery with cycle performance.
The mutual conversion that poly-organosulfur compound can carry out chemical energy and electrochemical energy by the depolymerization and the polymerization reaction of sulphur sulfide linkage in the molecule.It has that theoretical specific energy height, working temperature are low, the inexpensive low toxicity of raw material, biodegradation and structure designability are arranged, advantages such as easy copolymerizing and blending modification, its theoretical energy density is up to 1500Wh/kg～3500Wh/kg, thereby is considered to have one of positive electrode of development prospect most.
Summary of the invention
For overcome that the energy density that existing electrolytic aluminium battery exists is low, Open Circuit Potential is little and have be the shortcoming of primary cell, the invention provides a kind of secondary aluminium cell 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 secondary aluminium cell, 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, form is any in powder, silk, net, sheet, paper tinsel, the foam, is preferably the aluminum or aluminum alloy that activation processing is crossed; Compare lithium anode, both cheap, material source is extensive, again safety.Handle the aluminum or aluminum alloy sheet by chemical activation, increased the effecting reaction area of negative pole, improve activity, be difficult for producing dendrite, secondary aluminium cell capacity height, good cycle that modification combines simultaneously.
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 positive electrode active materials wherein is carbon sulphur composite material or sulfuration polyacrylonitrile, and other material is conventional positive electrode.Positive active material adopts the very high poly-organic sulfur compound of specific capacity such as carbon sulphur composite material or sulfuration polyacrylonitrile.Its structure is that many sulphur chain is grafted on the skeleton of polymer, and the S-S bond structure is fixed.Can solve elemental sulfur active material poorly conductive simultaneously, reduzate dissolves problems such as the skeleton that causes caves in.
Described positive electrode active materials sulfuration polyacrylonitrile prepare by following method: with polyacrylonitrile and sublimed sulfur according to 1: 3 mixed in molar ratio after in the adding ball grinder, it is even to add quantitative absolute ethyl alcohol and stirring according to the standard of the sublimed sulfur of 50mL/mol, at room temperature ball milling stirred 6 hours, and 80 ℃ of vacuumize is 24 hours then.Dried mixture is put into pressure pan heat compoundly, adopt the segmentation heating compound, 200 ℃ of insulations 2 hours, continue heating, 450 ℃ of insulations 3 hours, inert gas shielding obtained vulcanizing the polyacrylonitrile powder-product behind the natural cooling.
Carbon sulphur composite material is prepared by following method:
Active carbon and elemental sulfur are placed in the ball grinder with 1: 3 mixed of mass ratio, and with 1: 1 ratio of ratio of grinding media to material, rotating speed 200r/min carries out ball milling 6h; place in the resistance furnace then; under the condition of argon shield, 350 ℃ of compound 3h of heating obtain carbon sulphur composite material behind the natural cooling.
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 being used in combination;
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 mixtures;
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 method of described secondary aluminium cell, 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 sulfuration polyacrylonitrile or carbon sulphur composite material is positive electrode, add conductive agent and binding agent, make the positive electrode active materials slurry after in organic solvent, mixing;
Second step, the sulfuration polyacrylonitrile positive electrode active materials slurry that the first step is made or the positive electrode active materials slurry of carbon sulphur composite material are coated on the collector, 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 stamen and pack in the nickel plating box hat positive plate and glass fibre are non-then, add halogen aluminic acid ionic liquid again as electrolyte, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell.
Described secondary aluminium-sulfur battery also can be made 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 secondary aluminium cell of the present invention adopts the metal aluminum or aluminum alloy.Compare lithium anode, both cheap, material source is extensive, again safety.By 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.Secondary aluminium-sulfur battery capacity height, good cycle that modification combines.
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.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.
3. positive active material of the present invention is to adopt the very high poly-organic sulfur compound of specific capacity such as carbon sulphur composite material or sulfuration polyacrylonitrile.Its structure is that many sulphur chain is grafted on the skeleton of polymer, and the S-S bond structure is fixed.Can solve elemental sulfur active material poorly conductive simultaneously, easily decay, capacity is low, and reduzate dissolves problems such as the skeleton that causes caves in.
4. the invention provides the novel secondary aluminium 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, preparation cost is low, technology is simple, with this secondary aluminium cell energy density height for preparing, good cycle, and have the excellent safety energy, have a good application prospect.
Embodiment
Explain the present invention in detail below with reference to certain embodiments, yet these certain embodiments should not qualifications to the scope of the invention and coordinate thereof from being interpreted as in all senses.
Embodiment 1
Described positive electrode active materials sulfuration polyacrylonitrile prepare by following method: with polyacrylonitrile and sublimed sulfur according to 1: 3 mixed in molar ratio after in the adding ball grinder, it is even to add quantitative absolute ethyl alcohol and stirring according to the standard of the sublimed sulfur of 50mL/mol, at room temperature ball milling stirred 6 hours, and 80 ℃ of vacuumize is 24 hours then.Dried mixture is put into pressure pan heat compoundly, adopt the segmentation heating compound, 200 ℃ of insulations 2 hours, continue heating, 450 ℃ of insulations 3 hours, inert gas shielding obtained vulcanizing the polyacrylonitrile powder-product behind the natural cooling.
Embodiment 2
The negative electrode active material chemical activation is handled the preparation of aluminium flake: it is that the NaOH solution of 2mol/L was handled 1 minute that aluminium flake is put into concentration, cleans with distilled water then; Put into concentration again and be the HCl solution of 2mol/L and handled 2 minutes, clean with distilled water then; At last, put into the HNO that concentration is 40g/L
3Handled 90 seconds in the solution, clean natural air drying then with distilled water.
Embodiment 3
Active carbon and elemental sulfur mix with mass ratio 1: 3 and are placed in the ball grinder, and with ratio of grinding media to material 1: 1, rotating speed 200r/min carried out ball milling 6h, places then in the resistance furnace, and under the condition of argon shield, 350 ℃ of compound 3h of heating obtain carbon sulphur composite material behind the natural cooling.With carbon sulphur composite material (mass ratio 1: 3) is positive electrode, add conductive agent SUPER-P and adhesive PVDF, part by weight is 7: 2: 1, making the positive electrode active materials slurry in organic solvent is coated on the nickel foam substrate, oven dry is rolled into pole piece, knit barrier film and be wound into the electric stamen nickel plating box hat of packing into glass fibre is non-with the negative pole that aluminium flake is made as negative active core-shell material, add aluminium chloride and the phenyl trimethyl ammonium chloride il electrolyte of reaction formation in 2: 1 in proportion again, seal and make AA type cylindrical aluminium secondary cell.During the battery charging and discharging loop test, charge with 1C, 0.5C discharge, discharge cut-off voltage is 1.2V, and battery open circuit voltage is 1.81V, and high discharge capacity is 883mAh, and discharge capacity is 721mAh after 50 charge and discharge cycles.
Embodiment 4
Anodal preparation method is with embodiment 3, and negative electrode active material is that chemical activation is handled aluminium flake, carries out the assembling of battery by the method identical with embodiment 1.During the battery charging and discharging loop test, charge with 1C, 0.5C discharge, discharge cut-off voltage is 1.2V, and than embodiment 3, high discharge capacity has increased 91mAh, and the capacity attenuation rate has reduced by 30% after 50 charge and discharge cycles.
Embodiment 5
Sulfuration polyacrylonitrile material with preparation is a positive pole, and all the other anodal preparation processes are with embodiment 3.
The method of negative pole preparation is with embodiment 3, and the assembling of battery is with embodiment 3.During the battery charging and discharging loop test, charge with 1C, 0.5C discharge, discharge cut-off voltage is 1.2V, than embodiment 3,, high discharge capacity has increased 143mAh, and the capacity attenuation rate has reduced by 27% after 50 charge and discharge cycles.
Embodiment 6
Sulfuration polyacrylonitrile material with preparation is a positive pole, and all the other anodal preparation processes are with embodiment 3.
With chemical activation preliminary treatment aluminium flake is negative electrode active material, and all the other preparation processes of negative pole are with embodiment 3, and the assembling of battery is with embodiment 1.During the battery charging and discharging loop test, charge with 1C, 0.5C discharge, discharge cut-off voltage is 1.2V, and than embodiment 3, high discharge capacity has increased 202mAh, and the capacity attenuation rate has reduced by 24% after 50 charge and discharge cycles.
Claims (7)
1. secondary aluminium cell by positive pole, negative pole, electrolyte, barrier film, anodally is made 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 metal aluminum or aluminum alloy, any in the powder that form is, silk, net, sheet, paper tinsel, the foam;
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;
Anodal positive electrode active materials wherein is carbon sulphur composite material or sulfuration polyacrylonitrile, and other material is conventional positive electrode.
2. secondary aluminium cell as claimed in claim 1 is characterized in that, described electrolyte is the chlorine aluminic acid ionic liquid that aluminium chloride forms with quaternary ammonium salt.
3. secondary aluminium cell as claimed in claim 2 is characterized in that, described electrolyte is aluminium chloride-phenyl trimethyl ammonium chloride ionic liquid.
4. secondary aluminium cell as claimed in claim 1, it is characterized in that, described positive electrode active materials sulfuration polyacrylonitrile prepare by following method: with polyacrylonitrile and sublimed sulfur according to 1: 3 mixed in molar ratio after in the adding ball grinder, it is even to add quantitative absolute ethyl alcohol and stirring according to the standard of the sublimed sulfur of 50mL/mol, at room temperature ball milling stirred 6 hours, and 80 ℃ of vacuumize is 24 hours then.Dried mixture is put into pressure pan heat compoundly, adopt the segmentation heating compound, 200 ℃ of insulations 2 hours, continue heating, 450 ℃ of insulations 3 hours, inert gas shielding obtained vulcanizing the polyacrylonitrile powder-product behind the natural cooling.
5. secondary aluminium cell as claimed in claim 1 is characterized in that, described positive electrode active materials carbon sulphur composite material is prepared by following method:
Active carbon and elemental sulfur are placed in the ball grinder with 1: 3 mixed of mass ratio, and with 1: 1 ratio of ratio of grinding media to material, rotating speed 200r/min carries out ball milling 6h; place in the resistance furnace then; under the condition of argon shield, 350 ℃ of compound 3h of heating obtain carbon sulphur composite material behind the natural cooling.
6. secondary aluminium cell as claimed in claim 1, it is characterized in that, 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 being used in combination;
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 mixtures;
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.
7. the preparation method of secondary aluminium cell 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 sulfuration polyacrylonitrile or carbon sulphur composite material is positive electrode, add conductive agent and binding agent, make the positive electrode active materials slurry after in organic solvent, mixing;
Second step, the sulfuration polyacrylonitrile positive electrode active materials slurry that the first step is made or the positive electrode active materials slurry of carbon sulphur composite material are coated on the collector, 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 stamen and pack in the nickel plating box hat the positive plate glass fibre is non-then, add halogen aluminic acid ionic liquid again as electrolyte, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell.
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| CN103502284A (en) * | 2011-05-02 | 2014-01-08 | 罗伯特·博世有限公司 | Polyacrylonitrile-sulphur composite material |
| CN104078714A (en) * | 2014-07-08 | 2014-10-01 | 南京中储新能源有限公司 | Graphene secondary aluminum battery and preparation method for anode composite material of graphene secondary aluminum battery |
| CN104091964A (en) * | 2014-07-08 | 2014-10-08 | 南京中储新能源有限公司 | Graphene organic sulphate aluminium secondary battery and preparation method of positive electrode material of secondary battery |
| US8889293B2 (en) | 2012-05-11 | 2014-11-18 | Tsinghua University | Lithium ion battery |
| CN104201352A (en) * | 2014-08-29 | 2014-12-10 | 南京中储新能源有限公司 | Preparation and application of carbon-sulfur composite positive electrode based on CNT (carbon nano tube) sponge |
| CN104201355A (en) * | 2014-09-05 | 2014-12-10 | 南京中储新能源有限公司 | Conductive polymer coated carbon-sulfur composite positive electrode, preparation method thereof and secondary battery |
| CN104300127A (en) * | 2014-10-14 | 2015-01-21 | 南京中储新能源有限公司 | Sulfur-based composite material coated with carbon, preparation and application thereof |
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| WO2016054865A1 (en) * | 2014-10-09 | 2016-04-14 | 江苏华东锂电技术研究院有限公司 | Method for preparing sulfur-based positive electrode material |
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| CN104091964A (en) * | 2014-07-08 | 2014-10-08 | 南京中储新能源有限公司 | Graphene organic sulphate aluminium secondary battery and preparation method of positive electrode material of secondary battery |
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