CN101764254A - Secondary aluminum battery and preparation method of anode thereof - Google Patents
Secondary aluminum battery and preparation method of anode thereof Download PDFInfo
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- CN101764254A CN101764254A CN200910234518A CN200910234518A CN101764254A CN 101764254 A CN101764254 A CN 101764254A CN 200910234518 A CN200910234518 A CN 200910234518A CN 200910234518 A CN200910234518 A CN 200910234518A CN 101764254 A CN101764254 A CN 101764254A
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Abstract
The invention discloses a secondary aluminum battery and a preparation method of anode thereof; the secondary aluminum battery comprises a battery anode, a battery cathode, an electrolyte, a diaphragm and a current collector; the battery cathode is made of aluminum or aluminum alloy; the battery anode is made of polystyrene polysulfide or carbonyl sulfide composite material; and the electrolyte is halogen aluminic acid ionic liquid. The preparation method of secondary aluminum battery anode material (polystyrene polysulfide) comprises the following steps: (1) preparing chlorination polystyrene; (2) preparing polystyrene polysulfide; (3) slowly dropping sodium polysulfide solution into chlorination polystyrene solution according to the proportion of Na to C1 being 1: 1 at the temperature of 50 to 150 DEG C, stirring so as to react about 24 hours. Powder product is obtained after cleaning and extracting to obtain polystyrene polysulfide product dried about 24 hours in vacuum at the temperature of 80 DEG C.
Description
Technical field
The present invention relates to a kind of secondary aluminium cell and anodal preparation method thereof.
Background technology
Littler, lighter and more high performance electronic and communication apparatus, electric automobile, and the developing rapidly of new powers such as wind power generation, photovoltaic generation, to the battery performance of supporting power supply more and more higher requirement has been proposed.Commercial at present lead acid accumulator, nickel-cadmium cell, Ni-MH battery and lithium ion battery can not satisfy these requirements.Press for the exploitation have the energy height, the electrokinetic cell and the energy-storage battery of characteristics such as cost is low, the life-span is long, environmental protection, battery material aboundresources, reusable edible.With aluminum metal or aluminium alloy is that negative pole and sulfenyl material are that the secondary aluminium-sulfur battery of positive pole then is the most attractive battery system that meets these demands.
Aluminium is a kind of high-energy carrier.The aluminium electrode potential is-2.35V (vsSHE) that theoretical energy density is 2980mAh/g, is only second to lithium (3870mAh/g); And its volume energy density is 8050mAh/cm3, is 4 times of lithium, is higher than other all metal materials.In addition, the light weight of aluminium, cheap and aboundresources, pollution-free, reliability is high, safe in utilization, be desirable cell negative electrode material.
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 dissolving and the corrosion of aluminium in alkaline solution and produce a large amount of heat.
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.
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, compare with traditional positive electrode that all there is great advantage several aspects once: (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.So sulphur is as a kind of desirable cell positive material, but cooperate 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/sulfur?battery.Journal?of?Power?Sources，1993，3(45)：311-323)
Sulphur is as the positive electrode of lithium metal/sulphur battery, for example US 3532543,3907591,4469761, Rauh, et al, J.Electrochem.Soc., 1979,126 (4), 523-527, Yamin, et al, J Electrochem.Soc., 1988,135 (5), 1045-1048, Peled, etal, J.of Power Source, 1989,26,269-271.The polysulfide that lithium/sulphur battery forms when discharge is soluble in the electrolyte, produce self-discharge and stop up barrier film, in charging process, be easy to form passivation layer, be difficult to carry out ion and electron transfer, thereby cause the specific capacity decline and the cycle life of battery very poor on the positive active material surface.
Yet this positive electrode still has many shortcomings, the practicability of restriction lithium/sulphur battery: the one, and the electrical insulating property of elemental sulfur causes the utilance of active matter low; The 2nd, sulphur during discharge-sulfide linkage fracture, the micromolecule sulfide that produces is dissolved in electrolyte, generate the unordered sulphur of irreversible reaction, cause self-discharge of battery, the viscosity of electrolyte is increased, ions diffusion is obstructed, and the distribution of active matter in electrode alters a great deal, repeatedly after the circulation agglomeration may take place, cause capacity to decay rapidly, make the very fast decline of cycle performance of battery.
Summary of the invention
The present invention is the shortcoming that overcomes prior art, and a kind of extremely anodal preparation method of secondary aluminium cell who contains non-aqueous solution electrolysis plastidome is provided.
Technical scheme is:
A kind of secondary aluminium cell comprises anode, negative pole, electrolyte, barrier film, collector, and the material of battery cathode is an aluminum or aluminum alloy, and the material of anode is many sulfo-s polystyrene or carbon sulphur composite material, and electrolyte is halogen aluminic acid ionic liquid.
Described halogen aluminic acid ionic liquid is an aluminum halide with any is formed in quaternary ammonium salt Huo quaternary alkylphosphonium salt or the season sulfosalt.
Described halogen aluminic acid ionic liquid is aluminium chloride-phenyl trimethyl ammonium chloride ionic liquid.
A kind of preparation method of many sulfo-s of cell positive material polystyrene of secondary aluminium cell comprises the steps:
(1) preparation of chlorinated polyphenyl ethene: polystyrene is mixed according to mass ratio with alchlor at 8: 1, be added to then in the carbon tetrachloride solvent of 10ml/g (polystyrene) and reflux, after treating that it fully dissolves, feed chlorine, continued back flow reaction 6 hours, reaction finishes the back natural cooling, pours into then in the 200ml methyl alcohol, sedimentation products is with standby after product washing, filtration, the vacuumize;
(2) preparation of many sulfo-s polystyrene: with anhydrous sodium sulfide and sublimed sulfur according to 1: 1～1: 6 mixed in molar ratio after; standard according to the sublimed sulfur of 250ml/mol adds quantitative N; dinethylformamide; at room temperature stirred 2 hours; be warming up to 20～120 ℃ then; continue to stir 12 hours, inert gas shielding obtains sodium polysulfide solution.The chlorinated polyphenyl ethene of preparation is added N according to the standard of the chlorine of 1500ml/mol, and dinethylformamide obtains the chlorinated polyphenyl vinyl solution;
(3) under 50-150 ℃ of temperature, according to Na: Cl=1: 1 ratio, sodium polysulfide solution slowly is added drop-wise in the chlorinated polyphenyl vinyl solution, stir reaction was carried out 24 hours.Through washing, suction filtration obtains many sulfo-s polystyrene product, obtains powder-product through 80 ℃ of vacuumizes after 24 hours again.
Beneficial effect: solution of the present invention is that negative pole adopts the metal aluminum or aluminum alloy, compare lithium anode, both cheap, material source is extensive, and safety is handled aluminium flake by chemical activation again, 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 system 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.
Positive active material is to adopt the very high poly-organic sulfur compound of specific capacity.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.
The present invention be advantageous in that: the secondary aluminium cell positive electrode that is provided is that many sulphur chain is grafted on the skeleton of polystyrene, the S-S bond structure is fixed, the negative material that is provided is that electrochemical activation is handled aluminium flake, increased the effecting reaction area of negative pole, improve active, be difficult for producing dendrite, secondary aluminium cell capacity height, good cycle that modification combines simultaneously.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
A kind of secondary aluminium cell comprises anode, negative pole, electrolyte, barrier film, collector, and the material of described anode is the organic polysulfide compound, and the material of described battery cathode is an aluminum or aluminum alloy, and described electrolyte is halogen aluminic acid ionic liquid.
Described organic polysulfide compound is a carbyne polysulfide; Described organic polysulfide compound is many sulfo-s naphthalene or many sulfo-s aniline or many sulfo-s pyridine or many sulfo-s pyrroles or many sulfo-s thiophene or many thio-furans.
Described halogen aluminic acid ionic liquid is an aluminum halide with any is formed in quaternary ammonium salt Huo quaternary alkylphosphonium salt or the season sulfosalt; Halogen aluminic acid ionic liquid is the chlorine aluminic acid ionic liquid that aluminium chloride forms with quaternary ammonium salt.
A kind of preparation method of many sulfo-s of cell positive material polystyrene of secondary aluminium cell comprises the steps:
(1) preparation of chlorinated polyphenyl ethene: polystyrene is mixed according to mass ratio with alchlor at 8: 1, be added to then in the carbon tetrachloride solvent of 10ml/g (polystyrene) and reflux, after treating that it fully dissolves, feed chlorine, continued back flow reaction 6 hours, reaction finishes the back natural cooling, pours into then in the 200ml methyl alcohol, sedimentation products is with standby after product washing, filtration, the vacuumize;
(2) preparation of many sulfo-s polystyrene: with anhydrous sodium sulfide and sublimed sulfur according to 1: 1～1: 6 mixed in molar ratio after; standard according to the sublimed sulfur of 250ml/mol adds quantitative N; dinethylformamide; at room temperature stirred 2 hours; be warming up to 20-120 ℃ then; continue to stir 12 hours, inert gas shielding obtains sodium polysulfide solution.The chlorinated polyphenyl ethene of preparation is added N according to the standard of the chlorine of 1500ml/mol, and dinethylformamide obtains the chlorinated polyphenyl vinyl solution;
(3) under 50-150 ℃ of temperature, according to Na: Cl=1: 1 ratio, sodium polysulfide solution slowly is added drop-wise in the chlorinated polyphenyl vinyl solution, stir reaction was carried out 24 hours.Through washing, suction filtration obtains many sulfo-s polystyrene product, obtains powder-product through 80 ℃ of vacuumizes after 24 hours again.
Solution of the present invention is that negative pole adopts the metal aluminum or aluminum alloy.Compare lithium anode, both cheap, material source is extensive, again safety.Handle aluminium flake 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.
The mutual conversion that the sulfo-polymer 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.
Electrolyte system 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.
Positive active material is to adopt the very high poly-organic sulfur compound of specific capacity.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.
Negative pole
Be selected from aluminium and the alloy thereof any, 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 two or more, the form of aluminum or aluminum alloy is any in ultra micro, ultra-fine or nano powder, silk, net, sheet, paper tinsel, the foam, is preferably aluminium.
The preparation method of negative pole aluminium flake is: aluminium flake is immersed in the 2mol/LNaOH solution handled 1 minute, taking out the back washes repeatedly with distilled water, aluminium flake after treatment carries out constant-current electrolysis to be handled, aluminium flake and graphite cake are done in electrolysis tank electrode, treatment fluid is a HCl solution, concentration is 1～6mol/L, 1～5mol/L more preferably, most preferably be 1～3mol/L, current density is 0.1～0.5A/cm2, and more preferably 0.1～0.3A/cm2 most preferably is 0.2A/cm2, the electrochemical treatments time is 2 minutes, uses the HNO of 1mol/L then
3Handled 90 seconds, deionized water washes repeatedly, natural air drying.
Anodal
Constitute by positive electrode active materials, conductive agent, binding agent, organic solvent and the collector that is used to conduct electricity:
(1) above-mentioned positive electrode active materials is selected from sulphur or sulfur-based compound, be preferably the organic polysulfide compound: many sulfo-s naphthalene, many sulfo-s aniline, many sulfo-s pyridine, many sulfo-s pyrroles, many sulfo-s thiophene, many thio-furans and many sulfo-s polystyrene, more preferably many sulfo-s polystyrene.
The preparation method of above-mentioned many sulfo-s polystyrene active material is: the first step---the preparation of chlorinated polyphenyl ethene: polystyrene is mixed according to mass ratio with alchlor at 8: 1, be added to then in the carbon tetrachloride solvent of 10ml/g (polystyrene) and reflux, after treating that it fully dissolves, feed chlorine, continued back flow reaction 6 hours, reaction finishes the back natural cooling, pours into then in the 200ml methyl alcohol, sedimentation products is with standby after product washing, filtration, the vacuumize; Second step---the preparation of many sulfo-s polystyrene: with anhydrous sodium sulfide and sublimed sulfur mol ratio according to 1: 1～1: 6; more preferably 1: 2～1: 4; after most preferably being 1: 3 and mixing, add quantitative N, dinethylformamide according to the standard of the sublimed sulfur of 250mL/mol; at room temperature stirred 2 hours; be warming up to 20～120 ℃ then, more preferably 40～100 ℃, most preferably be 60～80 ℃ and continue to stir 12 hours; inert gas shielding obtains sodium polysulfide solution.The chlorinated polyphenyl ethene of preparation is added N according to the standard of the chlorine of 1500ml/mol, and dinethylformamide obtains the chlorinated polyphenyl vinyl solution.At 50～150 ℃, more preferably 60～120 ℃, most preferably be under 80～100 ℃ of temperature, according to Na: Cl=1: 1 ratio, sodium polysulfide solution slowly is added drop-wise in the chlorinated polyphenyl vinyl solution, stir reaction was carried out 24 hours.Through washing, suction filtration obtains many sulfo-s polystyrene product, obtains powder-product through 80 ℃ of vacuumizes after 24 hours again.
(2) conductive agent is selected from carbon back, graphite based conducting material and conducting polymer, specifically: be selected from active carbon, carbon black, acetylene carbon black, super carbon black (Super-P), graphite, polyaniline, polyacetylene, polypyrrole, the polythiophene any, above-mentioned electric conducting material uses separately or being used in combination of two or more above-mentioned electric conducting materials.
(3) binding agent is selected from polyvinyl acetate, polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone, polyvinylether, polymethyl methacrylate, Kynoar, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinyl pyridine, polystyrene, and in their derivative, mixture and the copolymer any or two or more.
(4) organic solvent is selected from any in acetonitrile, methyl alcohol, ethanol, acetone, oxolane, water and the isopropyl alcohol.
(5) collector is selected from any in the electric conducting material of stainless steel, carbon, copper, aluminium, nickel.Its form is selected from a kind of or carbon cloth in the foam, net, paper tinsel, sheet form of metal.
Electrolyte
Be selected from aluminum halide with any formed halogen aluminic acid ionic liquid in quaternary ammonium salt Huo 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.
Described secondary aluminium cell is selected from the square of individual layer button, multilaminate coiled cylindrical, multilayer folding, any in various ways and the specification.
The preparation of above-mentioned secondary aluminium cell has following steps:
1) preparation of many sulfo-s polystyrene positive electrode active materials slurry or carbon sulphur composite material are the preparation of positive electrode active materials slurry: with many sulfo-s polystyrene or carbon sulphur composite material is positive electrode, all add conductive agent respectively: in super conductive carbon black (SUPER-P), conductive black, acetylene black and the graphite powder a kind or multiple, and binding agent: one or more in Kynoar (PVDF), poly-oxireme (PEO), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), the ethylene-propylene rubber, ratio is 7: 2: 1, makes the positive electrode active materials slurry.
2) in the positive electrode active materials slurry of the above-mentioned many sulfo-s polystyrene positive electrode active materials slurry made or carbon sulphur composite material any is coated in following collector: on any matrix in nickel foam, stainless (steel) wire, carbon cloth, copper mesh, Copper Foil, the aluminium foil, oven dry is rolled into positive plate, handle the aluminium negative plate and be wound into the electric stamen nickel plating box hat of packing into non-barrier film and aluminium or the electrochemical activation knitted of glass fibre, add organic bath again, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell;
The preparation of many sulfo-s of positive active material polystyrene: the first step---the preparation of chlorinated polyphenyl ethene: polystyrene is mixed according to mass ratio with alchlor at 8: 1, be added to then in the carbon tetrachloride solvent of 10ml/g (polystyrene) and reflux, after treating that it fully dissolves, feed chlorine, continued back flow reaction 6 hours, reaction finishes the back natural cooling, pours into then in the 200ml methyl alcohol, sedimentation products is with standby after product washing, filtration, the vacuumize; Second step---the preparation of many sulfo-s polystyrene: with anhydrous sodium sulfide and sublimed sulfur according to 1: 3 mixed in molar ratio after; standard according to the sublimed sulfur of 250mL/mol adds quantitative N; dinethylformamide; at room temperature stirred 2 hours; being warming up to 60～80 ℃ then continues to stir 12 hours; inert gas shielding obtains sodium polysulfide solution.The chlorinated polyphenyl ethene of preparation is added N according to the standard of the chlorine of 1500ml/mol, and dinethylformamide obtains the chlorinated polyphenyl vinyl solution.Under 80～100 ℃ of temperature, according to Na: Cl=1: 1 ratio, sodium polysulfide solution slowly is added drop-wise in the chlorinated polyphenyl vinyl solution, stir reaction was carried out 24 hours.Through washing, suction filtration obtains many sulfo-s polystyrene product, obtains powder-product through 80 ℃ of vacuumizes after 24 hours again.
The negative electrode active material electrochemical activation is handled the preparation of aluminium flake: aluminium flake is immersed in the 2mol/L NaOH solution handled 1 minute, take out the back and wash repeatedly with distilled water.Aluminium flake after treatment carries out constant-current electrolysis to be handled.Aluminium flake and graphite cake are done in electrolysis tank electrode, and treatment fluid is the hydrochloric acid of concentration 2mol/L, and current density is 0.2A/cm2, and the electrochemical treatments time is 2 minutes, use the nitric acid treatment 90 seconds of 1mol/L then, and deionized water washes repeatedly, natural air drying.
Embodiment 1
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, ratio is 7: 2: 1, making the positive electrode active materials slurry is coated on the nickel foam substrate, the pole piece that oven dry is rolled into, knit barrier film and be wound into the electric core 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 alchlor and phenyl trimethyl ammonium chloride il electrolyte again, seal and make AA type cylindrical aluminium secondary cell with ratio formation in 2: 1.During the battery charging and discharging loop test, charge to 2.4V with 1C, 0.5C is discharged to 1.2V, discharges and recharges data and lists in the table 1.
Embodiment 2
Anodal preparation method is with embodiment 1, and negative electrode active material is that electrochemical 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 to 2.4V with 1C, 0.5C is discharged to 1.2V.
Embodiment 3
Many sulfo-s polystyrene material with preparation is a positive pole, and all the other anodal preparation processes are with embodiment 1.
The method of negative pole preparation is with embodiment 1, and the assembling of battery is with embodiment 1.During the battery charging and discharging loop test, charge to 2.4V with 1C, 0.5C is discharged to 1.2V, discharges and recharges data and lists in the table 1.
Embodiment 4
Many sulfo-s polystyrene material with preparation is a positive pole, and all the other anodal preparation processes are with embodiment 1.
Handling aluminium flake with electrochemical activation is negative electrode active material, and all the other preparation processes of negative pole are with embodiment 1, and the assembling of battery is with embodiment 1.During the battery charging and discharging loop test, charge to 2.4V with 1C, 0.5C is discharged to 1.2V, discharges and recharges data and lists in the table 1.
Table 1. battery charging and discharging tables of data
| Positive electrode active materials | Negative active core-shell material | Open circuit voltage/V | Initial discharge capacity/mAh | Capacity/mAh after 50 times circulates | |
| Embodiment 1 | ??C-S | ??Al | ??1.81 | ??883 | ??721 |
| Embodiment 2 | ??C-S | Electrochemical activation is handled aluminium flake | ??1.82 | ??1086 | ??977 |
| Embodiment 3 | Many sulfo-s polystyrene | ??Al | ??1.82 | ??1075 | ??968 |
| Embodiment 4 | Many sulfo-s polystyrene | Electrochemical activation is handled aluminium flake | ??1.82 | ??1109 | ??1014 |
Claims (4)
1. a secondary aluminium cell comprises anode, negative pole, electrolyte, barrier film, collector.It is characterized in that: the material of described battery cathode is an aluminum or aluminum alloy, and the material of described anode is many sulfo-s polystyrene or carbon sulphur composite material, and described electrolyte is halogen aluminic acid ionic liquid.
2. secondary aluminium cell according to claim 1 is characterized in that: described halogen aluminic acid ionic liquid is an aluminum halide with any is formed in quaternary ammonium salt Huo quaternary alkylphosphonium salt or the season sulfosalt.
3. secondary aluminium cell according to claim 1 is characterized in that: described halogen aluminic acid ionic liquid is aluminium chloride-phenyl trimethyl ammonium chloride ionic liquid.
4. the preparation method of many sulfo-s of secondary aluminium cell positive electrode polystyrene according to claim 1 is characterized in that, comprises the steps:
(1) preparation of chlorinated polyphenyl ethene: polystyrene is mixed according to mass ratio with alchlor at 8: 1, be added to then in the carbon tetrachloride solvent of 10ml/g polystyrene and reflux, after treating that it fully dissolves, feed chlorine, continued back flow reaction 6 hours, reaction finishes the back natural cooling, pours into then in the 200ml methyl alcohol, sedimentation products is with standby after product washing, filtration, the vacuumize;
(2) preparation of many sulfo-s polystyrene: with anhydrous sodium sulfide and sublimed sulfur according to 1: 1-1: after 6 the mixed in molar ratio; standard according to the sublimed sulfur of 250mL/mol adds quantitative N; dinethylformamide; at room temperature stirred 2 hours; be warming up to 20～120 ℃ then; continue to stir 12 hours, inert gas shielding obtains sodium polysulfide solution.The chlorinated polyphenyl ethene of preparation is added N according to the standard of the chlorine of 1500ml/mol, and dinethylformamide obtains the chlorinated polyphenyl vinyl solution;
(3) under 50-150 ℃ of temperature, according to Na: Cl=1: 1 ratio, sodium polysulfide solution slowly is added drop-wise in the chlorinated polyphenyl vinyl solution, stir reaction was carried out 24 hours.Through washing, suction filtration obtains many sulfo-s polystyrene product, obtains powder-product through 80 ℃ of vacuumizes after 24 hours again.
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| CN1197183C (en) * | 2000-03-01 | 2005-04-13 | 东芝株式会社 | Aluminum battery |
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| CN111354905A (en) * | 2020-02-10 | 2020-06-30 | 北京理工大学 | Composite interlayer type diaphragm for aluminum-sulfur battery and preparation method thereof |
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