CN101662021A - Preparation methods of nano-coated positive electrode materials and secondary aluminium cell using nano-coated positive electrode materials - Google Patents
Preparation methods of nano-coated positive electrode materials and secondary aluminium cell using nano-coated positive electrode materials Download PDFInfo
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Abstract
The invention discloses a novel high-energy secondary aluminium cell and a preparation method. The aim is to provide a method for preparing nano material-coated positive electrode active materials, bycoating the positive and negative electrode active materials with the nano materials, it is possible to subject the positive and negative electrode active materials to nano treatment; therefore, thehigh-energy secondary aluminium cell features obviously improved properties, simple material composition, low cost, simple technology, environmentally friendly synthesis path, relatively high capacityand relatively good cycle property and market prospect. The secondary aluminium cell comprises the positive and negative electrodes prepared by the modified positive and negative electrode active materials coated by the nano material surfaces, or any one electrode in the singly coated positive or negative electrode active materials, polyelectrolyte (ionic liquid) and a diaphragm. The coating materials are semimetals, oxides, salts or conductive polymers. The invention uses the nano materials in the secondary aluminium cell for the first time; therefore, the cell has higher open circuit voltage and reversible capacity and better cycle property.
Description
Technical field
The present invention relates to a kind of preparation method of positive electrode active materials and secondary aluminium cell and preparation method thereof, more particularly, the preparation method who relates to a kind of nanometer clad anode active material, positive and negative electrode nano double coat secondary aluminium cell of the arbitrary electrode in secondary aluminium cell of active material and preparation method thereof or single clad anode of nanometer or the negative active core-shell material and preparation method thereof.
Background technology
Along with people to the craving for of high-energy-density power supply, press for exploitation and the application of cheapness, safety, environmental protection and high performance secondary cell.With aluminium and alloy thereof is that negative material, sulphur based material are that the secondary aluminium-sulfur battery of positive pole then is one of battery that satisfies above-mentioned requirements.Aluminium, sulfur materials safety, environmental protection, cheap and aboundresources, battery security is good.The metallic aluminium theoretical energy density is only second to lithium metal (3862mAh/g) up to 2980mAh/g.Its volume and capacity ratio is 8050mAh/cm
3, be about lithium (2040mAh/cm
3) 4 times, the aluminium electrode potential in neutrality and acid medium is-1.66V, is-2.35V that elementary sulfur also has bigger theoretical energy density (1670mAh/g), all is desirable high-energy battery material in alkaline medium.
People such as Li Guangwen (CN 1199936A) study aluminum-air cell neutral, alkaline system, and as primary cell, aluminum-air cell is used at aspects such as portable set, fixed power source and ocean purposes.Yet, be an aluminum cell of representative with the aluminum-air cell, because electrolyte body is the aqueous solution, can't charge, can not recycle.
The form of sulphur is a lot, elemental sulfur is the insulator of ion and electronics at ambient temperature, and the micromolecule organic sulfur compound that produces when sulphur-sulfide linkage ruptures is dissolved in electrolyte, generates the unordered sulphur of irreversible reaction, cause problems such as the rapid decay of self discharge and capacity, make the very fast decline of cycle performance of battery.
For fear of the problems referred to above and give the performance of battery with excellence, Naoi has synthesized two phenothiazine polymer positive electrode (J.Electrochem.Soc. first in 1997,1997,144 (6): L173) and in the lithium battery system, obtained good application, but because the preparation expensive raw material price of this class material, therefore the synthesis technique complexity is difficult to obtain practical application; US Pat 5441831, US Pat 5460905 disclose carbon-sulphur compound among US Pat 5601947 and the US Pat 5609720, but there is the low problem of theoretical capacity in it, and is not easy regeneration molecular structure identical materials; Skothcim will gather carbon disulfide (PCS) electrode and be applied to serondary lithium battery and obtained capacity and cycle performance (US Pat 5460905) preferably, but the pollution that in the building-up process environment is produced can not be ignored; Wang Jiulin adopts the method for high-temperature dehydrogenation sulfuration to realize the branching crosslinked (CN1339839A) of S-S structure on polymeric matrixs such as polyethylene glycol oxide, Kynoar, owing to constantly produce corrosive gas in the building-up process, to creating a great impression of environment and equipment, thereby make this route of synthesis have certain defective.
Aluminium as negative material equally also exists the problem that some can not be ignored: the real work current potential of (1) aluminium is high more a lot of than theoretical value; Very strong affinity is arranged between aluminium alloy and the oxygen, and in the air and the aqueous solution, the surface generates the passive oxidation film of one deck densification, makes the electrode potential of aluminium not reach due theoretical electrode potential, 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 oxide-film destroyed will being corroded rapidly in a single day.Therefore, the aluminium negative pole as electrode material should have excellent electrochemical properties and decay resistance.
Summary of the invention
Existence in view of above problem, the present invention coats and the absorption elemental sulfur with nanometer conductive polymer and porous material, so both improved the conductivity of material, can suppress elemental sulfur effectively again and product is dissolved in the electrolyte, the nano anode material of a kind of high-performance, route of synthesis environmental protection is provided.
Concluded, the objective of the invention is to, overcome the shortcoming of prior art, provide a kind of preparation method with nano material clad anode active material and nano material double-contracting to cover the single clad anode of both positive and negative polarity active material or nanometer or one of them electrode of negative active core-shell material, make both positive and negative polarity active material equal nanometer, or a kind of material nano in the negative or positive electrode active material, performance is obviously improved, material forms simple, production cost is low, technology is simple, the synthesis path environmental protection, have higher charge/discharge capacity and the high energy secondary aluminium cell and preparation method thereof of cycle performance and market prospects preferably.
It is as follows that the Nanosurface of positive electrode active materials elemental sulfur of the present invention coats the principle of handling: some predecessor A of an amount of clad material is dissolved in appropriate solvent, is mixed into even mixed liquor with active material powder to be coated.The solution of other predecessors B of clad material is joined in the mixed liquor in the stirring gradually, and the pH value of control mixture is coated on surface of active material with the precursor A and the sediment that B reacts generation of coating.Filter through cyclic washing, the filtrate that obtains heats under suitable temperature and atmosphere, can obtain the composite material covered with nano surface positive electrode active materials.
In the prepared secondary aluminium cell of the present invention, anodal preparation process principle is as follows: take by weighing active material, conductive agent, binding agent by weight, the adding proper amount of solvent stirs repeatedly and makes batch mixing evenly be paste after mixing, and coats on the flow collection sheet, after treating solvent evaporates, standby after the vacuumize.
In the prepared secondary aluminium cell of the present invention, the preparation process principle of negative pole is as follows: take by weighing active material, binding agent by weight, the adding proper amount of solvent stirs repeatedly and makes batch mixing evenly be paste after mixing, and coats on the flow collection sheet, after treating solvent evaporates, standby after the vacuumize.
The secondary aluminium cell of arbitrary electrode and the preparation method of secondary aluminium cell in the preparation method of the positive electrode active materials of Nanosurface coating modification elemental sulfur of the present invention and nano double coating or single clad anode or the negative active core-shell material, be achieved by following technical proposals
Nanometer conductive polymer surface coats the preparation method of the positive electrode active materials of sulphur: above-mentioned conducting polymer is selected from: polyaniline, polythiophene, polypyrrole, polyacetylene with and derivative in a kind of, it is characterized in that: this method has following steps: be the elemental sulfur of 1-100g with quality, pack in the there-necked flask of 200-300ml, add again the hydrochloric acid that volume is 10-100ml, behind the ultrasonic oscillation 0.5-1.5h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With aniline or thiophene or pyrroles or acetylene with and derivative in a kind of; mol ratio is 1: 0.5-5; add be dissolved with aniline or thiophene or pyrroles or acetylene with and derivative in a kind of aqueous hydrochloric acid solution of monomer, magnetic agitation drips Ammonium Persulfate 98.5 (NH with dropping funel under nitrogen protection
4)
2S
2O
8Solution is as oxidant, the control rate of addition, solution was added dropwise to complete in 0.1-5 hour, make reaction carry out stopping to stir behind the 5-7h, in whole process, reaction is at room temperature carried out, (described room temperature refers to 16-35 ℃, as follows) the reaction end, product is carried out centrifugation, and under ul-trasonic irradiation, use the deionized water washed product, until washing lotion is colourless, end product namely obtains the positive electrode active materials that the nanometer conductive polymer surface coats sulphur behind 70-90 ℃ of lower vacuum drying 20-28h.It more than is the general method of this positive electrode active materials of preparation.
Nanometer conductive polymer surface as previously discussed coats the preparation method of the positive electrode active materials of sulphur: it is characterized in that: above-mentioned nanometer conductive polymer is nano polyaniline, this method has following steps: be the elemental sulfur of 1-100g with quality, pack in the there-necked flask of 200-300ml, add again the hydrochloric acid that volume is 10-100ml, behind the ultrasonic oscillation 0.5-1.5h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With the aniline mol ratio be 1: 0.5-5, add the aqueous hydrochloric acid solution be dissolved with aniline monomer, magnetic agitation drips Ammonium Persulfate 98.5 (NH with dropping funel under nitrogen protection
4)
2S
2O
8Solution is as oxidant, the control rate of addition was added dropwise to complete solution in 0.1-5 hour, make reaction carry out stopping to stir behind the 5-7h, in whole process, reaction is at room temperature carried out, and described room temperature is 16-35 ℃, and reaction finishes, product is carried out centrifugation, and under ul-trasonic irradiation, use the deionized water washed product, until washing lotion is colourless, end product namely obtains the positive electrode active materials that nano polyaniline coats sulphur behind the vacuum drying 20-28h under 70-90.It more than is the method preferably of this positive electrode active materials of preparation.
Nanometer conductive polymer surface as previously discussed coats the preparation method of the positive electrode active materials of sulphur, it is characterized in that: above-mentioned nanometer conductive polymer is a nano polyaniline, this method has following steps: be the elemental sulfur of 10-30g with quality, pack in the there-necked flask of 200-300ml, add the hydrochloric acid that volume is 20-80ml again, behind the ultrasonic oscillation 1h, according to Ammonium Persulfate 98.5 and aniline mol ratio is 1: 1-3, add the aqueous hydrochloric acid solution that is dissolved with aniline monomer, the control rate of addition, solution was added dropwise to complete in 0.5-1.5 hour, make reaction carry out stopping to stir behind the 6h, end product promptly obtains the positive electrode active materials that nano polyaniline coats sulphur behind 80 ℃ of following vacuumize 24h.It more than is the method preferably of this positive electrode active materials of preparation.
Nanometer conductive polymer surface as previously discussed coats the preparation method of the positive electrode active materials of sulphur, it is characterized in that: above-mentioned nanometer conductive polymer is nano polyaniline, this method has following steps: be the elemental sulfur of 3-5g with quality, pack in the there-necked flask of 250ml, add again the hydrochloric acid that volume is 30-50ml, behind the ultrasonic oscillation 1h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With the aniline mol ratio be 1: 1, add the aqueous hydrochloric acid solution that is dissolved with aniline monomer, the control rate of addition was added dropwise to complete solution in 1 hour, make reaction carry out stopping to stir behind the 6h, end product namely obtains the positive electrode active materials that the nano polyaniline surface coats sulphur behind 80 ℃ of lower vacuum drying 24h.It more than is the best way of this positive electrode active materials of preparation.
Secondary aluminium cell, consisted of by positive pole, negative pole and electrolyte, barrier film, it is characterized in that: it is by any positive pole as positive electrode active materials that coats take Nanosurface in modification elemental sulfur or the C-S composite, coat any negative pole as negative active core-shell material among modified aluminium and aluminium alloy or Al or the Al-Zn take Nanosurface, in organic or inorganic electrolyte solution or polymer dielectric or the solid electrolyte any is electrolyte, barrier film, collector, battery case and lead-in wire form; Should be noted that: above-mentioned anodal clad material is selected from one or more the mixture in the following various types of materials: 1) semimetal: material with carbon element: be selected from various hard carbon materials, soft material with carbon element, graphite, graphitized material and the modified graphite class material any one or more; 2) oxide or composite oxides: be selected from MgO, Al
2O
3, SiO
2, SnO, TiO
2, SnO
2, V
2O
5, VO
2, MnO
2, Fe
2O
3, Fe
3O
4In any one or more; 3) salt material: be selected from AlPO
4, Mg
3(PO
4)
2In any; 4) conducting polymer: be selected from polyaniline, polythiophene, polypyrrole polyacetylene with and derivative in any one or more; Above-mentioned negative pole clad material is selected from one or more the mixture in the following various types of materials: 1) semimetal: material with carbon element is selected from various hard carbon materials, soft material with carbon element, graphite, graphitized material and the modified graphite class material any one or more; 2) conducting polymer: be selected from polyaniline, polythiophene, polypyrrole polyacetylene with and derivative in any one or more, this secondary aluminium cell is made into any in individual layer button, multi-layer coiling column shape, the square various ways of multilayer folding and the specification.More than be the basic structure of general secondary aluminium cell of the present invention.
Secondary aluminium cell as previously discussed, by positive pole, negative pole and electrolyte, barrier film constitutes, it is characterized in that: the positive electrode active materials of above-mentioned Nanosurface coating modification elemental sulfur is the positive electrode active materials that the nano polyaniline surface coats sulphur, the negative active core-shell material of above-mentioned Nanosurface coating modification aluminium and aluminium alloy is the negative active core-shell material that the nano-sized carbon surface coats aluminium powder and Al alloy powder, this secondary aluminium cell is by the positive pole that coats the positive electrode active materials of sulphur with the nano polyaniline surface, coat the negative pole of the negative active core-shell material of aluminium powder and Al alloy powder with the nano-sized carbon surface, in organic or inorganic electrolyte solution or polymer dielectric or the solid electrolyte any is electrolyte, barrier film, collector, battery case and lead-in wire are formed.More than be the basic structure of best secondary aluminium cell of the present invention.
The preparation method of secondary aluminium cell is characterized in that: this method has following steps:
1) preparation or the carbon sulphur composite of the positive electrode active materials slurry of nanometer conductive polymer surface coating sulphur are the preparation of positive electrode active materials slurry: be the elemental sulfur of 1-100g with quality, pack in the there-necked flask of 200-300ml, add again the hydrochloric acid that volume is 10-100ml, behind the ultrasonic oscillation 0.5-1.5h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With aniline or thiophene or pyrroles or acetylene take and derivative in a kind of mol ratio as 1: 0.5-5; add be dissolved with aniline or thiophene or pyrroles or acetylene with and derivative in a kind of aqueous hydrochloric acid solution of monomer; magnetic agitation drips Ammonium Persulfate 98.5 (NH with dropping funel under nitrogen protection
4)
2S
2O
8Solution is as oxidant, the control rate of addition, solution was added dropwise to complete in 0.1-5 hour, make reaction carry out stopping to stir behind the 5-7h, in whole process, reaction is at room temperature carried out, above-mentioned room temperature refers to 16-35 ℃, reaction finishes, product is carried out centrifugation, and under ul-trasonic irradiation, use the deionized water washed product, until washing lotion is colourless, end product namely obtains the positive electrode that the nanometer conductive polymer surface coats sulphur behind 70-90 ℃ of lower vacuum drying 20-28h, or take mass ratio as 1: 3 carbon sulphur composite as positive electrode, all add respectively conductive agent: super conductive carbon black (SUPER-P), conductive black, in acetylene black and the graphite powder one or more and binding agent: Kynoar (PVDF), Pluronic F-127 (PEO), polytetrafluoroethylene (PTFE) (PTFE), sodium carboxymethylcellulose (CMC), in the EP rubbers one or more, ratio is 6-8: 1-3: 0.5-1.5, makes the positive electrode active materials slurry;
The nanometer conductive polymer surface of 2) making above-mentioned coats in the positive electrode active materials slurry of the positive electrode active materials slurry of sulphur or carbon sulphur composite material any and is coated in the thick collector of 0.5-0.7mm: nickel foam, stainless (steel) wire, carbon cloth, copper mesh, Copper Foil, on wantonly a kind of matrix in the aluminium foil, oven dry roll to 0.2-0.4mm be cut into 30-50mm wide * the long positive plate of 140-160mm, knit barrier film and be wound into the electric stamen nickel plating box hat of packing into the thick glass fibre of 0.1-0.2mm is non-with any the negative plate among the surface coated aluminium powder of nanometer C and Al alloy powder or Al or the Al-Zn as the negative active core-shell material preparation, add organic bath again, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell; The preparation method of the negative material of above-mentioned nanometer C surface coating modification aluminium and aluminum alloy materials is: aluminum or aluminum alloy and poly-oxireme (PEO) powder that grinds after sieving are pressed mass ratio 1: 1-10, putting into grinding in ball grinder mixes, aluminum or aluminum alloy and coating precursor PEO are mixed, mixture is placed in the tube type resistance furnace, under the condition of argon shield, the compound 0.5-10h of heating and decomposition under 50-400 ℃ of condition, in heating process, PEO is decomposed into the carbon of nano aperture fully, thereby be coated on the surface of aluminum or aluminum alloy mixed uniformly with it, aluminum or aluminum alloy is filled in the nano aperture of carbon, natural cooling, get final product the negative material of the surface coated aluminium powder of nano-sized carbon and Al alloy powder; Above-mentioned negative plate preparation method is: with purity be 99.5% aluminium flake be cut into 35-45mm wide * size that 150-170mm length * 0.1mm is thick, as negative plate; Perhaps with aluminium powder and alloy thereof as negative electrode active material, the active material dry powder of 3-5g is applied on the collector, roll to 0.2-0.4mm be cut into 35-45mm wide * the long pole piece of 150-170mm is as negative plate; Solvent is selected from wantonly a kind in water, ethanol, acetonitrile, the N-methyl pyrrolidone; Electrolyte is selected from the organic electrolyte that contains aluminium salt or contains in the aluminum ions ionic liquid wantonly a kind.
The preparation method of secondary aluminium cell as previously discussed is characterized in that: this method has following steps:
1) above-mentioned nanometer conductive polymer is: nano polyaniline, preparation or carbon sulphur composite that this nano polyaniline surface coats the positive electrode active materials slurry of sulphur are the preparation of positive electrode active materials slurry: be the elemental sulfur of 1-100g with quality, pack in the there-necked flask of 200-300ml, add again the hydrochloric acid that volume is 10-100ml, behind the ultrasonic oscillation 0.5-1.5h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With the mol ratio of aniline be 1: 0.5-5, add the aqueous hydrochloric acid solution be dissolved with aniline monomer, magnetic agitation drips Ammonium Persulfate 98.5 (NH with dropping funel under nitrogen protection
4)
2S
2O
8Solution is as oxidant, the control rate of addition, solution was added dropwise to complete in 0.1-5 hour, make reaction carry out stopping to stir behind the 5-7h, in whole process, reaction is at room temperature carried out, described room temperature refers to 16-35 ℃, reaction finishes, product is carried out centrifugation, and under ul-trasonic irradiation, use the deionized water washed product, until washing lotion is colourless, end product namely obtains the positive electrode that the nano polyaniline surface coats sulphur behind 70-90 ℃ of lower vacuum drying 20-28h, or take mass ratio as 1: 3 carbon sulphur composite as positive electrode, all add respectively conductive agent: super conductive carbon black (SUPER-P), conductive black, in acetylene black and the graphite powder one or more and adhesive PVDF, PEO, PTFE, CMC, in the EP rubbers one or more, ratio is 6-8: 1-3: 0.5-1.5, makes the positive electrode active materials slurry;
The nano polyaniline surface of 2) making above-mentioned coats in the positive electrode active materials slurry of the positive electrode active materials slurry of sulphur or carbon sulphur composite material any and is coated in the thick collector of 0.5-0.7mm: nickel foam, stainless (steel) wire, carbon cloth, copper mesh, Copper Foil, on wantonly a kind of matrix in the aluminium foil, oven dry roll to 0.2-0.4mm be cut into 30-50mm wide * the long positive plate of 140-160mm, knit barrier film and be wound into the electric stamen nickel plating box hat of packing into the thick glass fibre of 0.1-0.2mm is non-with any the negative pole among the surface coated aluminium powder of nanometer C and Al alloy powder or Al or the Al-Zn as the negative active core-shell material preparation, add organic bath again, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell; The preparation method of the negative material of above-mentioned nanometer C surface coating modification aluminium and aluminum alloy materials is: the PEO powder after aluminum or aluminum alloy and grinding are sieved is by mass ratio 1: 1-10, putting into grinding in ball grinder mixes, aluminum or aluminum alloy and coating precursor PEO are mixed, mixture is placed in the tube type resistance furnace, under the condition of argon shield, the compound 0.5-10h of heating and decomposition under 50-400 ℃ of condition, in heating process, PEO is decomposed into the carbon of nano aperture fully, thereby be coated on the surface of aluminum or aluminum alloy mixed uniformly with it, aluminum or aluminum alloy is filled in the nano aperture of carbon, natural cooling, get final product the negative material of the surface coated aluminium powder of nano-sized carbon and Al alloy powder; Above-mentioned negative pole preparation method is: with purity be 99.5% aluminium flake be cut into 35-45mm wide * size that 150-170mm length * 0.1mm is thick, as negative plate; Perhaps with aluminium powder and alloy thereof as negative electrode active material, the active material dry powder of 3-5g is applied on the collector, roll to 0.2-0.4mm be cut into 35-45mm wide * the long pole piece of 150-170mm is as negative plate; Solvent is selected from wantonly a kind in water, ethanol, acetonitrile, the N-methyl pyrrolidone; Electrolyte is selected from the organic electrolyte that contains aluminium salt or contains in the aluminum ions ionic liquid wantonly a kind.
The preparation method of secondary aluminium cell as previously discussed is characterized in that: this method has following steps:
1) above-mentioned nanometer conductive polymer is a nano polyaniline, this nano polyaniline surface coats the preparation of the positive electrode active materials slurry of sulphur: with quality is the elemental sulfur of 10-30g, pack in the there-necked flask of 200-300ml, add the hydrochloric acid that volume is 20-80ml again, behind the ultrasonic oscillation 1h, according to Ammonium Persulfate 98.5 and aniline mol ratio is 1: 1-3, add the aqueous hydrochloric acid solution that is dissolved with aniline monomer, the control rate of addition, solution was added dropwise to complete in 0.5-1.5 hour, make reaction carry out stopping to stir behind the 6h, end product promptly obtains the positive electrode that the nano polyaniline surface coats sulphur behind 80 ℃ of following vacuumize 24h, add conductive agent: super conductive carbon black (SUPER-P) and adhesive PVDF, ratio is 7: 2: 1, makes above-mentioned positive electrode active materials slurry;
2) the above-mentioned positive electrode active materials slurry of making is coated on the thick nickel foam substrate of 0.6mm, oven dry roll to 0.3mm be cut into 40mm wide * the long pole piece of 150mm, knit barrier film and be wound into the electric stamen nickel plating box hat of packing into the thick glass fibre of 0.16mm is non-with the negative pole of the preparation of surface coated aluminium powder of nanometer C and Al alloy powder, add organic bath again, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell; The preparation method of the negative material of above-mentioned nanometer C surface coating modification aluminium and aluminum alloy materials is: the PEO powder after aluminum or aluminum alloy and grinding are sieved is by mass ratio 1: 2-5, put into grinding in ball grinder and mix the compound 2-6h of heating and decomposition under 100-350 ℃ of condition; The preparation method of above-mentioned negative pole is: purity be 99.5% aluminium flake be cut into 35-45mm wide * size that 150-170mm length * 0.1mm is thick, as negative plate; Perhaps with aluminium powder and alloy thereof as negative electrode active material, the active material dry powder of 3-5g is applied on the collector, roll to 0.2-0.4mm be cut into 35-45mm wide * the long pole piece of 150-170mm is as negative plate.Should be noted that: be preferably the process conditions except the process conditions that adopt nano double clad anode and negative pole and use among this secondary aluminium cell preparation method, the additive method step is with above-described identical.
The preparation method of secondary aluminium cell as previously discussed is characterized in that: this method has following steps:
1) above-mentioned nanometer conductive polymer is nano polyaniline, this nano polyaniline surface coats the preparation of the positive electrode active materials slurry of sulphur: be the elemental sulfur of 3-5g with quality, pack in the there-necked flask of 250ml, add again the hydrochloric acid that volume is 30-50ml, behind the ultrasonic oscillation 1h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With the aniline mol ratio be 1: 1, add the aqueous hydrochloric acid solution that is dissolved with aniline monomer, the control rate of addition was added dropwise to complete solution in 1 hour, make reaction carry out stopping to stir behind the 6h, end product namely obtains the positive electrode that the nano polyaniline surface coats sulphur behind 80 ℃ of lower vacuum drying 24h; Add conductive agent SUPER-P and adhesive PVDF, ratio is 7: 2: 1, makes the positive electrode active materials slurry;
2) the above-mentioned positive electrode active materials slurry of making is coated on the thick nickel foam substrate of 0.6mm, oven dry roll to 0.3mm be cut into 40mm wide * the long pole piece of 150mm; Knit barrier film and be wound into the electric stamen nickel plating box hat of packing into the thick glass fibre of 0.16mm is non-with the negative pole of the preparation of surface coated aluminium powder of nanometer C and Al alloy powder; Add organic bath again, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell; The preparation method of the negative material of above-mentioned nanometer C surface coating modification aluminium and aluminum alloy materials is: is 1: 3 to put into grinding in ball grinder mix under 250-350 ℃ condition heating and decomposition compound 3-5h with the PEO powder that grinds after sieving by mass ratio with aluminum or aluminum alloy; The preparation method of above-mentioned negative pole is: purity be 99.5% aluminium flake be cut into 35-45mm wide * size that 150-170mm length * 0.1mm is thick, as negative plate; Perhaps with aluminium powder and alloy thereof as negative electrode active material, the active material dry powder of 3-5g is applied on the collector, roll to 0.2-0.4mm be cut into 35-45mm wide * the long pole piece of 150-170mm is as negative plate.Should be noted that: except the process conditions that adopt nano double clad anode and negative pole and use were best process conditions, the additive method step was with above-described identical among this secondary aluminium cell preparation method.
The preparation method of secondary aluminium cell as previously discussed is characterized in that: coat sulphur and negative active core-shell material employing Al or Al-Zn except positive electrode active materials adopts the nano polyaniline surface; Or negative active core-shell material employing nano-carbon coated Al-2Zn, positive electrode active materials adopts outside the C-S composite, and other steps are identical with above-described step.
Nanosurface of the present invention coats the preparation method of the elemental sulfur positive electrode active materials of handling and the preparation method of secondary aluminium cell and secondary aluminium cell has following beneficial effect compared with prior art:
1. coat processing by the secondary aluminium cell positive electrode active materials being carried out nano-material surface, change surface physics and the chemical characteristic of positive electrode active materials, thereby specific capacity and the specific energy of positive electrode have been improved, the cyclicity that has guaranteed simultaneously positive electrode does not reduce, improve the energy density of battery, improve the charge-discharge performance of battery;
More particularly: Nanosurface coats the elemental sulfur positive electrode of handling, its physicochemical properties with coat before material compared very big change: (1) nano material coats elemental sulfur, make elemental sulfur in the nano-scale particle degree, be embedded in the electric conducting material, so little simple substance sulphur granule can improve the electrochemical reaction utilance of active material to a great extent; (2), improve the defective of elemental sulfur and electrochemical reaction product electric conductivity difference thereof with the compound conductivity that can whole raising system of electric conducting material; (3) elemental sulfur fully is embedded in contact with it on the electric conducting material of bigger serface or the molecular level, can play to suppress elemental sulfur and the electrochemical reaction product is dissolved in the electrolyte, improves the cycle performance of sulfur electrode;
2. secondary aluminium cell reversible capacity height of the present invention, good cycle, technology are simple, environment friendly and pollution-free, safe and reliable, applicable multiple occasion, fields such as for example occasion of removable power supplys such as mobile phone, notebook computer, mobile electronic device, and electric motor car, hybrid-power electric vehicle;
3. whole process of production is pollution-free, and preparation cost is low, and technology is simple, the secondary aluminium cell energy density height of preparation.
Embodiment
The positive electrode Nanosurface coats modification elemental sulfur material preparation principle: the elemental sulfur of certain mass is packed in the there-necked flask of 250ml; drop into again the hydrochloric acid of certain mass; behind the ultrasonic oscillation 1h; add a certain proportion of aqueous hydrochloric acid solution that is dissolved with aniline monomer; magnetic agitation drips Ammonium Persulfate 98.5 (NH with dropping funel with certain speed under nitrogen protection
4)
2S
2O
8Solution makes reaction carry out stopping to stir behind the 6h as oxidant, and in whole process, reaction is at room temperature carried out, and described room temperature refers to 16-35 ℃.Reaction finishes, and product is carried out centrifugation, and use the deionized water wash product under the ultrasonic wave effect, and is colourless up to washing lotion, and end product promptly obtains the positive electrode active materials that nano polyaniline coats sulphur behind 80 ℃ of following vacuumize 24h.
Embodiment 1
At C: the S mass ratio is in the positive electrode active materials of making in 1: 3 the carbon sulphur composite material, add conductive agent: super conductive carbon black (SUPER-P) and adhesive PVDF, ratio is 7: 2: 1, making the positive electrode active materials slurry is coated on the thick nickel foam substrate of 0.6mm, oven dry roll to 0.3mm be cut into 40mm wide * the long pole piece of 150mm, knit barrier film and be wound into the electric stamen nickel plating box hat of packing into the thick glass fibre of 0.16mm is non-with the negative pole that aluminium flake is made as negative active core-shell material, add organic bath again, seal and make AA type cylinder secondary aluminium cell.During the battery charging and discharging loop test, charge with 0.5C, the 1C discharge, discharge cut-off voltage is 1.2V, discharges and recharges data and lists in the table 1.
Embodiment 2
Anodal preparation method is with embodiment 1, and negative active core-shell material is coated on the nickel foam collector for the Al-2Zn alloy, carries out the assembling of battery by the method identical with embodiment 1.During the battery charging and discharging loop test, charge with 0.5C, the 1C discharge, discharge cut-off voltage is 1.2V, discharges and recharges data and lists in the table 1.
Embodiment 3
Anodal preparation method is with embodiment 1, and negative active core-shell material is that nanometer C surface coats the Al-2Zn alloy, is coated on the nickel foam collector, carries out the assembling of battery by the method identical with example 1.During the battery charging and discharging loop test, charge with 0.5C, the 1C discharge, discharge cut-off voltage is 1.2V, discharges and recharges data and lists in the table 1.
Embodiment 4
With the surface coated elemental sulfur of nano polyaniline is positive electrode, 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 with 0.5C, the 1C discharge, discharge cut-off voltage is 1.2V, discharges and recharges data and lists in the table 1.
Embodiment 5
Anodal preparation is with embodiment 4, and the preparation of negative pole and battery is with embodiment 2.During the battery charging and discharging loop test, charge with 0.5C, the 1C discharge, discharge cut-off voltage is 1.2V, discharges and recharges data and lists in the table 1.
Embodiment 6
Anodal preparation is with embodiment 4, and the preparation of negative pole and battery is with embodiment 3.During the battery charging and discharging loop test, charge with 0.5C, the 1C discharge, discharge cut-off voltage is 1.2V, the battery charging and discharging data are listed 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 | 1.57 | 883 | 721 |
| Embodiment 2 | C-S | Al-2Zn | 1.68 | 976 | 864 |
| Embodiment 3 | C-S | Nanometer C coats Al-2Zn | 1.72 | 1032 | 930 |
| Embodiment 4 | Nano polyaniline coats S | Al | 1.62 | 1007 | 879 |
| Embodiment 5 | Nano polyaniline coats S | Al-2Zn | 1.73 | 1094 | 1001 |
| Embodiment 6 | Nano polyaniline coats S | Nanometer C coats Al-2Zn | 1.78 | 1145 | 1072 |
Can find out from the data of table 1: 1) positive electrode active materials or negative active core-shell material have, when no nano material coats, initial discharge capacity and the circulation 50 times after capacity be distinguishing, namely anodal and negative pole all adopts nano material to coat the secondary aluminium cell of the both positive and negative polarity preparation of preparation, initial discharge capacity is the highest, the capacity that circulates after 50 times is also the highest, cycle life is the longest, 2) only with the nano material clad anode or only coat the secondary cell of the both positive and negative polarity preparation of negative pole preparation with nano material, initial discharge capacity or circulate that capacity takes second place after 50 times, the secondary aluminium cell of the both positive and negative polarity preparation of preparation when 3) anodal and negative pole does not all adopt nano material to coat, initial discharge capacity or the capacity that circulates after 50 times are minimum, also have any different when 4) negative material adopts Al or Al-2Zn: when positive electrode all adopts the C-S composite, initial discharge capacity or circulate higher when the Capacity Ratio negative pole adopts Al after 50 times when negative pole adopts Al-2Zn.
Therefore, compare with above-mentioned other secondary cells, the secondary aluminium cell that forms when positive electrode active materials of the present invention and negative active core-shell material all come double-contracting to cover with nano material is best.
Claims (10)
1. nanometer conductive polymer surface coats the preparation method of the positive electrode active materials of sulphur: above-mentioned conducting polymer is selected from: polyaniline, polythiophene, polypyrrole, polyacetylene with and derivative in a kind of, it is characterized in that: this method has following steps: be the elemental sulfur of 1-100g with quality, pack in the there-necked flask of 200-300ml, add again the hydrochloric acid that volume is 10-100ml, behind the ultrasonic oscillation 0.5-1.5h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With aniline or thiophene or pyrroles or acetylene with and derivative in a kind of; mol ratio is 1: 0.5-5; add be dissolved with aniline or thiophene or pyrroles or acetylene with and derivative in a kind of aqueous hydrochloric acid solution of monomer, magnetic agitation drips Ammonium Persulfate 98.5 (NH with dropping funel under nitrogen protection
4)
2S
2O
8Solution is as oxidant, the control rate of addition was added dropwise to complete solution in 0.1-5 hour, make reaction carry out stopping to stir behind the 5-7h, in whole process, reaction is at room temperature carried out, and described room temperature refers to 16-35 ℃, and reaction finishes, product is carried out centrifugation, and under ul-trasonic irradiation, use the deionized water washed product, until washing lotion is colourless, end product namely obtains the positive electrode active materials that nanometer conductive polymer coats sulphur behind 70-90 ℃ of lower vacuum drying 20-28h.
2. nanometer conductive polymer as claimed in claim 1 surface coats the preparation method of the positive electrode active materials of sulphur: it is characterized in that: above-mentioned nanometer conductive polymer is nano polyaniline, this method has following steps: be the elemental sulfur of 1-100g with quality, pack in the there-necked flask of 200-300ml, add again the hydrochloric acid that volume is 10-100ml, behind the ultrasonic oscillation 0.5-1.5h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With the aniline mol ratio be 1: 0.5-5, add the aqueous hydrochloric acid solution be dissolved with aniline monomer, magnetic agitation drips Ammonium Persulfate 98.5 (NH with dropping funel under nitrogen protection
4)
2S
2O
8Solution is as oxidant, the control rate of addition was added dropwise to complete solution in 0.1-5 hour, make reaction carry out stopping to stir behind the 5-7h, in whole process, reaction is at room temperature carried out, and described room temperature refers to 16-35 ℃, and reaction finishes, product is carried out centrifugation, and under ul-trasonic irradiation, use the deionized water washed product, until washing lotion is colourless, end product namely obtains the positive electrode active materials that the nano polyaniline surface coats sulphur behind 70-90 ℃ of lower vacuum drying 20-28h.
3. nanometer conductive polymer as claimed in claim 2 surface coats the preparation method of the positive electrode active materials of sulphur, it is characterized in that: above-mentioned nanometer conductive polymer is a nano polyaniline, this method has following steps: be the elemental sulfur of 10-30g with quality, pack in the there-necked flask of 200-300ml, add the hydrochloric acid that volume is 20-80ml again, behind the ultrasonic oscillation 1h, according to Ammonium Persulfate 98.5 and aniline mol ratio is 1: 1-3, add the aqueous hydrochloric acid solution that is dissolved with aniline monomer, the control rate of addition, solution was added dropwise to complete in 0.5-1.5 hour, make reaction carry out stopping to stir behind the 6h, end product promptly obtains the positive electrode active materials that the nano polyaniline surface coats sulphur behind 80 ℃ of following vacuumize 24h.
4. nanometer conductive polymer as claimed in claim 2 surface coats the preparation method of the positive electrode active materials of sulphur, it is characterized in that: above-mentioned nanometer conductive polymer is nano polyaniline, this method has following steps: be the elemental sulfur of 3-5g with quality, pack in the there-necked flask of 250ml, add again the hydrochloric acid that volume is 30-50ml, behind the ultrasonic oscillation 1h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With the aniline mol ratio be 1: 1, add the aqueous hydrochloric acid solution that is dissolved with aniline monomer, the control rate of addition was added dropwise to complete solution in 1 hour, make reaction carry out stopping to stir behind the 6h, end product namely obtains the positive electrode active materials that the nano polyaniline surface coats sulphur behind 80 ℃ of lower vacuum drying 24h.
5. secondary aluminium cell, consisted of by positive pole, negative pole and electrolyte, barrier film, it is characterized in that: it is by any positive pole as positive electrode active materials that coats take Nanosurface in modification elemental sulfur or the C-S composite, coat any negative pole as negative active core-shell material among modified aluminium and aluminium alloy or Al or the Al-Zn take Nanosurface, in organic or inorganic electrolyte solution or polymer dielectric or the solid electrolyte any is electrolyte, barrier film, collector, battery case and lead-in wire form; Should be noted that: above-mentioned anodal clad material is selected from one or more the mixture in the following various types of materials: 1) semimetal: material with carbon element: be selected from various hard carbon materials, soft material with carbon element, graphite, graphitized material and the modified graphite class material any one or more; 2) oxide or composite oxides: be selected from MgO, Al
2O
3, SiO
2, SnO, TiO
2, SnO
2, V
2O
5, VO
2, MnO
2, Fe
2O
3, Fe
3O
4In any one or more; 3) salt material: be selected from AlPO
4, Mg
3(PO
4)
2In any; 4) conducting polymer: be selected from polyaniline, polythiophene, polypyrrole polyacetylene with and derivative in any one or more; Above-mentioned negative pole clad material is selected from one or more the mixture in the following various types of materials: 1) semimetal: material with carbon element is selected from various hard carbon materials, soft material with carbon element, graphite, graphitized material and the modified graphite class material any one or more; 2) conducting polymer: be selected from polyaniline, polythiophene, polypyrrole polyacetylene with and derivative in any one or more, this secondary aluminium cell is made into any in individual layer button, multi-layer coiling column shape, the square various ways of multilayer folding and the specification.
6. secondary aluminium cell as claimed in claim 5, by positive pole, negative pole and electrolyte, barrier film constitutes, it is characterized in that: the positive electrode active materials of above-mentioned Nanosurface coating modification elemental sulfur is the positive electrode active materials that the nano polyaniline surface coats sulphur, the negative active core-shell material of above-mentioned Nanosurface coating modification aluminium and aluminium alloy is the negative active core-shell material that the nano-sized carbon surface coats aluminium powder and Al alloy powder, this secondary aluminium cell is by the positive pole that coats the positive electrode active materials of sulphur with the nano polyaniline surface, coat the negative pole of the negative active core-shell material of aluminium powder and Al alloy powder with the nano-sized carbon surface, in organic or inorganic electrolyte solution or polymer dielectric or the solid electrolyte any is electrolyte, barrier film, collector, battery case and lead-in wire are formed.
7. the preparation method of secondary aluminium cell, it is characterized in that: this method has following steps:
1) preparation or the carbon sulphur composite of the positive electrode active materials slurry of nanometer conductive polymer surface coating sulphur are the preparation of positive electrode active materials slurry: be the elemental sulfur of 1-100g with quality, pack in the there-necked flask of 200-300ml, add again the hydrochloric acid that volume is 10-100ml, behind the ultrasonic oscillation 0.5-1.5h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With aniline or thiophene or pyrroles or acetylene take and derivative in a kind of mol ratio as 1: 0.5-5; add be dissolved with aniline or thiophene or pyrroles or acetylene with and derivative in a kind of aqueous hydrochloric acid solution of monomer; magnetic agitation drips Ammonium Persulfate 98.5 (NH with dropping funel under nitrogen protection
4)
2S
2O
8Solution is as oxidant, the control rate of addition, solution was added dropwise to complete in 0.1-5 hour, make reaction carry out stopping to stir behind the 5-7h, in whole process, reaction is at room temperature carried out, described room temperature refers to 16-35 ℃, reaction finishes, product is carried out centrifugation, and under ul-trasonic irradiation, use the deionized water washed product, until washing lotion is colourless, end product namely obtains the positive electrode that nanometer conductive polymer coats sulphur behind 70-90 ℃ of lower vacuum drying 20-28h, or take mass ratio as 1: 3 carbon sulphur composite as positive electrode, all add respectively conductive agent: super conductive carbon black (SUPER-P), conductive black, in acetylene black and the graphite powder one or more and binding agent: Kynoar (PVDF), Pluronic F-127 (PEO), polytetrafluoroethylene (PTFE) (PTFE), sodium carboxymethylcellulose (CMC), in the EP rubbers one or more, ratio is 6-8: 1-3: 0.5-1.5, makes the positive electrode active materials slurry;
The nanometer conductive polymer surface of 2) making above-mentioned coats in the positive electrode active materials slurry of the positive electrode active materials slurry of sulphur or carbon sulphur composite material any and is coated in the thick collector of 0.5-0.7mm: nickel foam, stainless (steel) wire, carbon cloth, copper mesh, Copper Foil, on wantonly a kind of matrix in the aluminium foil, oven dry roll to 0.2-0.4mm be cut into 30-50mm wide * the long positive plate of 140-160mm, knit barrier film and be wound into the electric stamen nickel plating box hat of packing into the thick glass fibre of 0.1-0.2mm is non-with any the negative plate among the surface coated aluminium powder of nanometer C and Al alloy powder or Al or the Al-Zn as the negative active core-shell material preparation, add organic bath again, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell; The preparation method of the negative material of above-mentioned nanometer C surface coating modification aluminium and aluminum alloy materials is: aluminum or aluminum alloy and poly-oxireme (PEO) powder that grinds after sieving are pressed mass ratio 1: 1-10, putting into grinding in ball grinder mixes, aluminum or aluminum alloy and coating precursor PEO are mixed, mixture is placed in the tube type resistance furnace, under the condition of argon shield, the compound 0.5-10h of heating and decomposition under 50-400 ℃ of condition, in heating process, PEO is decomposed into the carbon of nano aperture fully, thereby be coated on the surface of aluminum or aluminum alloy mixed uniformly with it, aluminum or aluminum alloy is filled in the nano aperture of carbon, natural cooling, get final product the negative material of the surface coated aluminium powder of nano-sized carbon and Al alloy powder; Above-mentioned negative plate preparation method is: with purity be 99.5% aluminium flake be cut into 35-45mm wide * size that 150-170mm length * 0.1mm is thick, as negative plate; Perhaps with aluminium powder and alloy thereof as negative electrode active material, the active material dry powder of 3-5g is applied on the collector, roll to 0.2-0.4mm be cut into 35-45mm wide * the long pole piece of 150-170mm is as negative plate; Solvent is selected from wantonly a kind in water, ethanol, acetonitrile, the N-methyl pyrrolidone; Electrolyte is selected from the organic electrolyte that contains aluminium salt or contains in the aluminum ions ionic liquid wantonly a kind.
8. the preparation method of secondary aluminium cell as claimed in claim 7, it is characterized in that: this method has following steps:
1) above-mentioned nanometer conductive polymer is: nano polyaniline, preparation or carbon sulphur composite that this nano polyaniline surface coats the positive electrode active materials slurry of sulphur are the preparation of positive electrode active materials slurry: be the elemental sulfur of 1-100g with quality, pack in the there-necked flask of 200-300ml, add again the hydrochloric acid that volume is 10-100ml, behind the ultrasonic oscillation 0.5-1.5h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With the mol ratio of aniline be 1: 0.5-5, add the aqueous hydrochloric acid solution be dissolved with aniline monomer, magnetic agitation drips Ammonium Persulfate 98.5 (NH with dropping funel under nitrogen protection
4)
2S
2O
8Solution is as oxidant, the control rate of addition, solution was added dropwise to complete in 0.1-5 hour, make reaction carry out stopping to stir behind the 5-7h, in whole process, reaction is at room temperature carried out, described room temperature refers to 16-35 ℃, reaction finishes, product is carried out centrifugation, and under ul-trasonic irradiation, use the deionized water washed product, until washing lotion is colourless, end product namely obtains the positive electrode that the nano polyaniline surface coats sulphur behind 70-90 ℃ of lower vacuum drying 20-28h, or take mass ratio as 1: 3 carbon sulphur composite as positive electrode, all add respectively conductive agent: super conductive carbon black (SUPER-P), conductive black, in acetylene black and the graphite powder one or more and adhesive PVDF, PEO, PTFE, CMC, in the EP rubbers one or more, ratio is 6-8: 1-3: 0.5-1.5, makes the positive electrode active materials slurry;
The nano polyaniline surface of 2) making above-mentioned coats in the positive electrode active materials slurry of the positive electrode active materials slurry of sulphur or carbon sulphur composite material any and is coated in the thick collector of 0.5-0.7mm: nickel foam, stainless (steel) wire, carbon cloth, copper mesh, Copper Foil, on wantonly a kind of matrix in the aluminium foil, oven dry roll to 0.2-0.4mm be cut into 30-50mm wide * the long positive plate of 140-160mm, knit barrier film and be wound into the electric stamen nickel plating box hat of packing into the thick glass fibre of 0.1-0.2mm is non-with any the negative pole among the surface coated aluminium powder of nanometer C and Al alloy powder or Al or the Al-Zn as the negative active core-shell material preparation, add organic bath again, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell; The preparation method of the negative material of above-mentioned nanometer C surface coating modification aluminium and aluminum alloy materials is: the PEO powder after aluminum or aluminum alloy and grinding are sieved is by mass ratio 1: 1-10, putting into grinding in ball grinder mixes, aluminum or aluminum alloy and coating precursor PEO are mixed, mixture is placed in the tube type resistance furnace, under the condition of argon shield, the compound 0.5-10h of heating and decomposition under 50-400 ℃ of condition, in heating process, PEO is decomposed into the carbon of nano aperture fully, thereby be coated on the surface of aluminum or aluminum alloy mixed uniformly with it, aluminum or aluminum alloy is filled in the nano aperture of carbon, natural cooling, get final product the negative material of the surface coated aluminium powder of nano-sized carbon and Al alloy powder; Above-mentioned negative pole preparation method is: with purity be 99.5% aluminium flake be cut into 35-45mm wide * size that 150-170mm length * 0.1mm is thick, as negative plate; Perhaps with aluminium powder and alloy thereof as negative electrode active material, the active material dry powder of 3-5g is applied on the collector, roll to 0.2-0.4mm be cut into 35-45mm wide * the long pole piece of 150-170mm is as negative plate; Solvent is selected from wantonly a kind in water, ethanol, acetonitrile, the N-methyl pyrrolidone; Electrolyte is selected from the organic electrolyte that contains aluminium salt or contains in the aluminum ions ionic liquid wantonly a kind.
9. the preparation method of secondary aluminium cell as claimed in claim 7, it is characterized in that: this method has following steps:
1) above-mentioned nanometer conductive polymer is a nano polyaniline, this nano polyaniline surface coats the preparation of the positive electrode active materials slurry of sulphur: with quality is the elemental sulfur of 10-30g, pack in the there-necked flask of 200-300ml, add the hydrochloric acid that volume is 20-80ml again, behind the ultrasonic oscillation 1h, according to Ammonium Persulfate 98.5 and aniline mol ratio is 1: 1-3, add the aqueous hydrochloric acid solution that is dissolved with aniline monomer, the control rate of addition, solution was added dropwise to complete in 0.5-1.5 hour, make reaction carry out stopping to stir behind the 6h, end product promptly obtains the positive electrode that nano polyaniline coats sulphur behind 80 ℃ of following vacuumize 24h, add conductive agent: super conductive carbon black (SUPER-P) and adhesive PVDF, ratio is 7: 2: 1, makes above-mentioned positive electrode active materials slurry;
2) the above-mentioned positive electrode active materials slurry of making is coated on the thick nickel foam substrate of 0.6mm, oven dry roll to 0.3mm be cut into 40mm wide * the long pole piece of 150mm, knit barrier film and be wound into the electric stamen nickel plating box hat of packing into the thick glass fibre of 0.16mm is non-with the negative pole of the preparation of surface coated aluminium powder of nanometer C and Al alloy powder, add organic bath again, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell; The preparation method of the negative material of above-mentioned nanometer C surface coating modification aluminium and aluminum alloy materials is: the PEO powder after aluminum or aluminum alloy and grinding are sieved is by mass ratio 1: 2-5, put into grinding in ball grinder and mix the compound 2-6h of heating and decomposition under 100-350 ℃ of condition; The preparation method of above-mentioned negative pole is: purity be 99.5% aluminium flake be cut into 35-45mm wide * size that 150-170mm length * 0.1mm is thick, as negative plate; Perhaps with aluminium powder and alloy thereof as negative electrode active material, the active material dry powder of 3-5g is applied on the collector, roll to 0.2-0.4mm be cut into 35-45mm wide * the long pole piece of 150-170mm is as negative plate.
10. the preparation method of secondary aluminium cell as claimed in claim 7, it is characterized in that: this method has following steps:
1) above-mentioned nanometer conductive polymer is nano polyaniline, this nano polyaniline surface coats the preparation of the positive electrode active materials slurry of sulphur: be the elemental sulfur of 3-5g with quality, pack in the there-necked flask of 250ml, add again the hydrochloric acid that volume is 30-50ml, behind the ultrasonic oscillation 1h, according to Ammonium Persulfate 98.5 (NH
4)
2S
2O
8With the aniline mol ratio be 1: 1, add the aqueous hydrochloric acid solution that is dissolved with aniline monomer, the control rate of addition was added dropwise to complete solution in 1 hour, make reaction carry out stopping to stir behind the 6h, end product namely obtains the positive electrode that the nano polyaniline surface coats sulphur behind 80 ℃ of lower vacuum drying 24h; Add conductive agent: super conductive carbon black (SUPER-P) and adhesive PVDF, ratio is 7: 2: 1, makes the positive electrode active materials slurry;
2) the above-mentioned positive electrode active materials slurry of making is coated on the thick nickel foam substrate of 0.6mm, oven dry roll to 0.3mm be cut into 40mm wide * the long pole piece of 150mm; Knit barrier film and be wound into the electric stamen nickel plating box hat of packing into the thick glass fibre of 0.16mm is non-with the negative pole of the preparation of surface coated aluminium powder of nanometer C and Al alloy powder; Add organic bath again, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell; The preparation method of the negative material of above-mentioned nanometer C surface coating modification aluminium and aluminum alloy materials is: is 1: 3 to put into grinding in ball grinder mix under 250-350 ℃ condition heating and decomposition compound 3-5h with the PEO powder that grinds after sieving by mass ratio with aluminum or aluminum alloy; The preparation method of above-mentioned negative pole is: purity be 99.5% aluminium flake be cut into 35-45mm wide * size that 150-170mm length * 0.1mm is thick, as negative plate; Perhaps with aluminium powder and alloy thereof as negative electrode active material, the active material dry powder of 3-5g is applied on the collector, roll to 0.2-0.4mm be cut into 35-45mm wide * the long pole piece of 150-170mm is as negative plate.
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| NZ230197A (en) * | 1988-08-09 | 1990-11-27 | Alcan Int Ltd | Aluminium battery with an aluminium alloy anode and containing tin in the anode and/or the electrolyte |
| CN1050449C (en) * | 1996-12-26 | 2000-03-15 | 中国科学院长春应用化学研究所 | Preparation of material for anode of solid lithium battery |
| US6589692B2 (en) * | 2000-03-01 | 2003-07-08 | Kabushiki Kaisha Toshiba | Aluminum battery with aluminum-containing negative electrode |
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