CN104300127A - Sulfur-based composite material coated with carbon, preparation and application thereof - Google Patents
Sulfur-based composite material coated with carbon, preparation and application thereof Download PDFInfo
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- CN104300127A CN104300127A CN201410541258.2A CN201410541258A CN104300127A CN 104300127 A CN104300127 A CN 104300127A CN 201410541258 A CN201410541258 A CN 201410541258A CN 104300127 A CN104300127 A CN 104300127A
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- carbon
- polyacrylonitrile
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a novel high-energy secondary aluminum battery. The novel high-energy secondary aluminum battery comprises a positive electrode, a negative electrode and electrolyte, wherein a positive electrode active material is a sulfur-based composite material coated with a carbon material, wherein the sulfur-based composite material is vulcanized polyacrylonitrile; the negative electrode is an aluminium-containing negative electrode, and the electrolyte is non-aqueous aluminium-containing electrolyte. The secondary aluminum battery disclosed by the invention is high in specific capacity and circulating performance; and a preparation process is simple and the novel high-energy secondary aluminum battery is suitable for industrial production.
Description
Technical field
The invention belongs to electrochemistry and new forms of energy product scope, relate to the preparation method of the coated sulfenyl composite material of a kind of carbon, the invention still further relates to a kind of secondary aluminium cell adopting this composite material and preparation method thereof.
Background technology
Along with developing rapidly of movable electronic and communication apparatus, the demand of secondary cell is more urgent, and more and more tends to the exploitation of battery of intensity, slim, small-sized, light-duty and high-energy-density.The energy density of aluminium is 2980mAh/g, and its quality is light, cheap, aboundresources, use safety, is desirable cell negative electrode material; The energy density of sulphur is 1675mAh/g, nature rich reserves, safety and environmental protection, and cheap, application is in the secondary battery comparatively extensive.Therefore with aluminum metal or aluminium alloy for secondary aluminium-sulfur battery that negative pole and sulfenyl material are positive pole is the battery system of the most attraction meeting demand.
The operation principle of secondary aluminium-sulfur battery is the Reversible redox reaction between sulphur and aluminium.At present, the technical bottleneck of aluminium-sulfur battery is that the intermediate poly sulfide that sulfur-based positive electrode material also exists active material loss, poorly conductive, reduction process produce is soluble in electrolyte, the diffusion of partly soluble poly sulfide arrives metallic aluminium negative terminal surface and produces self discharge reaction and be deposited on negative pole and make the problems such as its passivation, finally causes that sulphur active material utilization is low, capacity attenuation is rapid, cycle performance of battery is poor.
Organic sulfur compound can be obtained the sulphur positive electrode of high stability for the preparation of sulfur-bearing char-forming material as carbon matrix precursor.In the secondary aluminium-sulfur battery that patent CN200910234924.7 provides, polyacrylonitrile mixes with sulphur and heats cyclization occurs, and the sulfurized polyacrylonitrile of formation is that one has long-range π key conjugated system polymer, and this polymer has higher specific capacity.But because the above-mentioned cyclisation degree preparing sulfurized polyacrylonitrile is not high, the conjugatedπbond playing electric action formed is less, thus makes the conductivity of sulfurized polyacrylonitrile lower, causes the utilance of sulphur positive active material low.And still can not avoid the dissolving of electric discharge intermediate product in battery charge and discharge process, circulating battery is poor.Carbon is coated is also one of the most important method improving positive electrode capacity, high rate performance, cyclical stability, and its Main Function is the conductivity improving positive active material, makes material have good chemical property under high magnification.But coated can being with of carbon serves negative effect, such as reduces the density of material, increase operation and cost etc., therefore the preparation technology of sulfur-based positive electrode material need optimize further.
Summary of the invention
(1) goal of the invention
Poor for overcoming sulfur-based positive electrode material conductivity in prior art, reactant is soluble in the defect of electrolyte, the invention provides the preparation method of the coated sulfur-based composite anode material of a kind of conductivity is high, reactant is insoluble to electrolyte carbon, and specific capacity is high, the secondary aluminium-sulfur battery of good cycle.
Polyacrylonitrile is with sulphur compound, and what reaction generated has stability and the conductivity that long-range π key conjugated system polymer effectively can improve electrode, improves utilance and the electrode specific capacity of active material sulphur simultaneously; The crosslinked action of the two sulphur-carbon chemical bond formed can limit the dissolving of polysulfide to a certain extent, suppresses to shuttle back and forth the destruction of effect to electrode, improves the cycle performance of battery.At the material with carbon element film of the coated one deck nano thickness of polyacrylonitrile/sulphur composite material surface, while raising conductance, avoid the direct contact of active material with electrolyte, the dissolving of polysulfide in electrochemical reaction process can be prevented further.The existence of material with carbon element layer and conducting polymer effectively can also alleviate sulphur bulk effect in charge and discharge process, improves the cycle performance of positive electrode to a great extent.In addition, prepare without the need to adding conductive agent in electrode process, further increase the specific capacity of electrode, energy density is also higher.
The present invention also aims to the preparation method that a kind of secondary aluminium cell is provided.
(2) technical scheme
For achieving the above object, the invention provides following technical scheme:
A kind of secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that:
A () positive pole, is characterized in that, positive active material is the coated sulfurized polyacrylonitrile of carbon;
B () is containing aluminum honeycomb;
C () non-water is containing aluminium electrolyte;
(d) barrier film.
Here is the description of the preferred positive pole of secondary aluminium cell of the present invention, negative pole, electrolyte and barrier film.
(1) positive pole
The positive pole of secondary aluminium cell of the present invention comprises positive active material, binding agent and collector.Because coated material with carbon element has good conductivity, without the need to adding conductive agent.
Positive active material of the present invention is the coated sulfurized polyacrylonitrile of carbon, and coated material with carbon element includes but not limited to agraphitic carbon, graphite, Graphene, graphite fibre, carbon fiber, carbon nano-tube etc.
The thickness of material with carbon element coating layer of the present invention is 5 ~ 10nm.
Positive active material of the present invention is the coated sulfurized polyacrylonitrile of carbon, and its preparation method is as follows:
1) sulfurized polyacrylonitrile preparation
By polyacrylonitrile and sublimed sulfur, (10:1 ~ 5:1) mixed grinding is even by a certain percentage, puts into the quartz ampoule of sealing, under inert gas (nitrogen or argon gas) condition, heats 5 ~ 8 hours, obtain the sulfurized polyacrylonitrile of black in 200 ~ 300 DEG C of temperature;
Or, polyacrylonitrile is dissolved in solvent dimethylformamide and prepares polyacrylonitrile solution, add Fe catalyst, stir and be heated to 200 DEG C simultaneously, keep 2 hours, then add elemental sulfur or sodium thiosulfate wherein, stir, be heated to 300 ~ 400 DEG C, keep 5 ~ 10 hours, obtain sulfurized polyacrylonitrile;
2) carbon coated material
Take material with carbon element and the sulfurized polyacrylonitrile of certain proportion (1:5 ~ 1:15), mix and be placed in airtight quartz ampoule, under inert gas (nitrogen or argon gas) condition, heat 0.5 ~ 1.5 hour in 300 ~ 400 DEG C of temperature, obtain the sulfurized polyacrylonitrile that positive active material carbon is coated;
Or, material with carbon element is scattered in alcohol solvent and forms mixed solution, sulfurized polyacrylonitrile is placed in one, be uniformly mixed and treat solvent evaporates, then under inert gas (nitrogen or argon gas) condition, be heated to 300 ~ 400 DEG C, keep 5 ~ 10 hours, obtain the sulfurized polyacrylonitrile that positive active material carbon is coated;
Or, adopt chemical gaseous phase depositing process to carry out carbon at sulfurized polyacrylonitrile material surface coated.
Adhesive of the present invention be aqueous binder LA132(Chengdu mattress happy), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), Kynoar (PVDF), polystyrenebutadienes copolymer (SBR), Viton and polyurethane, PVP, polyethyl acrylate, polyvinyl chloride, polyacrylonitrile, polycaprolactam, polybutadiene, polyisoprene, polyacrylic acid, and derivative, mixture or copolymer.Be preferably mattress ground, aqueous binder LA132(Chengdu happy).
Collector of the present invention includes but not limited to stainless steel, copper, nickel, titanium, aluminium.More preferably the aluminium collector of carbon coating, more easily covers the coating comprising positive active material, has lower contact resistance, and can suppress the corrosion of sulfide.
(2) negative pole
Of the present invention containing aluminum honeycomb active material, include but not limited to: aluminum metal, such as aluminium foil and the aluminium that is deposited on base material; Aluminium alloy, comprises the alloy containing at least one element be selected from Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Mn, Sn, Pb, Ma, Ga, In, Cr, Ge and Al.
(3) electrolyte
Non-water of the present invention is organic salt-aluminum halide system ionic liquid containing aluminium electrolyte, and wherein, the mol ratio of organic salt and aluminum halide is 1:1.1 ~ 3.0.
In organic salt of the present invention-aluminum halide system, the cation of organic salt comprises imidazol ion, pyridinium ion, pyrrolidinium ion, piperidines ion, morpholinium ion, quaternary ammonium salt ion ， quaternary alkylphosphonium salt ion and tertiary sulfosalt ion; The anion of organic salt comprises Cl
-, Br
-, I
-, PF
6 -, BF
4 -, CN
-, SCN
-, [N (CF
3sO
2)
2]
-, [N (CN)
2]
-plasma.
Organic salt of the present invention-aluminum halide system, is characterized in that, described aluminum halide is the one in aluminium chloride, aluminium bromide or silver iodide.
Organic salt of the present invention-aluminum halide system includes but not limited to aluminium chloride-triethylamine hydrochloride, aluminium chloride-chlorination 1-butyl-3-methylimidazole, aluminium chloride-phenyl trimethicone ammonium chloride, aluminium bromide-1-ethyl-3-methyllimidazolium bromide plasma liquid.
(4) barrier film
Secondary aluminium cell of the present invention also can comprise the barrier film between positive pole and negative pole.Suitable solid porous separator material includes but not limited to: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.Other example being applicable to diaphragm material of the present invention comprises microporous pseudo-boehmite layer, and it can be the form of free-standing film or be coated directly onto on an electrode.
The preparation method of secondary aluminium cell of the present invention is as follows: positive electrode active materials, binding agent (ratio is 8:2) are made active material slurry and be applied on the thick collector of 0.6mm, oven dry rolls to about 0.33mm, be cut into 40mm wide × the long pole piece of 15mm is as positive plate, the barrier film thick with 0.16mm and negative pole are wound into battery core and load nickel plating box hat, reinject electrolyte, and secondary aluminium cell is made in sealing.
(3) beneficial effect
The invention provides secondary aluminium cell of a kind of just very conducting polymer/carbon sulphur composite material and preparation method thereof, compared with the existing technology there is following advantage:
(1) in positive electrode, the existence of polyacrylonitrile can improve stability and the conductivity of positive pole, effectively can slow down again the destruction of change in volume to positive pole of sulphur in charge and discharge process, the crosslinked action of sulphur-carbon chemical bond that simultaneous reactions generates can limit the dissolving of polysulfide, suppress to shuttle back and forth the destruction of effect to electrode, effectively improve the cycle performance of secondary aluminium cell.
(2) because coated material with carbon element has good conductivity, the preparation of positive pole, without the need to adding conductive agent, improves specific capacity.
(3) the coated and existence that is conducting polymer of carbon effectively improves the chemical property of positive electrode active materials, on the one hand for the bulk effect in sulphur discharge and recharge provides certain cushion space, after carbon coated, the Electric Field Distribution of material is more even on the other hand, reduces the overpotential polarizing and cause.
(4) adopt no material with carbon element and different technique to carry out carbon coated, significantly improve the conductivity of carbon coated, improve the high rate performance of battery.
(5) the secondary aluminium cell specific capacity prepared by is high, good cycle, long service life.
(4) embodiment
Be described further below with reference to the technique effect of embodiment to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.The following examples describe several execution mode of the present invention, and they are only illustrative, and nonrestrictive.
embodiment 1
(1) prepare sulfurized polyacrylonitrile: by polyacrylonitrile and sublimed sulfur even in 10:1 ratio mixed grinding, put into the quartz ampoule of sealing, under inert gas (nitrogen or argon gas) condition, be warming up to 300 DEG C and keep 8 hours, obtain the sulfurized polyacrylonitrile of black.
(2) carbon coated material: the sucrose and the sulfurized polyacrylonitrile that take 1:8 ratio, mix and be placed in airtight quartz ampoule, under inert gas (nitrogen or argon gas) condition, first be rapidly heated to 200 DEG C, slowly be warming up to 400 DEG C again, keep 1 hour, obtain the sulfurized polyacrylonitrile that positive active material carbon is coated.
(3) secondary aluminium cell is prepared: be 8:2 by sulfurized polyacrylonitrile coated for positive electrode active materials carbon, binding agent LA132(ratio) make active material slurry and be applied on the thick nickel foam substrate of 0.6mm, oven dry rolls to about 0.33mm, be cut into 40mm wide × the long pole piece of 15mm is as positive plate, the glass fibre thick with 0.16mm be non-to be knitted barrier film and negative pole and is wound into battery core and loads nickel plating box hat, reinject aluminium chloride-triethylamine hydrochloride ionic liquid, and AA type cylinder secondary aluminium cell is made in sealing.
During battery charging and discharging loop test, carry out charging to 2.5V with 1C, 0.1C discharges, and discharge cut-off voltage is 1.2V.Battery open circuit voltage is 1.76V, and most high discharge capacity is 683mAh, and after 50 charge and discharge cycles, discharge capacity is 486mAh.
embodiment 2
(1) sulfurized polyacrylonitrile is prepared: polyacrylonitrile is dissolved in solvent dimethylformamide and prepares polyacrylonitrile solution, add Fe catalyst, stir and be heated to 200 DEG C simultaneously, keep 2 hours, then add elemental sulfur wherein, polyacrylonitrile and elemental sulfur ratio are 5:1, stir, be heated to 350 DEG C, keep 10 hours, obtain sulfurized polyacrylonitrile.
(2) carbon coated material: material with carbon element is scattered in alcohol solvent and forms mixed solution, sulfurized polyacrylonitrile is placed in one, material with carbon element and sulfurized polyacrylonitrile ratio are 1:10, be uniformly mixed and treat solvent evaporates, then, under inert gas (nitrogen or argon gas) condition, be first rapidly heated to 200 DEG C, be more slowly heated to 350 DEG C, keep 5 hours, obtain the sulfurized polyacrylonitrile that positive active material carbon is coated.
(3) secondary aluminium cell is prepared: be 8:2 by sulfurized polyacrylonitrile coated for positive electrode active materials carbon, binding agent PVDF(ratio) make active material slurry and be applied on the aluminium collector of the thick carbon coating of 0.6mm, oven dry rolls to about 0.33mm, be cut into 40mm wide × the long pole piece of 15mm is as positive plate, the glass fibre thick with 0.16mm be non-to be knitted barrier film and negative pole and is wound into battery core and loads nickel plating box hat, reinject aluminium chloride-triethylamine hydrochloride ionic liquid, and AA type cylinder secondary aluminium cell is made in sealing.
During battery charging and discharging loop test, carry out charging to 2.5V with 1C, 0.1C discharges, and discharge cut-off voltage is 1.2V.Battery open circuit voltage is 1.70V, and most high discharge capacity is 690mAh, and after 50 charge and discharge cycles, discharge capacity is 503mAh.
embodiment 3
(1) preparation of sulfurized polyacrylonitrile is with embodiment 1.
(2) carbon coated material: change sucrose into cellulose acetate, is first rapidly heated to 300 DEG C, is more slowly warming up to 450 DEG C, and all the other are with embodiment 2.
(3) preparation of secondary aluminium cell is with embodiment 2.
During battery charging and discharging loop test, carry out charging to 2.5V with 1C, 0.1C discharges, and discharge cut-off voltage is 1.2V.Battery open circuit voltage is 1.71V, and most high discharge capacity is 674mAh, and after 50 charge and discharge cycles, discharge capacity is 472mAh.
embodiment 4
(1) preparation of sulfurized polyacrylonitrile is with embodiment 1.
(2) carbon coated material: take acetylene as carbon source, Fe is catalyst, hydrogen and nitrogen are carrier gas, adopt chemical gaseous phase depositing process to carry out carbon at sulfurized polyacrylonitrile material surface in 600 ~ 700 DEG C coated, the sulfurized polyacrylonitrile of obtained positive active material nano-carbon coated.
(3) preparation of secondary aluminium cell is with embodiment 2.
During battery charging and discharging loop test, carry out charging to 2.5V with 1C, 0.1C discharges, and discharge cut-off voltage is 1.2V.Battery open circuit voltage is 1.78V, and most high discharge capacity is 697mAh, and after 50 charge and discharge cycles, discharge capacity is 512mAh.
embodiment 5
(1) preparation of sulfurized polyacrylonitrile is with embodiment 1.
(2) carbon coated material: configuration concentration is the graphene oxide water solution of 10mg/mL; ultrasonic disperse 10h; then the sulfurized polyacrylonitrile prepared is added wherein; add reducing agent ammoniacal liquor to it simultaneously, under ultrasound condition, react 24h, obtain the sulfurized polyacrylonitrile of the few layer graphene lamella of Surface coating; after taking out product washing, drying; under inert nitrogen gas protection, be warming up to 700 DEG C, keep 5 ~ 10h, the sulfurized polyacrylonitrile that obtained positive active material carbon is coated.
(3) preparation of secondary aluminium cell is with embodiment 1.
During battery charging and discharging loop test, carry out charging to 2.5V with 1C, 0.1C discharges, and discharge cut-off voltage is 1.2V.Battery open circuit voltage is 1.72V, and most high discharge capacity is 686mAh, and after 50 charge and discharge cycles, discharge capacity is 480mAh.
Although reference embodiment is to invention has been detailed description, but those skilled in the art is to be understood that, when not departing from the spirit and scope of the present invention described in appended claims and equivalent thereof, various amendment and replacement can be made to it.
Claims (10)
1. a secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that:
A () positive pole, is characterized in that, positive active material is the coated sulfurized polyacrylonitrile of carbon;
B () is containing aluminum honeycomb;
C () non-water is containing aluminium electrolyte;
(d) barrier film.
2. secondary aluminium cell according to claim 1, is characterized in that, described positive pole comprises positive active material, binding agent and collector, because coated material with carbon element has good conductivity, without the need to adding conductive agent.
3. secondary aluminium cell according to claim 1, is characterized in that, the coated material with carbon element of described positive active material includes but not limited to agraphitic carbon, graphite, Graphene, graphite fibre, carbon fiber, carbon nano-tube etc.
4. secondary aluminium cell according to claim 1, is characterized in that, the thickness of described material with carbon element coating layer is 5 ~ 10nm.
5. secondary aluminium cell according to claim 1, is characterized in that, the preparation method of described positive active material comprises:
(1) sulfurized polyacrylonitrile preparation
By polyacrylonitrile and sublimed sulfur, (10:1 ~ 5:1) mixed grinding is even by a certain percentage, puts into the quartz ampoule of sealing, under inert gas (nitrogen or argon gas) condition, heats 5 ~ 8 hours, obtain the sulfurized polyacrylonitrile of black in 200 ~ 300 DEG C of temperature;
Or, polyacrylonitrile is dissolved in solvent dimethylformamide and prepares polyacrylonitrile solution, add Fe catalyst, stir and be heated to 200 DEG C simultaneously, keep 2 hours, then add elemental sulfur or sodium thiosulfate wherein, stir, be heated to 300 ~ 400 DEG C, keep 5 ~ 10 hours, obtain sulfurized polyacrylonitrile;
(2) carbon coated material
Take material with carbon element and the sulfurized polyacrylonitrile of certain proportion (1:5 ~ 1:15), mix and be placed in airtight quartz ampoule, under inert gas (nitrogen or argon gas) condition, heat 0.5 ~ 1.5 hour in 300 ~ 400 DEG C of temperature, obtain the sulfurized polyacrylonitrile that positive active material carbon is coated;
Or, material with carbon element is scattered in alcohol solvent and forms mixed solution, sulfurized polyacrylonitrile is placed in one, be uniformly mixed and treat solvent evaporates, then under inert gas (nitrogen or argon gas) condition, be heated to 300 ~ 400 DEG C, keep 5 ~ 10 hours, obtain the sulfurized polyacrylonitrile that positive active material carbon is coated;
Or, adopt chemical gaseous phase depositing process to carry out carbon at sulfurized polyacrylonitrile material surface at 600 ~ 700 DEG C of temperature coated.
6. secondary aluminium cell according to claim 1, is characterized in that, the described aluminum honeycomb that contains comprises aluminum metal or aluminium alloy.
7. secondary aluminium cell according to claim 1, is characterized in that, described non-water comprises organic salt-aluminum halide system ionic liquid containing aluminium electrolyte, and wherein, the mol ratio of organic salt and aluminum halide is 1:1.1 ~ 3.0.
8. secondary aluminium cell according to claim 6, is characterized in that, the cation of described organic salt comprises imidazol ion, pyridinium ion, pyrrolidinium ion, piperidines ion, morpholinium ion, quaternary ammonium salt ion ， quaternary alkylphosphonium salt ion and tertiary sulfosalt ion; The anion of organic salt comprises Cl
-, Br
-, I
-, PF
6 -, BF
4 -, CN
-, SCN
-, [N (CF
3sO
2)
2]
-, [N (CN)
2]
-plasma.
9. secondary aluminium cell according to claim 1, is characterized in that, comprises the barrier film between positive pole and negative pole, and described diaphragm material includes but not limited to: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.
10. the preparation method of a secondary aluminium cell according to claim 1, it is characterized in that, positive electrode active materials, binding agent (ratio is 8:2) are made active material slurry and be applied on the thick collector of 0.6mm, oven dry rolls to about 0.33mm, be cut into 40mm wide × the long pole piece of 15mm is as positive plate, the barrier film thick with 0.16mm and negative pole are wound into battery core and load nickel plating box hat, and reinject electrolyte, and secondary aluminium cell is made in sealing.
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| CN106602129A (en) * | 2016-12-12 | 2017-04-26 | 北京科技大学 | Multi-ion battery and preparation method thereof |
| CN106920937A (en) * | 2017-03-30 | 2017-07-04 | 青岛亨迈新能源有限公司 | A kind of preparation method of electrode composite material |
| CN108140881A (en) * | 2015-12-15 | 2018-06-08 | 里兰斯坦福初级大学理事会 | For improved electrolyte, current-collector and the adhesive of chargeable metal ion battery |
| CN110364720A (en) * | 2019-07-26 | 2019-10-22 | 南京海泰纳米材料有限公司 | Positive electrode active materials and preparation method thereof, anode pole piece and preparation method based on positive electrode active materials preparation |
| CN110790236A (en) * | 2019-09-26 | 2020-02-14 | 西安交通大学 | Method for coating nano ammonium perchlorate by graphene wet process |
| CN111668536A (en) * | 2020-05-27 | 2020-09-15 | 北京科技大学 | Preparation method of metal aluminum-cyano organic matter secondary battery |
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| CN108140881A (en) * | 2015-12-15 | 2018-06-08 | 里兰斯坦福初级大学理事会 | For improved electrolyte, current-collector and the adhesive of chargeable metal ion battery |
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| CN110790236A (en) * | 2019-09-26 | 2020-02-14 | 西安交通大学 | Method for coating nano ammonium perchlorate by graphene wet process |
| CN111668536A (en) * | 2020-05-27 | 2020-09-15 | 北京科技大学 | Preparation method of metal aluminum-cyano organic matter secondary battery |
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Application publication date: 20150121 |