CN106558730A - Secondary aluminium cell - Google Patents
Secondary aluminium cell Download PDFInfo
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- CN106558730A CN106558730A CN201510630963.4A CN201510630963A CN106558730A CN 106558730 A CN106558730 A CN 106558730A CN 201510630963 A CN201510630963 A CN 201510630963A CN 106558730 A CN106558730 A CN 106558730A
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- aluminium
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- aluminium cell
- negative pole
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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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 kind of secondary aluminium cell, belongs to electrochemistry and new forms of energy product scope.The secondary aluminium cell, including positive pole, negative pole, barrier film and non-aqueous containing aluminium electrolyte, just extremely the silicon-carbon anode composite, wherein Graphene and silicon nanopowder of the positive electrode active materials for Surface coating carbon material layer；The negative pole is formed by aluminium-carbon aerogel composite material cutting, wherein aluminium with the formal distribution that permeates or spread in the skeleton structure of carbon aerogels.The secondary aluminium cell, high with energy density height, negative pole utilization rate, cyclical stability is excellent.
Description
Technical field
The invention belongs to electrochemistry and new forms of energy product scope, are related to a kind of secondary aluminium cell.
Background technology
In order to meet the growth requirement of electric automobile, intelligent grid and mobile terminal device, research and develop high-energy-density and inexpensive environmentally friendly secondary aluminium cell becomes the focus of field of batteries, secondary aluminium cell is given birth to as a kind of application of high energy density cells system.At present, the research and development of secondary aluminium cell still suffer from many problems, especially this block of electrode, more sulphur positive pole is studied now due to sulphur poorly conductive, and the small molecule organic sulfur compound produced during sulphur-sulfur bonds is dissolved in the unordered sulphur that electrolyte can generate irreversible reaction so that active material is lost in, and has a strong impact on the cycle performance of battery, and the polysulfide that sulphur electric discharge is produced can shuttle to negative pole generation self discharge reaction, accelerate the corrosion of aluminum honeycomb.
The content of the invention
For above-mentioned prior art, the technical problem to be solved in the present invention is to provide a kind of secondary aluminium cell.The secondary aluminium cell includes positive pole, negative pole, barrier film and non-aqueous containing aluminium electrolyte, just extremely the silicon-carbon anode composite, wherein Graphene and silicon nanopowder of the positive electrode active materials for Surface coating carbon material layer；The negative pole is formed by aluminium-carbon aerogel composite material cutting, wherein aluminium with the formal distribution that permeates or spread in the skeleton structure of carbon aerogels.Above-mentioned secondary aluminium cell, high with energy density height, negative pole utilization rate, cyclical stability is excellent.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of secondary aluminium cell, including positive pole, negative pole, barrier film and non-aqueous containing aluminium electrolyte, just extremely the silicon-carbon anode composite, wherein Graphene and silicon nanopowder of the positive electrode active materials for Surface coating carbon material layer；The negative pole is formed by aluminium-carbon aerogel composite material cutting, wherein aluminium with the formal distribution that permeates or spread in the skeleton structure of carbon aerogels.
In the positive active material, carbon material layer is pyrolyzed by glucose or sucrose and is formed.
The thickness of the carbon material layer is 1-20 nanometers, and it is 1%-2% that carbon material layer accounts for the proportion of positive active material.
The graphite and silicon nanopowder particle diameter are 30-50 microns.
The graphite and silicon nanopowder are obtained using ball milling.
Positive active material account for silicon-carbon anode composite mass percent be 80%-85%, binding agent mass percent 5%-20%.
Negative pole aluminium-the carbon aerogel composite material, the mass ratio of carbon aerogels is 10～90%, and the mass ratio of aluminium is 90～10%.
In the negative pole, aluminium includes aluminum metal or aluminium alloy.
Above-mentioned positive pole is made up of positive active material, binding agent and collector etc., wherein binding agent be in polyvinyl alcohol, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, Kynoar, polystyrenebutadienes copolymer, butadiene-styrene rubber, Viton and polyurethane and its derivative, copolymer any one or appoint several mixtures, collector is stainless steel, copper, nickel, titanium, any one in aluminium.Positive active material and binding agent are proportionally well mixed, collection liquid surface is coated in, drying is rolled and then cutting is very suitably sized obtains positive plate.
Above-mentioned negative pole preparation method includes：In an inert atmosphere, carbon aerogels and aluminum or aluminum alloy mixture are heated to more than the fusing point of aluminium, are kept for 1～10 hour at 800～2000 DEG C, be cooled to room temperature, aluminium carbon aerogel composite material is obtained, then drying is cut to suitable dimension and obtains final product negative plate.
Beneficial effects of the present invention are as follows：Silicon-carbon anode composite has good conductivity, high, safe and reliable, the cheap advantage of energy density；Negative pole is by the heating in metallic aluminium, so that there is directional realignment in metallic aluminium in the amorphous carbon particles in carbon aerogels, define the structure of stratiform carbon, improve its conductive power and increase contact area with electrolyte, be conducive to diffusion of the electrolyte solution in electrode material, and then improve the reactivity and capacity of negative pole, molten aluminum is permeated in the connected pore channel in carbon aerogels three-dimensional network skeleton, is spread with nano shape simultaneously, further improves the activity and capacity of aluminum honeycomb.Thus the secondary aluminium cell stable cycle performance for preparing.
Specific embodiment
The technique effect of the design, concrete structure and generation of the present invention is described further below with reference to embodiment, to be fully understood from the purpose of the present invention, feature and effect.The following examples describe the several embodiments of the present invention, and they are merely illustrative, and nonrestrictive.
Embodiment 1
It is prepared by positive active material：It is 3 by 2kg mass ratioes:The silica flour of 1 graphite powder and 40 microns mechanical ball mill 10h in argon atmosphere, rotational speed of ball-mill is 100rpm, and graphite and silicon nanopowder is obtained；Then 500g glucose is dissolved in 2.5L distilled water, adds above-mentioned graphite and silicon nanopowder, stir；Above-mentioned solution is put into 110 DEG C of oven drying 6h again, after naturally cooling to room temperature, 20min is ground with agate, graphite crucible is then placed in, graphite crucible is put into into tube furnace, 700 DEG C are risen to the heating rate of 50 DEG C/h under argon atmosphere and be incubated 3h, it is naturally cooling to room temperature meeting, 30min is ground with agate again, 200 mesh sieve is then crossed, is obtained positive active material.
It is prepared by positive pole：By above-mentioned positive active material and binding agent with mass ratio 15:1 is well mixed, and is coated on nickel foam substrate, and drying is cut into the positive plate of suitable size after rolling.
It is prepared by negative pole：Resorcinol is dissolved in the furfural of 2 times of quality and forms solution A, then micro hexamethylenetetramine is dissolved in into formation second liquid in isopropanol.Solution A is added drop-wise in the second liquid under stirring formation organic solvent performed polymer at normal temperatures, pours in semitight container that the aging 36h of gel obtains the organic alcogel of bolarious intermediate product under the conditions of 80 DEG C into.Unlimited closure, at a temperature of 60 DEG C continues to be dried 12h or so, and the quality to aeroge is no longer reduced, and forms organic aerogel.Organic aerogel is placed in vacuum sintering funace, in 900 DEG C of vacuum environment sintering 2h, room temperature is naturally cooled to, is obtained black bulk carbon aerogels.By carbon aerogels and metallic aluminium with 1:1 mass ratio mixing, places them in alumina crucible with cover, is placed in tube furnace, in nitrogen atmosphere, aluminium melting is heated to, is again heated to 800 DEG C of insulation 3h, room temperature is cooled to, aluminium carbon aerogel composite material is obtained, the negative plate of suitable size after rolling, is cut into.
It is prepared by secondary aluminium cell：Above-mentioned positive plate and fibreglass diaphragm and negative plate are wound into into battery core and load nickel plating box hat, reinject aluminium chloride-triethylamine hydrochloride ionic liquid, secondary aluminium cell is made in sealing.
Embodiment 2
It is prepared by positive active material：It is 8 by 4.5kg mass ratioes:The silica flour of 1 graphite powder and 30 microns mechanical ball mill 10h in argon atmosphere, rotational speed of ball-mill is 200rpm, and graphite and silicon nanopowder is obtained；Then 500g glucose is dissolved in 5L distilled water, adds above-mentioned graphite and silicon nanopowder, stir；Above-mentioned solution is put into 130 DEG C of oven drying 8h again, after naturally cooling to room temperature, 20min is ground with agate, graphite crucible is then placed in, graphite crucible is put into into tube furnace, 700 DEG C are risen to the heating rate of 50 DEG C/h under argon atmosphere and be incubated 5h, it is naturally cooling to room temperature meeting, 50min is ground with agate again, 200 mesh sieve is then crossed, is obtained positive active material.
It is prepared by positive pole：By above-mentioned positive active material and binding agent with mass ratio 8:2 are well mixed, and are coated on nickel foam substrate, and drying is cut into the positive plate of suitable size after rolling.
It is prepared by negative pole：Respectively resorcinol (5.0g) and cetyl trimethylammonium bromide (0.1g) are added in the formaldehyde (6.0g) and water (7.0ml) solution of advance preparation; after being stirred well to uniformly; the solution is moved in the ground conical flask with glass stopper entirely; 5 days are incubated in 85 DEG C of water-bath; obtain translucent gel; spontaneously dried after taking-up at room temperature 2 days; then 5h is irradiated under infrared lamp; and 5h is dried at 110 DEG C; black carbon aerogels are obtained final product in 800 DEG C of constant temperature 3h under nitrogen protection again.By carbon aerogels and metallic aluminium with 1:1 mass ratio mixing, places them in alumina crucible with cover, is placed in tube furnace, in nitrogen atmosphere, aluminium melting is heated to, is again heated to 800 DEG C of insulation 3h, room temperature is cooled to, aluminium carbon aerogel composite material is obtained, the negative plate of suitable size after rolling, is cut into.
It is prepared by secondary aluminium cell：Above-mentioned positive plate and fibreglass diaphragm and negative plate are wound into into battery core and load nickel plating box hat, reinject aluminium chloride-triethylamine hydrochloride ionic liquid, secondary aluminium cell is made in sealing.
Embodiment 3
It is prepared by positive active material：It is 5 by 3kg mass ratioes:The silica flour of 1 graphite powder and 50 microns mechanical ball mill 8h in argon atmosphere, rotational speed of ball-mill is 400rpm, and graphite and silicon nanopowder is obtained；Then 400g glucose is dissolved in 3L distilled water, adds above-mentioned graphite and silicon nanopowder, stir；Above-mentioned solution is put into 120 DEG C of oven drying 5h again, after naturally cooling to room temperature, 20min is ground with agate, graphite crucible is then placed in, graphite crucible is put into into tube furnace, 700 DEG C are risen to the heating rate of 50 DEG C/h under argon atmosphere and be incubated 3h, it is naturally cooling to room temperature meeting, 60min is ground with agate again, 200 mesh sieve is then crossed, is obtained positive active material.
It is prepared by positive pole：By above-mentioned positive active material and binding agent with mass ratio 9:1 is well mixed, and is coated on nickel foam substrate, and drying is cut into the positive plate of suitable size after rolling.
It is prepared by negative pole：Catalyst is made with sodium carbonate, by resorcinol, formaldehyde with 1:2 mixed in molar ratio, plus redistilled water is made into the mixed liquor that concentration is 40%, and mixed liquor is moved in closed glass container, is put in insulating box (55 ± 3 DEG C).Through the reaction of 4 days, red organogel is generated.Organogel is put in acetone, exchange of solvent 3 days, period constantly changes acetone, is then placed on air drying 3 days, that is, obtain organic aerogel.Dried organic aerogel under nitrogen protection, is warmed up to 800 DEG C and maintains 3h, so that its charing is uniform, obtains final product black carbon aerogels.By carbon aerogels and metallic aluminium with 1:1 mass ratio mixing, places them in alumina crucible with cover, is placed in tube furnace, in nitrogen atmosphere, aluminium melting is heated to, is again heated to 800 DEG C of insulation 3h, room temperature is cooled to, aluminium carbon aerogel composite material is obtained, the negative plate of suitable size after rolling, is cut into.
It is prepared by secondary aluminium cell：Above-mentioned positive plate and fibreglass diaphragm and negative plate are wound into into battery core and load nickel plating box hat, reinject aluminium chloride-triethylamine hydrochloride ionic liquid, secondary aluminium cell is made in sealing.
Embodiment 4
Charge and discharge cycles test is carried out to made battery, 2.2V is charged to 1C, 0.5C electric discharges, discharge cut-off voltage is 1.2 V, and test result is as follows：
（1）After the made battery of one product of embodiment, open-circuit voltage 1.86V, first discharge capacity 720mAh, circulation 50 times, capability retention is 73.2%.
（2）After the made battery of two product of embodiment, open-circuit voltage 1.85V, first discharge capacity 695mAh, circulation 50 times, capability retention is 75.7%.
（3）After the made battery of three product of embodiment, open-circuit voltage 1.87V, first discharge capacity 706mAh, circulation 50 times, capability retention is 74.2%.
Although being described in detail to the present invention with reference to embodiment, but those skilled in the art should be understood, in the case of without departing from the spirit and scope of the present invention described in appended claims and its equivalent, can to its various modification can be adapted and replace.
Claims (8)
1. a kind of secondary aluminium cell, including positive pole, negative pole, barrier film and non-aqueous containing aluminium electrolyte, it is characterised in that：The just extremely silicon-carbon anode composite, wherein positive electrode active materials Graphene and silicon nanopowder for Surface coating carbon material layer；The negative pole is formed by aluminium-carbon aerogel composite material cutting, wherein aluminium with the formal distribution that permeates or spread in the skeleton structure of carbon aerogels.
2. secondary aluminium cell according to claim 1, it is characterised in that：In the positive active material, carbon material layer is pyrolyzed by glucose or sucrose and is formed.
3. secondary aluminium cell according to claim 1 and 2, it is characterised in that：The thickness of the carbon material layer is 1-20 nanometers, and it is 1%-2% that carbon material layer accounts for the proportion of positive active material.
4. secondary aluminium cell according to claim 1, it is characterised in that：The graphite and silicon nanopowder particle diameter are 30-50 microns.
5. the secondary aluminium cell according to claim 1 or 4, it is characterised in that：The graphite and silicon nanopowder are obtained using ball milling.
6. secondary aluminium cell according to claim 1, it is characterised in that：Positive active material account for silicon-carbon anode composite mass percent be 80%-85%, binding agent mass percent 5%-20%.
7. secondary aluminium cell according to claim 1, it is characterised in that：Negative pole aluminium-the carbon aerogel composite material, the mass ratio of carbon aerogels is 10～90%, and the mass ratio of aluminium is 90～10%.
8. secondary aluminium cell according to claim 1, it is characterised in that：In the negative pole, aluminium includes aluminum metal or aluminium alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510630963.4A CN106558730A (en) | 2015-09-29 | 2015-09-29 | Secondary aluminium cell |
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| CN201510630963.4A CN106558730A (en) | 2015-09-29 | 2015-09-29 | Secondary aluminium cell |
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| CN106558730A true CN106558730A (en) | 2017-04-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI790812B (en) * | 2021-11-10 | 2023-01-21 | 亞福儲能股份有限公司 | Management method for alluminum battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI790812B (en) * | 2021-11-10 | 2023-01-21 | 亞福儲能股份有限公司 | Management method for alluminum battery |
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