CN105958121A - Electrolyte for rapidly charging and discharging aluminum battery and aluminum battery containing electrolyte - Google Patents
Electrolyte for rapidly charging and discharging aluminum battery and aluminum battery containing electrolyte Download PDFInfo
- Publication number
- CN105958121A CN105958121A CN201610533101.4A CN201610533101A CN105958121A CN 105958121 A CN105958121 A CN 105958121A CN 201610533101 A CN201610533101 A CN 201610533101A CN 105958121 A CN105958121 A CN 105958121A
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- Prior art keywords
- electrolyte
- aluminum
- fluorinated
- carbon
- methyl
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 52
- 239000003792 electrolyte Substances 0.000 title claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000007599 discharging Methods 0.000 title claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- -1 1-butyl-2,3-dimethyl fluorinated glyoxaline Chemical class 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 238000005520 cutting process Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000002322 conducting polymer Substances 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 238000003682 fluorination reaction Methods 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 241001597008 Nomeidae Species 0.000 claims description 2
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005269 aluminizing Methods 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- 229950000845 politef Drugs 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 229940045105 silver iodide Drugs 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 claims description 2
- POSYVRHKTFDJTR-UHFFFAOYSA-M tetrapropylazanium;fluoride Chemical compound [F-].CCC[N+](CCC)(CCC)CCC POSYVRHKTFDJTR-UHFFFAOYSA-M 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 11
- 230000004087 circulation Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000007747 plating Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000002460 imidazoles Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- UGHBKTSSBSCAMR-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-1,2-dihydroimidazol-1-ium bromide Chemical group [Br-].CCCC[NH+]1C=CN(C)C1C UGHBKTSSBSCAMR-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AQLLBJAXUCIJSR-UHFFFAOYSA-N OC(=O)C[Na] Chemical compound OC(=O)C[Na] AQLLBJAXUCIJSR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
An electrolyte of an aluminum battery capable of being rapidly charged and discharged and the aluminum battery containing the electrolyte are disclosed, wherein the electrolyte of the electrolyte is a fluoride ionic liquid-aluminum halide system. The battery prepared by the electrolyte provided by the invention has the advantages of high speed, high-capacity charge and discharge, long cycle life and the like.
Description
Technical field
Electrochemical energy source domain of the present invention, particularly relates to a kind of model electrochemical energy field, particularly relates to one
Plant the electrolyte of novel fast charging and discharging aluminum cell and the aluminum cell containing this electrolyte.
Background technology
Currently, the non-renewable fuel source such as coal and oil is the most exhausted, greenhouse effect, environmental pollution and
Population problem constantly deteriorates, and energy scarcity and environmental conservation become two hang-ups of facing mankind, therefore, open
Send out new green power and become the focus of current research.Lithium ion battery, as novel energy storage component, has low
Self discharge, high-energy-density, good circulation performance and advantages of environment protection, increasingly closed by the mankind
Note, and it is considered the main selection of extensive energy-storage battery such as following electric automobile, energy-accumulating power station etc., but lithium money
Seedbed shell content few and production cost is expensive etc. that factor hinders its large-scale application.Therefore, development money
Source is enriched, novel battery system with low cost, is the optimum growth side of following extensive energy storage system
To.
Aluminum is the metallic element that content is maximum in the earth's crust, and its exploitation and production cost are the lowest, technical maturity.
Additionally, an aluminium ion can shift three electronics, its theoretical capacity is 2980mAh/g, is only second to lithium
(3870mAh/g), volume and capacity ratio is 8050mAh/cm3, it is the highest in metal material.At present
The relevant aluminum cell having been reported that has water system aluminium-air cell, as disclosed in CN 103329342A, and chlorination ion
The aluminum cell of liquid system, as disclosed in CN 104078705A.Wherein aluminium-air cell theoretical energy density
Up to 8.1kWh/kg, but the factors of aluminum electrode and aqueous electrolyte limits, the energy of actual application
Density only has 0.35kWh/kg.The aluminum cell of chloride ionic liquid system is due to electrolyte electrochemical window
< 1.5V, causes running voltage and capacity on the low side, and sensitive in atmosphere, and production cost is high, above unfavorable
The development of factor restriction aluminum cell.
Therefore, develop the ionic liquid electrolyte of a kind of novel stabilising aluminium ion battery, improve the ratio of aluminum cell
Capacity, improves cycle performance, has highly important theory significance and commercial value.
Summary of the invention
For problem above, an object of the present invention is to provide the electrolysis of a kind of fast charging and discharging aluminum cell
Liquid, described electrolyte comprises fluoride ion liquid and aluminum chloride electrolyte system.Electricity provided by the present invention
Solve the battery prepared of liquid and have quickly, high power capacity discharge and recharge and the advantage such as have extended cycle life.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
A kind of electrolyte of fast charging and discharging aluminum cell, described electrolyte for fluoride ion liquid-aluminum halide
System.The specific capacity that this electrolyte system can improve aluminum cell is higher, and cycle performance is excellent.For the present invention
Electrolyte, there is following reaction during work:
Negative reaction: Al+7Al2ClxF4-x -→4Al2ClxF7-x -+3e-
Positive pole reacts: Cn[ClxF4-x]+e-→Cn+Al2ClxF4-x -
As preferably, described fluoride ion liquid is(fluorinated glyoxaline),(fluorination methylimidazole),(fluorinated pyridine),(quaternary ammonium fluoride salt) orOne or both in (fluorinated pyrrolo)
Above combination,
Wherein, R is alkyl, preferably straight chained alkyl, more preferably C1～C6Straight chained alkyl, special
You Xuanwei CH3 -、CH3CH2 -、CH3CH2CH2 -Or CH3CH2CH2CH2 -。
Preferably, described fluoride ion liquid is 1,3-dimethyl fluorinated glyoxaline, and 1-ethyl-3-methyl is fluorinated
Imidazoles, 1-propyl group-3-methyl fluorinated glyoxaline, 1-butyl-3-methyl fluorinated glyoxaline, 1-ethyl-2,3-dimethyl fluorine
Change imidazoles, 1-propyl group-2,3-dimethylammonium chloride imidazoles, 1-butyl-2,3-dimethyl fluorinated glyoxaline, 1-hexyl
-2,3-dimethyl fluorinated glyoxaline, 1-octyl group-2,3-dimethyl fluorinated glyoxaline, N-ethyl fluorinated pyridine, N-butyl
Fluorinated pyridine, N-hexyl fluorinated pyridine, N-octyl group fluorinated pyridine, Methanaminium, N,N,N-trimethyl-, fluoride, tetraethyl are fluorinated
In ammonium, tetrapropyl ammonium fluoride, N-ethyl-N-methyl fluorinated pyrrolo or N-butyl-N-methyl fluorination piperidines one
Kind or two or more combinations.
As preferably, described aluminum halide is one or more in aluminum chloride, aluminium bromide or silver iodide
Combination.
As preferably, described fluoride ion liquid is 1:1～1:5 with the mol ratio of aluminum halide, for example, 1:1.2,
1:1.5,1:2,1:3.5,1:4,1:4.5 etc., preferably 1:1.5～3.0.
An object of the present invention also resides in a kind of aluminum cell of offer, and it comprises electrolyte of the present invention.
As preferably, aluminum cell of the present invention includes:
(I) positive pole of electroactive substance is comprised；
(II) negative pole containing aluminum active material；
(III) electrolyte of the present invention.
Preferably, described positive pole contains electroactive substance, conductive agent, binding agent and collector.
Preferably, described electroactive substance is graphite-structure material with carbon element and/or sulphur-containing substance.
Preferably, described graphite-structure material with carbon element be the one in graphite, carbon paper, carbon fiber paper or white carbon black or
Two or more combinations.
Preferably, described sulphur-containing substance is elemental sulfur, comprises sulphur atom and in the organosulfur compound of carbon atom
One or more combination.
Preferably, the one during described conductive agent is graphite-based material, carbon-based material or conducting polymer or two
Plant above combination.
Preferably, described graphite-based material is electrically conductive graphite.
Preferably, described carbon-based material be that Super P, Ketjen be black, one or two in acetylene black or white carbon black
Plant above combination.
Preferably, one during described conducting polymer is polyaniline, polypyrrole, polythiophene or polyacetylene or
Two or more combinations.
Preferably, described binding agent is polyvinyl alcohol (PVA), politef (PTFE), carboxymethyl
Sodium cellulosate (CMC), Kynoar (PVDF), polystyrenebutadienes copolymer (SBR) or
One or more combination in its derivant, mixture or copolymer.
Preferably, described collector is inert electrode, and preferably rustless steel, copper, nickel, titanium or aluminum, more excellent
Selecting aluminum collector, it is easier to cover the coating including positive active material, has relatively low contact resistance,
And the corrosion of sulfide can be suppressed.
As preferably, described negative pole is fine aluminium, aluminium alloy or material of aluminizing.
As preferably, described positive pole is prepared by: by electroactive substance, conductive agent, binding agent
Make on the collector that slurry is applied to, dry the pole piece rolling the suitable size of rear cutting.
Preferably, electroactive substance, conductive agent, binding agent quality are 4～15:0.5～3:0.5～3, such as
For 6:0.8:0.5,9:1.5:1,12:3:2,8:2:3 etc., preferably 8:1:1.
Preparing the diaphragm material used in aluminum cell can be that to have the glass fibre of ion permeability, polyethylene micro-
Hole or polypropylene micropore diaphragm etc. are usually used in the diaphragm material of aluminum cell.
Battery prepared by electrolyte provided by the present invention has quickly, high power capacity discharge and recharge and having extended cycle life
Etc. advantage, after 2000 circulations, discharge capacitance is still more than 93%, reaches as high as 99.7%..
Accompanying drawing explanation
Fig. 1 is the EMImF-AlCl of embodiment 13The cyclic voltammogram of (mol ratio 1:2.7) electrolyte system,
Wherein working electrode is carbon, is aluminum to electrode, and reference electrode is high-purity Al, sweep speed: 80mv/s.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art it will be clearly understood that
Described embodiment is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
In nmp solvent, add white carbon black: SUPER-P:PVDF=8:1:1 (mass ratio) and be prepared as slurry,
Coat on aluminium foil, dry the pole piece rolling the suitable size of rear cutting.Pole piece after cutting and polyethylene diagrams
And be wound in the box hat that battery core loads nickel plating as negative material with aluminium flake, adding mol ratio 1:2.7 is
1-ethyl-3-methyl fluorinated glyoxaline-aluminum chloride electrolyte, cylindrical aluminium battery is made in sealing.Fig. 1 is the present embodiment
EMImF-AlCl3The cyclic voltammogram of (mol ratio 1:2.7) electrolyte system.Battery charges to 1C
2.4V, is discharged to 0.5V, first discharge specific capacity 59.1mAh/g, and after 2000 circulations, discharge capacity is
58mAh/g。
Embodiment 2
In nmp solvent, add white carbon black: polyaniline: CMC=8:1:1 (mass ratio) is prepared as slurry, be coated with
It is distributed on aluminium foil, dries the pole piece rolling the suitable size of rear cutting.Pole piece after cutting and polypropylene diaphragm with
And be wound in the box hat that battery core loads nickel plating as negative material with aluminum-lithium sheet, adding mol ratio 1:1.4 is
1-butyl-2,3-dimethyl fluorinated glyoxaline-aluminum chloride electrolyte, cylindrical aluminium battery is made in sealing.Battery is with 1C
Charge to 2.4V, be discharged to 0.5V, first discharge specific capacity 58.5mAh/g, after 2000 circulations, discharge
Capacity is 55.1mAh/g.
Embodiment 3
In nmp solvent, add elemental sulfur: polyaniline: SBR=8:1:1 (mass ratio) is prepared as slurry,
Coat nickel sheet paper tinsel, dry the pole piece rolling the suitable size of rear cutting.Pole piece after cutting and polypropylene diaphragm
And the nickel sheet aluminized is wound in the box hat that battery core loads nickel plating as negative material, add mol ratio 1:2
For N-octyl group fluorinated pyridine-aluminum chloride electrolyte, cylindrical aluminium battery is made in sealing.Battery charges to 1C
2.4V, is discharged to 0.5V, first discharge specific capacity 55.7mAh/g, and after 2000 circulations, discharge capacity is
53.1mAh/g。
Embodiment 4
In nmp solvent, add sulfurized polyacrylonitrile: prepared by polyaniline: CMC=8:1:1 (mass ratio)
Form slurry, coats nickel sheet paper tinsel, dries the pole piece rolling the suitable size of rear cutting.Pole piece after cutting is with poly-
Propylene barrier film and the nickel sheet aluminized are wound in the box hat that battery core loads nickel plating as negative material, and addition rubs
You are tetrapropyl ammonium fluoride-aluminum chloride electrolyte than 1:2.4, and cylindrical aluminium battery is made in sealing.Battery fills with 1C
Electricity, to 2.4V, is discharged to 0.5V, first discharge specific capacity 57.7mAh/g, and after 2000 circulations, electric discharge is held
Amount is 54.1mAh/g.
Embodiment 5
Use Graphene tabletting in aluminium foil, dry the pole piece of the suitable size of cutting.Pole piece after cutting and glass
Fibre diaphragm and the nickel sheet aluminized are wound in the box hat that battery core loads nickel plating as negative material, and addition rubs
You are that N-butyl-N-methyl is fluorinated piperidines-aluminum chloride electrolyte than 1:1, and cylindrical aluminium battery is made in sealing.Electricity
Pond charges to 2.4V with 1C, is discharged to 0.5V, first discharge specific capacity 59.3mAh/g, 2000 circulations
After, discharge capacity is 59.1mAh/g.
Embodiment 6
Use Graphene tabletting in aluminium foil, dry the pole piece of the suitable size of cutting.Pole piece after cutting and glass
Fibre diaphragm and the nickel sheet aluminized are wound in the box hat that battery core loads nickel plating as negative material, and addition rubs
You are ionic liquid (1-ethyl-3-methyl fluorinated glyoxaline and 1-octyl group-2,3-dimethyl fluorinated glyoxaline ratio than 1:1.5
Example is 2:1)-aluminum halide (aluminum chloride and aluminium bromide ratio 3:1) electrolyte, cylindrical aluminium battery is made in sealing.
Battery charges to 2.4V with 1C, is discharged to 0.5V, first discharge specific capacity 58.5mAh/g, follows for 2000 times
After ring, discharge capacity is 58.1mAh/g.
Applicant states, the present invention illustrates detailed process equipment and the technique of the present invention by above-described embodiment
Flow process, but the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention
Have to rely on above-mentioned detailed process equipment and technological process could be implemented.Person of ordinary skill in the field should
This understands, any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. the electrolyte of a fast charging and discharging aluminum cell, it is characterised in that described electrolyte for fluoride
Ionic liquid-aluminum halide system.
Electrolyte the most according to claim 1, it is characterised in that described fluoride ion liquid is In one or more combination,
Wherein, R is alkyl, preferably straight chained alkyl, more preferably C1～C6Straight chained alkyl, special
You Xuanwei CH3 -、CH3CH2 -、CH3CH2CH2 -Or CH3CH2CH2CH2 -。
Electrolyte the most according to claim 1 and 2, it is characterised in that described fluoride ion liquid
It is 1,3-dimethyl fluorinated glyoxaline, 1-ethyl-3-methyl fluorinated glyoxaline, 1-propyl group-3-methyl fluorinated glyoxaline, 1-
Butyl-3-methyl fluorinated glyoxaline, 1-ethyl-2,3-dimethyl fluorinated glyoxaline, 1-propyl group-2,3-dimethylammonium chloride miaow
Azoles, 1-butyl-2,3-dimethyl fluorinated glyoxaline, 1-hexyl-2,3-dimethyl fluorinated glyoxaline, 1-octyl group-2,3-two
Methyl fluorinated glyoxaline, N-ethyl fluorinated pyridine, N-butyl fluorinated pyridine, N-hexyl fluorinated pyridine, N-are pungent
Base fluorinated pyridine, Methanaminium, N,N,N-trimethyl-, fluoride, tetraethyl ammonium fluoride, tetrapropyl ammonium fluoride, N-ethyl-N-methyl
One or more combination in fluorinated pyrrolo or N-butyl-N-methyl fluorination piperidines.
4. according to the electrolyte described in any one of claim 1-3, it is characterised in that described aluminum halide is chlorine
Change one or more the combination in aluminum, aluminium bromide or silver iodide.
5. according to the electrolyte described in any one of claim 1-4, it is characterised in that described fluoride ion
Liquid is 1:1～1:5 with the mol ratio of aluminum halide, preferably 1.5～3.0.
6. an aluminum cell, it is characterised in that it comprises the electrolyte described in any one of claim 1-5.
Aluminum cell the most according to claim 6, it is characterised in that including:
(I) positive pole of electroactive substance is comprised；
(II) negative pole containing aluminum active material；
(III) electrolyte described in any one of claim 1-5；
Preferably, described positive pole contains electroactive substance, conductive agent, binding agent and collector.
Aluminum cell the most according to claim 7, it is characterised in that described electroactive substance is stone
Ink structure material with carbon element and/or sulphur-containing substance；
Preferably, described graphite-structure material with carbon element be the one in graphite, carbon paper, carbon fiber paper or white carbon black or
Two or more combinations；
Preferably, described sulphur-containing substance is elemental sulfur, comprises sulphur atom and in the organosulfur compound of carbon atom
One or more combination；
Preferably, the one during described conductive agent is graphite-based material, carbon-based material or conducting polymer or two
Plant above combination；
Preferably, described graphite-based material is electrically conductive graphite；
Preferably, described carbon-based material be that Super P, Ketjen be black, one or two in acetylene black or white carbon black
Plant above combination；
Preferably, one during described conducting polymer is polyaniline, polypyrrole, polythiophene or polyacetylene or
Two or more combinations.
9. according to the aluminum cell described in claim 7 or 8, it is characterised in that described binding agent is polyethylene
Alcohol, politef, sodium carboxymethyl cellulose, Kynoar, polystyrenebutadienes copolymer or its
One or more combination in derivant, mixture or copolymer；
Preferably, described collector is inert electrode, and preferably rustless steel, copper, nickel, titanium or aluminum, more excellent
Choosing is coated with the aluminum collector of carbon；
As preferably, described negative pole is fine aluminium, aluminium alloy or material of aluminizing；
As preferably, described positive pole is prepared by: by electroactive substance, conductive agent, binding agent
Make on the collector that slurry is applied to, dry and roll rear cutting and get final product.
10. according to the aluminum cell described in any one of claim 7-8, it is characterised in that electro-chemical activity thing
Matter, conductive agent, binding agent quality are 4～15:0.5～3:0.5～3, preferably 8:1:1.
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| CN201610533101.4A CN105958121A (en) | 2016-07-07 | 2016-07-07 | Electrolyte for rapidly charging and discharging aluminum battery and aluminum battery containing electrolyte |
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| CN201610533101.4A CN105958121A (en) | 2016-07-07 | 2016-07-07 | Electrolyte for rapidly charging and discharging aluminum battery and aluminum battery containing electrolyte |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109546154A (en) * | 2018-12-13 | 2019-03-29 | 北京理工大学 | A kind of aluminium ion battery afflux liquid with protective layer |
| CN110010888A (en) * | 2019-04-01 | 2019-07-12 | 北京工业大学 | One kind can charge and discharge water system aluminium ion battery and its preparation process |
| TWI685489B (en) * | 2017-01-25 | 2020-02-21 | 財團法人工業技術研究院 | Aluminum-ion battery |
| TWI851950B (en) * | 2021-12-21 | 2024-08-11 | 亞福儲能股份有限公司 | Positive electrode composition for alluminum battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104078703A (en) * | 2014-05-23 | 2014-10-01 | 南京中储新能源有限公司 | Carbon nano tube/quinone anode and secondary aluminium cell with same as anode material |
| CN104078680A (en) * | 2014-05-23 | 2014-10-01 | 南京中储新能源有限公司 | Carbon-sulfur composite positive electrode and secondary aluminium-sulfur battery |
| CN105633371A (en) * | 2016-01-05 | 2016-06-01 | 北京金吕能源科技有限公司 | Aluminum-ion secondary battery employing nickel-sulfur compound as positive electrode and preparation technology of aluminum-ion secondary battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104078703A (en) * | 2014-05-23 | 2014-10-01 | 南京中储新能源有限公司 | Carbon nano tube/quinone anode and secondary aluminium cell with same as anode material |
| CN104078680A (en) * | 2014-05-23 | 2014-10-01 | 南京中储新能源有限公司 | Carbon-sulfur composite positive electrode and secondary aluminium-sulfur battery |
| CN105633371A (en) * | 2016-01-05 | 2016-06-01 | 北京金吕能源科技有限公司 | Aluminum-ion secondary battery employing nickel-sulfur compound as positive electrode and preparation technology of aluminum-ion secondary battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI685489B (en) * | 2017-01-25 | 2020-02-21 | 財團法人工業技術研究院 | Aluminum-ion battery |
| CN109546154A (en) * | 2018-12-13 | 2019-03-29 | 北京理工大学 | A kind of aluminium ion battery afflux liquid with protective layer |
| CN110010888A (en) * | 2019-04-01 | 2019-07-12 | 北京工业大学 | One kind can charge and discharge water system aluminium ion battery and its preparation process |
| TWI851950B (en) * | 2021-12-21 | 2024-08-11 | 亞福儲能股份有限公司 | Positive electrode composition for alluminum battery |
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