CN109742320A - A three-dimensional porous aluminum anode and its application in aluminum batteries - Google Patents
A three-dimensional porous aluminum anode and its application in aluminum batteries Download PDFInfo
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- CN109742320A CN109742320A CN201811644587.4A CN201811644587A CN109742320A CN 109742320 A CN109742320 A CN 109742320A CN 201811644587 A CN201811644587 A CN 201811644587A CN 109742320 A CN109742320 A CN 109742320A
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- aluminium
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- dimensional porous
- porous
- aluminum
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 112
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000005275 alloying Methods 0.000 claims abstract description 10
- 239000011241 protective layer Substances 0.000 claims abstract description 4
- 239000004411 aluminium Substances 0.000 claims description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- -1 polyethylene Polymers 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
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- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 4
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
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- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 2
- JAVAMPMGHYGCHA-UHFFFAOYSA-M N1C=NC=C1.[I-].C(C)[N+]1=CC(=CC=C1)C Chemical class N1C=NC=C1.[I-].C(C)[N+]1=CC(=CC=C1)C JAVAMPMGHYGCHA-UHFFFAOYSA-M 0.000 claims description 2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
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- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
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- 230000015572 biosynthetic process Effects 0.000 claims description 2
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims 2
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- 229920001807 Urea-formaldehyde Polymers 0.000 claims 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
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Classifications
-
- 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
- Cell Electrode Carriers And Collectors (AREA)
Abstract
本发明属于新能源电池技术领域，提供一种三维多孔铝负极的制备及其铝电池构筑。三维多孔铝负极包括：沉积于非金属三维基体上的多孔铝、沉积于金属三维基体上的多孔铝、表面具有保护层包覆的三维多孔铝、合金化三维多孔铝材料。通过对三维多孔铝的空间结构、孔道结构及比表面积调控、界面保护及合金化改性，优化电池电化学反应效率及动力学，提高铝负极的电化学稳定性，从而提升典型铝电池的比容量、倍率性能及循环寿命等关键性能。The invention belongs to the technical field of new energy batteries, and provides the preparation of a three-dimensional porous aluminum negative electrode and the construction of an aluminum battery. The three-dimensional porous aluminum negative electrode includes: porous aluminum deposited on a non-metal three-dimensional substrate, porous aluminum deposited on a metal three-dimensional substrate, three-dimensional porous aluminum coated with a protective layer on the surface, and alloyed three-dimensional porous aluminum material. By adjusting the spatial structure, pore structure and specific surface area, interface protection and alloying modification of three-dimensional porous aluminum, the electrochemical reaction efficiency and kinetics of the battery are optimized, the electrochemical stability of the aluminum anode is improved, and the ratio of typical aluminum batteries is improved. key performance such as capacity, rate capability and cycle life.
Description
Technical field
The present invention relates to a kind of preparation of three-dimensional porous aluminum honeycomb and its aluminum cell applications, belong to field of new energy technologies.
Background technique
Metallic aluminium has high theoretical specific capacity (2978mAh/g, or 8034mAh/cm3), high earth's crust content, low cost, peace
The advantages such as easy to operate entirely.Therefore, aluminum cell causes the extensive concern of researcher in recent years.However, the cathode of existing aluminum cell
Predominantly aluminium foil, that there are interfacial electrochemistry reaction efficiencies is low, be easy to be damaged by corrosion, multiplying power and cycle performance are poor, oxide layer
The problems such as acting on complicated difficult control and challenge.Therefore, for the interfacial electrochemistry characteristic of aluminum cell, it is negative that design prepares high-performance aluminum
Pole is one of the Key Strategy for promoting aluminum cell comprehensive performance.
Three-dimensional porous aluminium has many characteristics, such as that lightweight, large specific surface area, cellular structure are abundant, can be used as excellent electrode material
Material.Three-dimensional porous constructed of aluminium provided by the present invention, porosity with higher and excellent space structure are battery electrochemical
Reaction provides efficient interface, enhances the storage and transmittability of electrolyte, accelerates the dynamic process of electrochemical reaction,
The utilization efficiency for improving metallic aluminium enhances performance and coulombic efficiency of the battery under high magnification, and can effectively overcome or
Delay structure destruction and dendritic growth of the aluminum honeycomb in electrochemical deposition/dissolution, to improve the service life of aluminum cell.
Summary of the invention
When the present invention is to overcome aluminium foil as aluminum cell cathode, existing electrochemical efficiency is low, specific capacity and multiplying power
The problems such as performance is poor, perishable destruction, poor circulation, it is intended to improve the pass such as high rate performance and cycle life of aluminum secondary battery
Keyness energy.
The present invention provides a kind of three-dimensional porous aluminum honeycomb material.Include: be deposited on nonmetallic three dimensional matrix three-dimensional it is more
Hole aluminium, the three-dimensional porous aluminium being deposited on metal three dimensional matrix, surface have the three-dimensional porous aluminium of protective layer cladding, alloying three
Tie up porous aluminum material.The porosity of three-dimensional porous aluminium is 10%-95%, and (material i.e. between gap and gap, is similar to skeleton
The diameter of twine in metal mesh) diameter is 0.005mm-1mm, duct pattern is open duct and part closure duct, hole track forces
Very little to be distributed as macropore, mesoporous or micropore single or polynary distribution, duct orientation includes isotropism and anisotropy.Duct
Structural parameters are controlled by three dimensional porous matrix, and duct anisotropy is realized by applying mechanical external force as compressed or stretching.
The present invention provides the three-dimensional porous aluminium being deposited on nonmetallic three dimensional matrix.The nonmetallic three dimensional matrix includes
But it is not limited to the three-dimensional porous foams such as polyurethane, polystyrene, polyethylene, polyurethane, polyvinyl chloride, polypropylene, phenolic resin
The three-dimensional porous carbon material such as plastics and graphene, graphene assembly, carbon nanotube assembly, carbon fiber assembly.It is obtained
Porous aluminium electrode includes nonmetallic three dimensional matrix-porous aluminum combination electrode and the pure porous aluminum electricity for removing nonmetallic three dimensional matrix
Pole.
The present invention also provides the three-dimensional porous aluminium being deposited on metal three dimensional matrix.The metal three dimensional matrix include but
It is not limited to nickel foam, foam copper, foam ZnCu, NiCu, NiCrW, NiFe, NiCrFe alloy, nano-pore nickel, nano-pore copper, receives
The three-dimensional porous metal such as metre hole gold, nano-pore silver, nano-pore platinum, nano-pore palladium.Obtaining porous aluminium electrode includes metal three-dimensional
The porous Al alloy electrode of matrix-porous aluminum combination electrode and further alloying.
The above-mentioned three-dimensional porous aluminum honeycomb being deposited on nonmetallic or metal three dimensional matrix, by electrochemical deposition method or very
Empty vapour deposition method deposition preparation.Electrochemical deposition method: using nonmetallic or metal three dimensional matrix as cathode, rafifinal as anode,
Aluminum saline solution, aluminium salt organic solution or aluminium base ionic liquid are as electrolyte, by electrochemical deposition by al deposition in matrix
On, washing and dry acquisition are carried out after deposition.Preferred anodes are that (purity: 99.99%), preferably electrolyte is aluminium foil
EMICl/AlCl3(1/1.3) type ionic liquid, preferable temperature are room temperature, and preferably detergent is dehydrated alcohol.Vacuum vapour deposition:
Nonmetallic or metal three dimensional matrix is fixed in vacuum evaporation instrument, using rafifinal as target, heating evaporation metallic aluminium, deposition
In nonmetallic or metal three dimensional matrix.It is preferred that target is that (purity: 99.99%), preferably heating is electrical heating method to aluminium block.
The present invention also provides the three-dimensional porous aluminium with surface coating layer, to improve the electrochemical stability of cathode.It is described
Surface deposits include but is not limited to carbon, silicon, titanium, tungsten, nickel, Au Ag Pt Pd, zinc, carbon nanotube, graphene, graphite alkene, carbon
The one or more of fiber, polyacetylene, polythiophene, polypyrrole, polyaniline, polyhenylene, polyphenylene ethylene, poly bis alkynes etc., pass through
In three-dimensional porous aluminium surface high temperature or vapor deposition law technology is realized or forerunner's dispersion liquid is in the anti-of three-dimensional porous aluminium surface
It the methods of answers, adsorb, assemble and realize.
The present invention also provides a kind of three-dimensional porous aluminum materials of alloying.Alloying material include but is not limited to gallium,
Copper, chromium, iron, nickel, lead, bismuth, tin or silver.Alloying mode includes but is not limited to: preparing acieral, to carry out vacuum evaporation again heavy
Product, electro-deposition etc.；During preparing three-dimensional porous material while carrying out the vacuum evaporation deposition of multi-element metal, electro-deposition
Deng；The porous aluminum being deposited on metal three dimensional matrix is subjected to the three-dimensional porous aluminium of high-temperature alloy alloying obtained.It is different
The ratio of metal can be regulated and controled by modes such as the control of presoma ratio, thermal evaporations.
The present invention further provides the aluminum cells prepared with three-dimensional porous aluminum honeycomb, just extremely carbon material, sulphur subgroup simple substance
And its compound, transition metal oxide or haloid material, sulphur-carbon composite, three-dimensional porous aluminium-sulphur composite material etc.,
Including but not limited to: conductive carbon paper, graphite powder, acetylene black, sublimed sulfur, sedimentation sulphur, elemental selenium, molybdenum sulfide, artificial gold, five oxidations
The materials such as two vanadium；Electrolyte is aluminum halide and alkali halide, alkaline-earth halide, imidazoles organic salt, pyridines, acyl
The eutectic salts that the substances such as amine are formed, including but not limited to: aluminum halide and NaCl, KCl, LiCl, CsCl, MgCl2、BaCl2、NaBr、
1- ethyl -3- methy limidazolium, 1- ethyl -3- methylimidazolium chloride, 1- ethyl -3- methylpyridinium iodide imidazoles, urea,
The eutectic salts of the formation such as formamide, acetamide, propionamide.The battery structure assembled include: seal glass electrolytic cell,
The cell apparatus such as Swagelok battery, high temperature resistant soft-package battery, button cell.
Detailed description of the invention
Fig. 1 is cycle performance of battery schematic diagram described in embodiment 5；
Fig. 2 is electric deposition aluminum described in embodiment 7-nickel foam microscopic appearance figure.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
Polyurethane foam acetone, dilute hydrochloric acid and water are cleaned by ultrasonic 5 minutes respectively, and vacuum drying 12 is small at 80 DEG C
When, it is used as electric deposition aluminum matrix.With EMICl/AlCl3It (1/1.3) is deposited electrolyte.The polyurethane is cut into long 2cm, width
High-purity aluminium flake of the working electrode of 2cm, thickness 1mm size, identical size is used as to electrode and reference electrode, is fixed on containing electrolyte
Hermetic electrolyte pond in, apply constant voltage -0.6V deposit 2 hours.By post-depositional aluminium-polyurethane dehydrated alcohol and deionization
Water cleans up, and is dried in vacuo 12 hours at 80 DEG C.Above-mentioned gained sample can be used as battery cathode.
To be anode with a thickness of the graphite paper of 0.05mm, graphite paper is cut to the sheet of long 2cm, width 1cm；Using
Whatman GF/A fibreglass diaphragm is cut to sheet identical with positive area, and it is fixed on together with graphite paper
On collector molybdenum foil (thickness 0.1mm), anode and collector are fixed on together on platinum plate electrode folder；It is respectively with mass fraction
8.75%, 12.5%, 78.75% KCl, LiCl, AlCl3Mixture is electrolyte；Electrolyte raw material needed for weighing in proportion,
It is uniformly mixed, positive and negative anodes is fixed in electrolytic cell, be heated to 100 DEG C and keep the temperature, after matter to be electrolysed is melted to liquid,
Liquid level should be enough to infiltrate positive and negative anodes, infiltrate positive and negative best eight hours to complete activation, carry out battery performance test.The battery
It is compared compared with normal aluminium foil, though capacity maintains 98% without its cycle performance coulombic efficiency after 500 circles is obviously improved.
Embodiment 2
Cathode: the aluminum metal on nickel foam metallic matrix, nickel foam cleaning and drying are the same as embodiment 1.By the foam
Nickel is cut to long 2cm, width 2cm, thickness 1mm sheet, deposits 3 minutes aluminium using ion sputtering instrument, the aluminium-nickel foam is negative as battery
Pole.
Anode, electrolyte and battery assembly test are the same as embodiment 1.The battery is compared compared with embodiment 1, capacity boost
5%, and cycle performance is good.
Embodiment 3.
Cathode: preparing apply carbon pastes first, and mass ratio is carbon black, the acrylic acid (film forming agent), N- methyl of 4:3:92:1
How sodium sulfonate (dispersing agent) mixing is deployed into slurry sieving for pyrrolidones (solvent) and methylene two, utilizes reverse roll intaglio plate
Printing equipment carries out carbon-coating coating in the resulting porous aluminium surface of embodiment 2.After gained is applied the drying of carbon aluminium, then use deionized water
Ultrasonic cleaning, and secondary drying.The painting carbon aluminium is as battery cathode.
Anode, electrolyte and battery assembly test are the same as embodiment 1.
Embodiment 4.
Cathode: processing and deposition process are the same as embodiment 1 before and after foam copper surface deposited porous aluminium, foam copper.By the aluminium-
Foam copper is heat-treated 12 hours under 1100 DEG C of argon atmospheres, and Temperature fall is cooling.Gained alloy is as battery cathode.
Anode, electrolyte and battery assembly test are the same as embodiment 1.
Embodiment 5
Cathode: being about 1mm with a thickness of 3mm, porosity 70%, skeleton size, by 6Mpa, continues the mechanical compression of 5s
Three-dimensional porous fine aluminium, by its blunderbuss at the disk of diameter 12mm, and be held on platinum plate electrode folder on.
Anode, electrolyte and battery assembly test are the same as embodiment 1.
Fig. 1 is the battery long circulating performance schematic diagram of this example.As seen from Figure 1, under the high current density of 1A, the battery
2500 circles can be recycled without obvious decaying, and charge/discharge capacity is stablized in 80mAh/g, and coulombic efficiency is close to 100%, it is sufficient to prove
Its stable circulation performance.(note: the battery operating temperature is 100 DEG C)
Embodiment 6
Cathode: nickel foam is placed in ionic liquid (AlCl3: EMIC=1.3, mole ratio) in and as cathode, sun
Extremely pure aluminum foil, under -0.6V voltage, constant-potential electrolysis aluminium can plate to obtain one layer of aluminium film in nickel foam, will aluminize after the completion of plating
Nickel foam is used washes of absolute alcohol clean and is dried as battery cathode.
Anode, electrolyte and battery assembly test are the same as embodiment 1.The battery charging and discharging capacity is promoted compared with normal aluminium foil
10%, coulombic efficiency 90%-98%, battery performance are stablized.
Embodiment 7
Cathode: long 2cm, wide 2cm, the nickel foam with a thickness of 1mm, porosity 60%, skeleton having a size of 0.1mm-2mm.
With embodiment 1, constant current deposits 10h under 2A/g current density, and aluminium layer is plated in nickel foam for cleaning and drying process, later should
Electrode is directly as battery cathode.Its microscopic appearance SEM figure is as shown in Figure 2.
Anode, electrolyte and battery assembly test are the same as embodiment 1.
Embodiment 8
Cathode: being that the three-dimensional porous aluminium of 1mm-3mm carries out 6Mpa, holds by 3mm thickness, porosity 70%, skeleton size range
Continuous 5s mechanical compression, and it is dipped in AlCl3: it is impregnated for 24 hours in the ionic liquid of EMIC (molar ratio)=1.5, takes out and wipe
Clean surface remnants electrolyte, with washes of absolute alcohol and is dried, which is multistage etch pit.
Anode, electrolyte and battery assembly test are the same as embodiment 1.
Embodiment 9
Cathode: graphene coated is carried out to three-dimensional porous aluminium using microwave plasma CVD device.To be
System is evacuated to the pressure of foundation of 0.1Pa, after being purged for several times with argon gas, with 100 sccms (sccm) hydrogen
System is heated to 600 DEG C in 20 minutes.Then, 7sccm methane is introduced under the pressure of 15Pa, is opened with the power of 150W
Plasma generator generates methane plasma.Sedimentation time is 5-10 minutes, is then cooled fast to room temperature.So far it obtains
Obtain the three-dimensional porous aluminium of graphene coated.The thin slice for being 12mm at diameter by its blunderbuss is held on platinum plate electrode folder.Anode, electricity
Liquid and battery assembly test are solved with embodiment 1.
Embodiment 10
Cathode: such as embodiment 1.
Anode: by the sulphur-carbon composite being carried on ordered mesopore carbon CMK3 (carry sulfur content 50%) and conductive black and
The round pole piece of diameter 6mm is made in PTFE binder, and it is online to be pressed into collector molybdenum.Electrolyte: AlCl3- acetamide class
Ionic liquid (molar ratio 1.3:1)；Diaphragm: such as embodiment 1；Battery assembly: the battery is assembled using Swagelok model.
Embodiment 11
Cathode: melamine foamed plastic is utilized, is raised under nitrogen protection in tube furnace with the heating rate of 5 DEG C/min
800 DEG C, heat preservation 30min carbonization takes out after being cooled to room temperature and is used as electro-deposition matrix, deposition three-dimensional porous aluminum process such as embodiment
1.The three-dimensional porous aluminium is immersed into AlCl3: it is impregnated in the ionic liquid of EMIC (molar ratio)=1.5 for 24 hours, takes out simultaneously wiped clean
By surface residual electrolyte wiped clean, with washes of absolute alcohol and dry.The pole piece is as battery cathode.
Anode, electrolyte and battery assembly test are the same as embodiment 1.The battery performance compared with normal aluminium foil, circulation and again
Rate performance has certain promotion, and capacity can be stablized in 600mAh/g after 50 circle of circulation.
Claims (10)
1. a kind of three-dimensional porous aluminum honeycomb, which is characterized in that the aluminum honeycomb has three-dimensional porous appearance structure；It include: to be deposited on
Three-dimensional porous aluminium on nonmetallic three dimensional matrix, the three-dimensional porous aluminium being deposited on metal three dimensional matrix, surface have protective layer
Three-dimensional porous aluminium, the three-dimensional porous aluminium of alloying of cladding；The porosity of the three-dimensional porous aluminum honeycomb is 10%-98%, and skeleton is straight
Diameter is 0.005mm-1mm, and duct pattern is open duct and part closure duct, and pore size is distributed as macropore, mesoporous or micro-
The single or polynary distribution in hole, duct orientation are isotropism or anisotropy.
2. a kind of three-dimensional porous aluminum honeycomb according to claim 1, which is characterized in that be deposited on nonmetallic three dimensional matrix
Three-dimensional porous aluminium include: to be deposited on cellular polyurethane, polystyrene, polyethylene, polyurethane, polyvinyl chloride, polypropylene, phenol
Three-dimensional porous aluminium on the foamed plastics such as urea formaldehyde；It is porous to be deposited on the porous assembly of porous graphene, graphene, carbon nanotube
Three-dimensional porous aluminium on the porous carbon materials such as assembly, carbon fiber porous assembly.
3. a kind of three-dimensional porous aluminum honeycomb according to claim 1, which is characterized in that be deposited on metal three dimensional matrix
Three-dimensional porous aluminium includes: to be deposited on nickel foam, foam copper, foam NiCrFe, ZnCu, NiCu, NiCrW, NiFe alloy, nano-pore
Nickel, nano-pore copper, nano-hole golden, nano-pore silver, nano-pore platinum, nano-pore palladium etc. have the metal or alloy of three-dimensional porous structure
On three-dimensional porous aluminium.
4. a kind of three-dimensional porous aluminum honeycomb according to claim 1, which is characterized in that surface has the three of protective layer cladding
Dimension porous aluminum includes: that surface is deposited with the three-dimensional more of one or more of atoms such as carbon, silicon, titanium, tungsten, nickel, Au Ag Pt Pd, zinc
Hole aluminium；Surface is coated with carbon nanotube, graphene, graphite alkene, carbon fiber, polyacetylene, polythiophene, polypyrrole, polyaniline, polyphenyl
The three-dimensional porous aluminium of the materials such as support, polyphenylene ethylene, poly bis alkynes.
5. a kind of three-dimensional porous aluminum honeycomb according to claim 1, which is characterized in that the three-dimensional porous aluminum material packet of alloying
It includes: the binary or polynary porous alloy that aluminium and gallium, copper, chromium, iron, nickel, lead, bismuth, tin or silver are formed.
6. the three-dimensional porous aluminium according to claim 2 being deposited on nonmetallic three dimensional matrix, which is characterized in that al deposition
Method includes electrochemical deposition method and vacuum vapour deposition；Obtaining porous aluminium electrode includes that nonmetallic three dimensional matrix-porous aluminum is multiple
Composite electrode and the pure porous aluminium electrode for removing nonmetallic three dimensional matrix.
7. the three-dimensional porous aluminium according to claim 3 being deposited on metal three dimensional matrix, which is characterized in that al deposition side
Method includes electrochemical deposition method and vacuum vapour deposition；Obtaining porous aluminium electrode includes metal three dimensional matrix-porous aluminum compound electric
The porous Al alloy electrode of pole and further alloying.
8. the application of three-dimensional porous aluminium described in claim 1, three-dimensional porous aluminium is applied to aluminium ion battery, aluminium-sulfur battery, aluminium
The aluminum cells such as air cell, bis- (more) ion batteries containing aluminium.
9. aluminum cell according to claim 8, which is characterized in that aluminum cell is by anode, electrolyte, diaphragm and cathode structure
At wherein cathode is above-mentioned three-dimensional porous aluminium.
10. aluminum cell according to claim 8, which is characterized in that positive electrode includes: conductive carbon paper, graphite powder, acetylene
The materials such as black, sublimed sulfur, sedimentation sulphur, elemental selenium, molybdenum sulfide, artificial gold, vanadic anhydride；Electrolyte include: aluminum halide and
NaCl、KCl、LiCl、CsCl、MgCl2、BaCl2, NaBr, 1- ethyl -3- methy limidazolium, 1- ethyl -3- methyl chloride
The eutectic salts of the formation such as imidazoles, 1- ethyl -3- methylpyridinium iodide imidazoles, urea, formamide, acetamide, propionamide；Battery knot
Structure includes: the cell apparatus such as seal glass electrolytic cell, Swagelok battery, button cell, high temperature resistant soft-package battery.
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| US12195338B2 (en) | 2022-12-15 | 2025-01-14 | 6K Inc. | Systems, methods, and device for pyrolysis of methane in a microwave plasma for hydrogen and structured carbon powder production |
| EP4391098A1 (en) * | 2022-12-23 | 2024-06-26 | APh ePower Co., Ltd. | Negative electrode structure applied to aluminum battery |
| JP7671814B2 (en) | 2022-12-23 | 2025-05-02 | 亞福儲能股▲分▼有限公司 | Anode structure applied to aluminum batteries |
| TWI843384B (en) * | 2023-01-05 | 2024-05-21 | 亞福儲能股份有限公司 | Negative electrode structure of alluminum battery |
| EP4411885A1 (en) * | 2023-01-31 | 2024-08-07 | APh ePower Co., Ltd. | Negative electrode structure applied to aluminum battery |
| JP7695305B2 (en) | 2023-01-31 | 2025-06-18 | 亞福儲能股▲分▼有限公司 | Anode structure applied to aluminum batteries |
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Application publication date: 20190510 |