CN110289444A - It is a kind of to use liquid metal gallium for the aluminium ion battery of cathode - Google Patents
It is a kind of to use liquid metal gallium for the aluminium ion battery of cathode Download PDFInfo
- Publication number
- CN110289444A CN110289444A CN201910547362.5A CN201910547362A CN110289444A CN 110289444 A CN110289444 A CN 110289444A CN 201910547362 A CN201910547362 A CN 201910547362A CN 110289444 A CN110289444 A CN 110289444A
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- cathode
- gallium
- aluminium
- chloride
- aluminium ion
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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
-
- 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
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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
It is a kind of to use liquid metal gallium for the aluminium ion battery of cathode, belong to field of electrochemical batteries.Battery characteristics of the present invention are, liquid gallium cathode, anode, aluminium chloride and inorganic acid salt electrolyte comprising purity 99.9%-99.999% and the as the case may be diaphragm that selects.Liquid metal gallium is placed directly within battery bottom as cathode, or is placed in crucible as cathode.Using solid-state conductive material as liquid gallium negative lug.Charging process, aluminium ion are reduced to aluminium atom and dissolve diffuse into liquid gallium body phase, discharge process in liquid gallium negative terminal surface, and the aluminium atom being dissolved in liquid gallium, which diffuses to gallium surface and is oxidized to aluminium ion, enters electrolyte.Charging/discharging voltage range 0.1-2.4V, current density range 0.01-10A g‑1.Liquid gallium cathode of the present invention has anticorrosive, inhibition Al dendrite, and feature can be recycled.Aluminium ion battery based on the cathode, has the advantages that have extended cycle life, energy density is high, safety and stability, can be used for extensive energy storage or automobile power cell etc..
Description
Technical field
It uses liquid metal gallium for the aluminium ion battery of cathode the present invention relates to a kind of, belongs to field of electrochemical batteries, have
Body can get without dendrite, aluminium ion battery cathode anticorrosive, can be recycled, and finally obtain the long-life, high-energy density,
The extensive energy storage of safety and stability or automobile power aluminium ion battery.
Background technique
With the continuous reduction of the non-regeneration energies such as petroleum, coal, natural gas, and its caused by environmental problem highlight,
It develops and becomes current research hotspot using reproducible green novel energy source.Wherein, electric energy is undoubtedly a kind of clean, and
The important energy source of number of ways (such as waterpower, wind-force, solar energy) collection can be used.However, the collection process of electric energy often companion
With intermittent, noncontinuity process, it is therefore necessary to be stored in secondary cell, realize persistently answering for electric energy with this
With.
In the past few decades, lead-acid accumulator is because cheap, easily fabricated and be widely used, however its energy
Metric density is low, and pollution problem caused by old and useless battery is serious；Therefore, energy density height, the lesser lithium-ion electric of environmental pollution
Pond is developed rapidly.However, lithium content is less in the earth's crust, and lithium battery is easy to happen on fire, explosion during military service
Equal danger, therefore develop the research hotspot that novel secondary cell system is the current field.
In contrast, there are a large amount of aluminium elements in the earth's crust, and aluminium itself has excellent theoretical energy density
(2980mAh g-1, 8040mA h cm-3), while will not be occurred based on room temperature aluminium chloride-inorganic salt system aluminium ion battery
Burning and explosion.Therefore, aluminium ion battery be expected to become next-generation, low cost, can large-scale application secondary cell system.Thing
In reality, the research about aluminium ion battery has been achieved for tremendous development, and it is flat to have developed serial high capacity density, high work
The positive electrode (such as pyrolytic graphite, nickel sulfide, copper sulfide, tellurium, selenium) of platform.Meanwhile about novel flexible, wide temperature, wide electricity
The aluminium ion battery electrolytic solution of gesture window is also evolving.However, the negative electrode material of battery but there is no excessive concern,
Still using metallic aluminium as cathode.Although aluminum honeycomb is low in cost, theoretical duty density is high, however it is in cyclic process, because
Burn into dendrite problems caused by nonuniform deposition/dissolution of aluminium are serious, and eventually lead to cathode powdered, battery permanent failure.
In addition, the aluminum honeycomb of powdered can not utilize again, the waste of metallic aluminium is ultimately caused.
Summary of the invention
Based on the studies above background, the present invention proposes a kind of aluminium ion battery for using liquid metal gallium as cathode.Liquid
Gallium cathode will not generate dendrite in cyclic process, will not corrode, while the gallium cathode after circulation can follow again
Ring utilizes.To achieve the above object, the present invention the following technical schemes are provided:
It is a kind of to use liquid metal gallium for the aluminium ion battery of cathode, it is characterised in that include purity 99.9%-
99.999% liquid gallium cathode, anode, aluminium chloride and inorganic acid salt electrolyte and the as the case may be diaphragm of choosing.Liquid
State gallium is placed directly within battery bottom as cathode, or is placed in crucible as cathode.Using solid-state conductive material as liquid
State gallium negative lug.Charging process, aluminium ion are reduced to aluminium atom and dissolve diffuse into liquid gallium in liquid gallium negative terminal surface
Body phase, discharge process, the aluminium atom being dissolved in liquid gallium, which diffuses to gallium surface and is oxidized to aluminium ion, enters electrolyte.Charge and discharge
Piezoelectric voltage range 0.1-2.4V, current density range 0.01-10Ag-1。
The crucible can be corundum, quartz, polytetrafluoroethylene (PTFE), polyvinyl chloride, polypropylene or the glass earthenware of side-wall hole
Crucible, electrolyte are contacted by the hole of crucible wall with cathode liquid gallium.
The conduction tab is the inactive wires of high-melting-points, chemical property such as molybdenum, nickel, copper, tungsten, zirconium, hafnium, platinum, titanium
Or graphite rod, and its conduction will be made in the wire or graphite rod insertion liquid gallium cathode.
The anode can be carbonaceous material (graphite, carbon paper, pyrolytic graphite), two dimensional oxidation object (copper oxide, nickel oxide,
Zinc oxide etc.) or sulfide material (molybdenum sulfide, titanium sulfide, nickel sulfide, tungsten sulfide, cobalt sulfide, zinc sulphide etc.), metal chloride
One of (nickel chloride, copper chloride etc.) material.
Aluminium chloride purity is greater than 95% in the electrolyte, and inorganic acid salt is 1- butyl -3- methylimidazolium chloride, 1- third
One of base -3- methylimidazolium chloride, 1- ethyl-3-methylimidazole chloride, sodium chloride, lithium chloride, potassium chloride etc..
The aluminium chloride and inorganic acid salt molar ratio is 1:1~3:1.
The selection of the diaphragm specifically: when interpolar is away from being greater than 5mm between positive and negative electrode, and battery is not need mobile storage
When energy battery, it may be unnecessary to diaphragm；When interpolar needs to add diaphragm away from being less than when 5mm or battery need mobile between positive and negative electrode,
Diaphragm material can be glass fibre, or polypropylene micropore diaphragm.
Aluminium ion battery relative to tradition using aluminum metal as cathode, the present invention using liquid gallium as cathode, gained aluminium from
Sub- battery has many advantages, such as to have extended cycle life, energy density is high, safety and stability.
Compared with the existing technology, beneficial effects of the present invention are as follows:
1) Al dendrite, will not be generated in cathode cyclic process, reduces the risk of internal short-circuit of battery；
2), etching problem is not present in cathode, its effective affecting acreage will not change in cyclic process, therefore can be effective
Improve the cyclical stability of battery；
3) the gallium cathode after, recycling can be recycled further, therefore can reduce the cost of battery, reduce metallic aluminium
Waste.
Detailed description of the invention
Fig. 1 is the battery structure schematic diagram of embodiment 1.
Specific embodiment
The present invention will be described in more detail below by specific embodiment, but protection scope of the present invention is not limited
In these embodiments.
Embodiment 1
It uses corundum crucible for battery case (internal diameter 100mm, high 100mm), liquid metal gallium is placed in corundum crucible bottom
Layer (thickness 10mm) will be used as negative lug in metal molybdenum filament (diameter 1mm) insertion liquid metal gallium.Using carbon paper as anode
Material, and using metal tantalum connection carbon paper as plus plate current-collecting body；Use glass fibre cladding as anode carbon paper, it is final to use
Stainless steel connects metal tantalum as positive pole ear.Use molar ratio for the aluminium chloride of 1.3:1 and 1- ethyl -3- methylimidazolium chloride
For electrolyte, the liquid gallium upper layer of 10mm thickness is placed it in.Entire battery is protected using inert argon, and is sealed with this isolating oxygen
Gas and water.Battery immerses positive carbon paper in electrolyte in cyclic process, and in the potential range of 0.4-2.4V, with
0.01-10Ag-1Current density carry out charge and discharge cycles.
Embodiment 2
Use glass jar for battery case (internal diameter 100mm, high 100mm), it is (thick that liquid metal gallium is placed in glass jar bottom
Spend 10mm), negative lug will be used as in metallic silver wire (diameter 1mm) insertion liquid metal gallium.Using pyrolytic graphite as anode
Material, and using metal molybdenum connection pyrolytic graphite as plus plate current-collecting body；Glass fibre is used to coat as anode pyrolytic graphite,
Finally using stainless steel connection metal molybdenum as positive pole ear.Using molar ratio for the aluminium chloride of 1.5:1 and sodium chloride is electrolysis
Liquid places it in the liquid gallium upper layer of 10mm thickness.Entire battery is protected using inert argon, and seal with this starvation with
Water, the operating temperature of battery are 150 ± 10 DEG C.Battery immerses positive pyrolytic graphite in electrolyte in cyclic process, and
In the potential range of 1.0-2.4V, with 0.01-10Ag-1Current density carry out charge and discharge cycles.
Embodiment 3
Use quartzy tank for battery case (internal diameter 100mm, high 100mm), it is porose just that liquid metal gallium is placed in side wall
In beautiful crucible (internal diameter 10mm, side wall aperture 10mm), cathode pole will be used as in metal molybdenum filament (diameter 1mm) insertion liquid metal gallium
Ear.It uses the nickel sulfide being coated in tantalum foil for anode, and connects stainless steel as positive pole ear.Using the chlorination of 1.6:1
Aluminium and 1- propyl -3- methylimidazolium chloride are electrolyte.Entire battery is protected using inert argon, and is sealed with this starvation
And water.Battery immerses positive carbon paper in electrolyte in cyclic process, and charge and discharge is carried out in the potential range of 0.4-2.4V
Electricity circulation.
Embodiment 4
It uses polytetrafluoroethylene (PTFE) crucible for battery case (internal diameter 100mm, high 100mm), liquid metal gallium is placed in poly- four
Vinyl fluoride crucible bottom (thickness 10mm) will be used as negative lug in metal platinum filament (diameter 0.3mm) insertion liquid metal gallium.It adopts
Use carbon paper as positive electrode, and using metal tantalum connection carbon paper as plus plate current-collecting body；Carbon paper is coated with glass fibre and is made
For anode, metal tantalum is finally connected as positive pole ear using stainless steel.Use molar ratio for the aluminium chloride of 1.5:1 and 1- fourth
Base -3- methylimidazolium chloride is electrolyte, places it in the liquid gallium upper layer of 10mm thickness.Entire battery is protected using inert argon
Shield, and seal with this starvation and water.Battery immerses positive carbon paper in electrolyte in cyclic process, and in 0.4-2.4V
Potential range in, with 0.01-10Ag-1Current density carry out charge and discharge cycles.
Embodiment 5
Use glass jar for battery case (internal diameter 100mm, high 100mm), it is (thick that liquid metal gallium is placed in glass jar bottom
Spend 10mm), negative lug will be used as in metallic silver wire (diameter 1mm) insertion liquid metal gallium.Using pyrolytic graphite as anode
Material uses the cobalt sulfide being coated in tantalum foil for anode, and connects stainless steel as positive pole ear.Use molar ratio for 3:
1 aluminium chloride and potassium chloride is electrolyte, places it in the liquid gallium upper layer of 10mm thickness.Entire battery is protected using inert argon
Shield, and seal with this starvation and water, the operating temperature of battery is 170 ± 10 DEG C.Battery will be just very hot in cyclic process
It solves graphite to immerse in electrolyte, and in the potential range of 1.0-2.4V, with 0.01-10Ag-1Current density carry out charge and discharge
Circulation.
It should be noted that those skilled in the art are that this hair may be implemented completely according to the various embodiments described above of the present invention
Bright independent claims and the full scope of appurtenance, realize process and the same the various embodiments described above of method；And the present invention is not
It elaborates and partly belongs to techniques well known.
The above, part specific embodiment only of the present invention, but scope of protection of the present invention is not limited thereto, appoints
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, should all cover by what those skilled in the art
Within protection scope of the present invention.
Claims (8)
1. a kind of use liquid metal gallium for the aluminium ion battery of cathode, which is characterized in that include purity 99.9%-99.999%
Liquid gallium cathode, anode, aluminium chloride and inorganic acid salt electrolyte and as the case may be and select diaphragm；Liquid metal gallium
Battery bottom is placed directly within as cathode, or is placed in crucible as cathode.Using solid-state conductive material as liquid gallium cathode
Tab；Charging process, aluminium ion are reduced to aluminium atom and dissolve diffuse into liquid gallium body phase in liquid gallium negative terminal surface；Electric discharge
Process, the aluminium atom being dissolved in liquid gallium, which diffuses to gallium surface and is oxidized to aluminium ion, enters electrolyte；Charging/discharging voltage model
Enclose 0.1-2.4V, current density range 0.01-10Ag-1。
2. a kind of as described in claim 1 use liquid metal gallium for the aluminium ion battery of cathode, which is characterized in that the crucible
For the corundum of side-wall hole, quartz, polytetrafluoroethylene (PTFE), polyvinyl chloride, polypropylene or glass pot, electrolyte passes through crucible wall
Hole contacted with cathode liquid gallium.
3. a kind of as described in claim 1 use liquid metal gallium for the aluminium ion battery of cathode, which is characterized in that the conduction
Tab is molybdenum, nickel, copper, tungsten, zirconium, hafnium, titanium high-melting-point, the inactive wire of chemical property or graphite rod, and by the wire
Or make its conduction in graphite rod insertion liquid gallium cathode.
4. a kind of as described in claim 1 use liquid metal gallium for the aluminium ion battery of cathode, which is characterized in that the anode
It is one of carbonaceous material, two dimensional oxidation object or sulfide material, metal chloride material.
5. a kind of as claimed in claim 4 use liquid metal gallium for the aluminium ion battery of cathode, which is characterized in that the carbonaceous
Material is graphite, carbon paper, pyrolytic graphite；The two dimensional oxidation object is copper oxide, nickel oxide, zinc oxide；The sulfide material
For molybdenum sulfide, titanium sulfide, nickel sulfide, tungsten sulfide, cobalt sulfide, zinc sulphide；The metal chloride is nickel chloride, copper chloride.
6. a kind of as described in claim 1 use liquid metal gallium for the aluminium ion battery of cathode, which is characterized in that the electrolysis
Aluminium chloride purity is greater than 95% in liquid, and inorganic acid salt is 1- butyl -3- methylimidazolium chloride, 1- propyl -3- methylimidazole chlorine
One of compound, 1- ethyl-3-methylimidazole chloride, sodium chloride, lithium chloride, potassium chloride.
7. a kind of as described in claim 1 use liquid metal gallium for the aluminium ion battery of cathode, which is characterized in that the chlorine
Change aluminium and inorganic acid salt molar ratio is 1:1~3:1.
8. a kind of as described in claim 1 use liquid metal gallium for the aluminium ion battery of cathode, which is characterized in that the diaphragm
Selection specifically: when interpolar is away from being greater than 5mm between positive and negative electrode, and battery is when not needing mobile energy-storage battery, do not need every
Film；When interpolar needs to add diaphragm away from being less than between positive and negative electrode when 5mm or battery need mobile, diaphragm material selects glass fibers
Dimension, or selection polypropylene micropore diaphragm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910547362.5A CN110289444A (en) | 2019-06-24 | 2019-06-24 | It is a kind of to use liquid metal gallium for the aluminium ion battery of cathode |
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| CN201910547362.5A CN110289444A (en) | 2019-06-24 | 2019-06-24 | It is a kind of to use liquid metal gallium for the aluminium ion battery of cathode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111224149A (en) * | 2019-12-13 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation method of battery anode of graphene nanosheet based on electrochemical cathode stripping and aluminum ion battery |
| CN114939670A (en) * | 2022-05-27 | 2022-08-26 | 昆明理工大学 | Method for generating copper dendrite on surface of liquid metal gallium |
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| US20130143113A1 (en) * | 2011-12-06 | 2013-06-06 | John E. Stauffer | Aluminum storage battery |
| CN104241596A (en) * | 2014-08-22 | 2014-12-24 | 北京科技大学 | Rechargeable aluminum ion cell and preparation method thereof |
| CN108539148A (en) * | 2018-03-22 | 2018-09-14 | 中国科学院合肥物质科学研究院 | A kind of room temperature gallium base fluid state metal-silicon composite negative pole and preparation method thereof |
| 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 |
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2019
- 2019-06-24 CN CN201910547362.5A patent/CN110289444A/en active Pending
Patent Citations (4)
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| US20130143113A1 (en) * | 2011-12-06 | 2013-06-06 | John E. Stauffer | Aluminum storage battery |
| CN104241596A (en) * | 2014-08-22 | 2014-12-24 | 北京科技大学 | Rechargeable aluminum ion cell and preparation method thereof |
| CN108539148A (en) * | 2018-03-22 | 2018-09-14 | 中国科学院合肥物质科学研究院 | A kind of room temperature gallium base fluid state metal-silicon composite negative pole and preparation method thereof |
| 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 |
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111224149A (en) * | 2019-12-13 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation method of battery anode of graphene nanosheet based on electrochemical cathode stripping and aluminum ion battery |
| CN114939670A (en) * | 2022-05-27 | 2022-08-26 | 昆明理工大学 | Method for generating copper dendrite on surface of liquid metal gallium |
| CN114939670B (en) * | 2022-05-27 | 2024-04-02 | 昆明理工大学 | Method for generating copper dendrites on surface of liquid gallium metal |
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Application publication date: 20190927 |