CN104112865B - A kind of liquid metal cell device and assembly method thereof - Google Patents
A kind of liquid metal cell device and assembly method thereof Download PDFInfo
- Publication number
- CN104112865B CN104112865B CN201410350077.1A CN201410350077A CN104112865B CN 104112865 B CN104112865 B CN 104112865B CN 201410350077 A CN201410350077 A CN 201410350077A CN 104112865 B CN104112865 B CN 104112865B
- Authority
- CN
- China
- Prior art keywords
- metal
- electrolyte
- battery
- battery container
- mesh opening
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
- H01M8/143—Fuel cells with fused electrolytes with liquid, solid or electrolyte-charged reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
A kind of liquid metal cell device and assembly method thereof, this cell apparatus comprises the battery container of metal material, be provided with positive electrode, electrolyte and current collector successively from top to bottom in battery container, and the metal mesh opening divider separates that electrolyte is arranged in battery container becomes upper and lower two parts; Current collector comprise be located at electrolyte upper surface and immerse electrolytical be adsorbed with negative material metal polyporous material, be located at the metal perforated plate above metal polyporous material and be located at the metal electric current leading-off rods above metal perforated plate; The top center of battery container has hole, and hole is provided with sealed insulation ceramic member, and the top of metal electric current leading-off rods is stretched out outside hole, by sealed insulation ceramic member by the top of metal electric current leading-off rods and battery container fastening, seal and insulate.This cell apparatus can prevent internal short-circuit of battery, extends its service life, and its structure is simple, with low cost, highly effective.Its assembly method is simple and practical, is easy to industrialized production.
Description
Technical field
The invention belongs to electrochemical energy storage cell field, be specifically related to a kind of liquid metal cell device and assembly method thereof.
Background technology
The world today develops rapidly, and along with the consumption of mass energy, energy problem is increasingly serious, under limited resource, how to make good use of the hot issue that existing Energy output has become people's concern efficiently.As everyone knows, in electric power system, the peak load shifting of electric energy, the efficiency utilization of the intermittent energy such as new forms of energy generates electricity by way of merging two or more grid systems all needs efficient energy storage technology as support.Jumbo energy storage technology is mainly divided into chemical energy storage (as lithium ion battery, sodium-sulphur battery, flow battery etc.), physics energy storage (as pumped storage, compressed-air energy storage, flywheel energy storage etc.) and Power Flow (as superconducting energy storage, ultracapacitor etc.) three major types.Wherein chemical energy storage (battery technology) due to have energy conversion efficiency high, to environment with space requirement is low and the advantage such as advantage of lower cost, become the first-selection of extensive energy storage technology in following intelligent grid.The battery technology for energy storage of current several main flow mainly comprises lead-acid battery, sodium-sulphur battery, lithium ion battery and all-vanadium flow battery etc.Wherein the energy density of lead-acid battery is low, and charge/discharge rates is slow, and cycle life is short, and big for environment pollution; Sodium-sulphur battery is owing to adopting beta-alumina solid electrolyte, and its manufacturing cost is high and thermal stability is poor, easily breaks and causes serious security incident; The current density of lithium ion battery is low and manufacturing cost is higher; Flow battery is also faced with electrolyte, the electrode pad particularly technical problem of the critical material such as amberplex and energy storage problem on the high side.These limit its application in electrical network energy storage all to a certain extent, and another kind of make to measure for electrical network energy storage, with low cost, discharge rate is high, the life-span is long and very safe battery technology is born---liquid metal cell technology.
2007, " full liquid metal cell " the Objective Concept Massachusetts Institute Technology professor D.R.Sadoway for large-scale electrical power system energy storage proposed.At high temperature, two electrodes are liquid metal to this full liquid metal cell, and electrolyte is molten state inorganic salts, and electrode and electrolyte are due to different and the immiscible and natural layering of density, and two liquid metal electrodes separate by electrolyte nature.But, in some electrode systems, as battery negative material and positive electrode generation alloying in discharge process of positive electrode containing metal antimony (Sb) etc., generate compound between the solid metallic under high temperature, and proceed along with discharge process, the composition of the intermetallic compound of generation changes thereupon, thus produces internal stress in intermetallic compound inside and intermetallic compounds layer is arched upward, positive pole and negative pole are coupled together, causes internal short-circuit of battery.(Bradwell D J,Kim H,Sirk A H C,et al.Magnesium–Antimony Liquid Metal Battery for Stationary EnergyStorage[J].Journal of the American Chemical Society,2012,134(4):1895-1897.)
Summary of the invention
The object of the present invention is to provide a kind of liquid metal cell device and assembly method thereof, utilize the design of metal mesh opening separator to stop the generation of short circuit between positive electrode and negative material in liquid metal cell, thus extend the service life of liquid metal cell.Effectively can prevent internal short-circuit of battery, thus make battery obtain stable and efficient chemical property.
For achieving the above object, the technical solution used in the present invention is:
A kind of liquid metal cell device, comprise the battery container of metal material, be disposed with positive electrode, electrolyte and current collector from top to bottom in battery container, and the metal mesh opening divider separates that electrolyte is arranged in battery container becomes upper and lower two parts; Current collector comprise be adsorbed with negative material metal polyporous material, be fixed on the metal perforated plate with some through holes above metal polyporous material and be fixed on the metal electric current leading-off rods above metal perforated plate; The bottom of metal polyporous material is immersed in electrolyte, the center at battery container top is offered porose, hole is provided with sealed insulation ceramic member, the top of metal electric current leading-off rods is stretched out outside hole, and be fastened on the upper surface of battery container by sealed insulation ceramic member, and the top of the top of metal electric current leading-off rods and battery container is by sealed insulation ceramic member sealing also mutual insulating; Wherein the top of metal electric current leading-off rods is battery cathode, and battery container is anode; Under battery operation state, positive electrode, electrolyte and the negative material be adsorbed on metal polyporous material are all in a liquid state, negative material infiltrates metal polyporous material, and the density of positive electrode is greater than electrolytical density, electrolytical density is greater than the density of negative material, objectionable intermingling between positive electrode, electrolyte, negative material.
Described positive electrode is one or more the mixture in Al, Zn, Ga, Cd, In, Sn, Sb, Te, Hg, Ti, Pb, Bi; Negative material is one or more the mixture in Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba; Electrolyte is one or more the mixture in the halogen family inorganic salts that negative material is corresponding.
Described metal mesh opening separator is welded in battery container, and the material of metal mesh opening separator is stainless steel or titanium alloy; The wire netting that metal mesh opening separator comprises metal mesh opening supporting bracket and is arranged in metal mesh opening supporting bracket; Wherein the mesh aperture of metal mesh opening supporting bracket is 3 ~ 6mm, and thickness is 3 ~ 5mm; The mesh aperture of wire netting is less than 1mm, and thickness is less than 1mm.
Described electrolytical integral thickness is 1 ~ 3cm, and electrolyte is (1.5 ~ 2.5) by the upper and lower two-part Thickness Ratio that metal mesh opening divider separates becomes: 1.
Distance between the edge of described metal polyporous material and the sidewall of battery container is 8 ~ 15mm.
The material of described metal polyporous material is nickel, zirconium, titanium or its alloy, and the average pore diameter of metal polyporous material is less than 1mm, and porosity is 70 ~ 85%.
The material of described sealed insulation ceramic member is aluminium oxide or zirconia.
The material of described battery container is stainless steel or titanium alloy, and the shape of battery container is square.
The material of described metal perforated plate is stainless steel or titanium alloy;
The material of described metal electric current leading-off rods is stainless steel or titanium alloy, and diameter is 1 ~ 2cm.
The assembly method of liquid metal cell device, comprises the following steps:
1) battery container is made up of metal top cover with holes, metal tube and metal end, is welded in metal tube by metal mesh opening separator, then metal end is welded on the bottom of metal tube, obtains battery compartment;
2) metal perforated plate is fixed on metal polyporous material, then metal electric current leading-off rods is fixed on metal perforated plate, composition current collector; Then on the hole of metal top cover, install sealed insulation ceramic member, by sealed insulation ceramic member, the top of metal electric current leading-off rods and metal top cover are fastenedly connected;
3) negative material is heated to fusing, utilize the metal polyporous material of current collector and the wettability of negative material, current collector is made to absorb liquid negative material, cooling after absorption completes, then successively positive electrode and electrolyte are placed in battery compartment, electrolyte is become upper and lower two parts by metal mesh opening divider separates, then in battery compartment, inert gas is filled with, again the metal top cover be fastenedly connected with current collector is welded on battery compartment, is warming up to operating temperature and obtains full rechargeable battery;
Or at room temperature, successively positive electrode, negative material and electrolyte are placed in battery compartment, electrolyte is become upper and lower two parts by metal mesh opening divider separates, then in battery compartment, inert gas is filled with, again the cell cover be fastenedly connected with current collector is welded on battery compartment, is warming up to operating temperature and obtains full discharge battery.
Relative to prior art, beneficial effect of the present invention is:
Liquid metal cell device provided by the invention obviously can strengthen the ability of battery opposing external environment change, there is very high working life, and there is higher energy conversion efficiency, its structure is simple, with low cost, highly effective, utilize metal mesh opening separator to stop the generation of short circuit between positive electrode and negative material in liquid metal cell, thus extend the service life of liquid metal cell.Effectively can prevent internal short-circuit of battery, thus make battery obtain stable and efficient chemical property.Also have the following advantages in addition:
1. liquid metal cell two liquid electrode and fused electrolyte are due to the different AUTOMATIC ZONING of density, negative material and positive electrode alloying in discharge process, generate compound between the solid metallic under high temperature, and proceed intermetallic compound inside generation internal stress along with discharge process and intermetallic compounds layer is arched upward, positive pole and negative pole are coupled together, causes internal short-circuit of battery.The present invention expands to negative pole by arranging metal mesh opening separator to suppress the solid alloy generated in positive polar region, to reach the object avoiding battery premature failure, this liquid metal cell is had longer life-span and more stable performance, makes it really be applicable to long-term static stored energy application.
2. liquid metal cell device provided by the invention, by using the technology of the sealing-in of pottery and metal, sealed insulation ceramic member is used between battery container and metal electric current leading-off rods fastening, sealing and insulation, overcome burn into sealing and the Insulation Problems of material under high temperature, can greatly reduce costs.
3. present invention eliminates in conventional liquid/semi-liquid metal cell apparatus in metal cylinder enclosure interior coating dielectric ceramic layer or the design installing insulating ceramics pipe additional, direct use has good infiltrating metal polyporous material to adsorb negative material with liquid negative material, creatively achieve the separation of negative pole and positive pole sidewall, significantly reduce cost.
The assembly method of liquid metal cell device provided by the invention, has simple and practical advantage, can assemble out full rechargeable battery or full discharge battery, be beneficial to industrialized production, have a good application prospect according to different situations.
Accompanying drawing explanation
Fig. 1 is the structural representation of liquid metal cell device;
Fig. 2 is the liquid metal cell single cyclic voltage curve including metal mesh opening separator
Fig. 3 is the liquid metal cell cycle performance curve including metal mesh opening separator;
Wherein, 1 is battery container, and 2 is electrolyte, and 3 is positive electrode, and 4 is metal polyporous material, and 5 is metal perforated plate, and 6 is sealed insulation ceramic member, and 7 is metal electric current leading-off rods, and 8 is metal mesh opening separator.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Provided by the invention have following important improvement point:
1., when the capacity of liquid metal cell becomes very large, the design of battery is a very crucial factor.Three kinds of different liquids that liquid metal cell comprises are based on the difference of mutual unmixability and density and natural layering, the liquid metal that one deck electronegativity is lower is positioned at top, another kind of liquid metal (or liquid metal alloy) is positioned at bottom, and molten salt electrolyte is positioned between the two.Have lower electronegative metal level as negative pole, higher electronegative metal level is as positive pole.Adopt the battery of this design can bear very high current density but only cause inappreciable Charger transfer overpotential, structure simply, is easily assembled simultaneously.But in the process of battery charging and discharging circulation, between solid metallic, compound can at the Interface debond of electrolyte and positive pole, between solid metallic, chemical composition change can produce internal stress, in some cases between solid metallic compound layer can arch upward, through electrolyte, positive pole and negative pole are linked together, cause internal short-circuit of battery, thus make battery failure, shorten cell operating lifetime.The short-circuit failure that the design of liquid metal cell before this does not still have effective measures to cause to stop battery because intermetallic compound generates.And in the electrolyte of the present invention between both positive and negative polarity, install metal mesh opening separator additional, for limiting the distortion of compound between solid metallic, thus prevent battery failure.Metal mesh opening separator should meet low cost, high strength and allow the condition of ionic charge fast transport, the position that can't change at inside battery because of the growth of compound between solid metallic.Experimental result shows, the metal mesh opening separator that the present invention proposes can prevent the generation of internal short-circuit of battery effectively, thus make battery obtain stable and efficient chemical property, extend the service life of battery, this is proved by the runnability that battery is stable.And the design of metal mesh opening separator is cheap and easy to implement, does not almost have fringe cost.
2. because liquid metal cell is 300 ~ 700 DEG C of operations, and the ceramic block of metal sealing and metal material must between different temperatures expansion rate basically identical, otherwise sealing structure can produce thermal stress because the expansion rate of pottery and metal material is inconsistent, sealing layer is ftractureed, lost efficacy.Mainly comprising with the ceramic material of metal sealing of existing maturation: alumina ceramic, beryllia ceramic, magnesia ceramics, zirconium oxide porcelain, forsterite ceramic, steatite ceramic, spinelle porcelain and Mullite porcelain etc., metal adopts erosion-resisting metal material in concrete electrode and electrolyte system, as stainless steel, titanium alloy etc.So, realize the sealing-in of the ceramic materials such as the boron nitride of anti-negative material corrosion or coating and metal, first will find and a kind ofly have the metal material mated with its expansion rate, it is very big that this technology implements difficulty, the very high (Chinese Patent Application No.: 201310131587.5) of cost.And the sealed insulation ceramic member for insulated enclosure that the present invention relates to is not owing to directly contacting with electrode material, no longer need expensive ceramic material or the coatings such as the boron nitride of strict anti-negative material corrosion, the potteries such as the most ripe in current art, that cost is minimum aluminium oxide, zirconia can be adopted.In addition, the size of the sealed insulation ceramic member that the present invention relates to is very little, and be simple cylindrical shape, full-size is between 10 ~ 20mm, this makes the material cost of sealed insulation ceramic member itself very little, and the sealing surface area of the battery container of sealed insulation ceramic member and metal material is also very little, make the cost of liquid metal cell device provided by the invention very low.
3. for adsorb the metal polyporous material of negative material choose needs consider following some: 1). need, under the operating temperature of concrete electrode and electrolyte system, there is enough intensity, not yielding under high temperature; 2). only more than uniform temperature, just meeting and concrete liquid negative material have enough wettabilities to metal polyporous material, so choosing of metal polyporous material needs to consider that it and liquid negative material produce enough infiltrating temperature, this critical temperature lower than the actual motion temperature of battery, thus must ensure the good adsorption of anticathode material.Find after deliberation, the material that metal polyporous material can be chosen has nickel, zirconium, titanium and titanium alloys.3). the hole of metal polyporous material is less, and adsorptivity is stronger, but the amount of the liquid negative material of absorption is also fewer, so the size of hole is also a parameter affecting adsorptivity.Experiment finds, when the average pore diameter size of metal polyporous material is within 1mm, porosity adsorption effect about 80% time is best.
4. because liquid negative material has certain solubility in its corresponding halogen family molten salt electrolyte, experiment finds, distance between the periphery and the sidewall of battery container of current collector little to 5 ~ 7mm time, be adsorbed on and have the negative material in good infiltrating metal polyporous material can form the path of leakage current in cell operation with negative material, filament or faciola shape current path is formed with the form of pure matter negative material, the periphery of metal polyporous material and the sidewall of battery container are coupled together, the micro-short circuit of this form can continue expansion, finally cause battery failure, i.e. thorough short circuit.So the distance between the periphery of designing requirement current collector of the present invention and the sidewall of battery container is greater than 8mm, thus prevents the appearance of micro-short circuit.
5. battery container is squared design, save space, more be applicable to connection in series-parallel to connect in groups, and positive electrode not easily swashes from the sidewall of battery container, short circuit can be prevented, ensure that battery has desirable service life, make cell really can become energy-storage module primitive in large-scale energy storage system.
Find through experiment, to cancel in conventional liquid metal battery device after the dielectric ceramic layer of round metal tubular enclosure interior coating or the insulating ceramics pipe that installs additional, positive electrode is owing to directly contacting with the sidewall of round metal barrel-type casing, and with housing sidewall, there is certain wettability, positive electrode can be swashed along housing sidewall in cell operation, and this part can strengthen this micro-short circuit forming process along the positive electrode that housing sidewall is swashed in the place nearest with the metal polyporous material being adsorbed with negative material, positive electrode subparticipation forms filament or the periphery of metal polyporous material and housing sidewall couple together by faciola shape current path.Swash to assist negative material simple substance to diffuse to housing sidewall from metal polyporous material along housing sidewall to limit positive electrode, final formation leakage current paths, cause the phenomenon of battery micro-short circuit, research finds when the shape of the battery container of metal becomes square from circle, due to four and the existence at rough excessive right angle, positive electrode successfully can not swash in these right angle due to the effect of tension force, the positive electrode upwards climbed is pinned at the bottom of battery compartment by these four right angles as four nails, thus well limit the phenomenon that positive electrode swashes and occur.And, significantly, the design of square battery container more efficiently utilizes space than the design of circular battery container on horizontal and vertical, and be more beneficial to stacking to be connected with connection in series-parallel, this forms energy storage module for cell connection in series-parallel and lays a good foundation, and makes cell really become energy-storage module primitive in large-scale energy storage system.
See Fig. 1, liquid metal cell device provided by the invention comprises square battery container 1, metal mesh opening separator 8, current collector, positive electrode 3, negative material and electrolyte 2;
Be disposed with positive electrode 3, electrolyte 2 and current collector in battery container 1 from top to bottom, and the metal mesh opening separator 8 that electrolyte 2 is arranged in battery container 1 is separated into upper and lower two parts;
As shown in Figure 2, the material of metal mesh opening separator 8 is stainless steel or titanium alloy; The wire netting that metal mesh opening separator 8 comprises metal mesh opening supporting bracket and is arranged in metal mesh opening supporting bracket; Wherein metal mesh opening supporting bracket is used for providing physical strength to metal mesh opening separator 8, and its mesh aperture is 3 ~ 6mm, and thickness is 3 ~ 5mm; Wire netting generates on cell cross-section for preventing uneven solid phase, and its mesh aperture is less than 1mm, and thickness is less than 1mm.
Current collector forms by with the metal perforated plate 5 of some through holes, metal polyporous material 4, metal electric current leading-off rods 7 and several pieces of fastening bolts; Metal polyporous material 4 is positioned at the upper surface of electrolyte 2, and is adsorbed with negative material; Metal perforated plate 5 is fastened on the top of metal polyporous material 4 by fastening bolt; Metal electric current leading-off rods 7 is fixed on the center above metal perforated plate 5.
Battery container 1 comprises battery compartment, metal top cover and sealed insulation ceramic member 6.Battery compartment is welded by metal side tube and the metal square end cover rim being positioned at bottom; Metal top cover is for having the square end cap of certain size (coordinating with sealed insulation ceramic member 6, the about 10 ~ 20mm of diameter) circular hole at the over center position; The upper end of battery compartment is docked with metal top cover, docks and is realized along utilizing to weld by the upper edge of battery compartment and the lower of metal top cover; The top of metal electric current leading-off rods 7 is stretched out outside circular hole, utilizes sealed insulation ceramic member 6 to make the end sealing of the circular hole of metal top cover and metal electric current leading-off rods 7, insulate, be fastenedly connected.The top of metal electric current leading-off rods 7 is battery cathode, and battery container 1 is anode.
Positive electrode 3 is inert metal, as Al, Zn, Ga, Cd, In, Sn, Sb, Te, Hg, Ti, Pb, Bi etc. and alloy thereof; Negative material is active metal, as Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba etc. and alloy thereof; Electrolyte 2 is one or more the mixture in the halogen family inorganic salts of corresponding negative material.The integral thickness of electrolyte 2 is 1 ~ 3cm, and electrolyte 2 is (1.5 ~ 2.5) by the upper and lower two-part Thickness Ratio that metal mesh opening separator 8 is separated into: 1.
Positive electrode, negative material and electrolyte under cell operating temperature (300 ~ 700 DEG C) are all in liquid state, because density is different and do not dissolve each other, the electrolyte that positive electrode and negative material are melted state separates, positive electrode is positioned at bottom, contact with the bottom of battery container, negative material is positioned at above the electrolyte of molten state, and infiltrates current collector.
Distance between the edge of metal polyporous material 4 and the sidewall of battery container 1 is 8 ~ 15mm.The material of metal polyporous material 4 is nickel, zirconium, titanium and titanium alloys.The average pore diameter of metal polyporous material 4 is less than 1mm, and porosity is 70 ~ 85%.The material of sealed insulation ceramic member 6 is aluminium oxide or zirconia.The material of battery container 1, metal perforated plate 5 and metal electric current leading-off rods 7 is stainless steel or titanium alloy, and the diameter of metal electric current leading-off rods 7 is 1 ~ 2cm.
The assembly method of liquid metal cell device provided by the invention, comprises the following steps:
1) battery container 1 is made up of the square end cap of metal top cover with holes, metal side tube and metal, is welded in metal side tube by metal mesh opening separator 8, then square for metal end cap is welded on the bottom of metal side tube, obtains battery compartment;
2) metal perforated plate 5 is fixed on metal polyporous material 4, then metal electric current leading-off rods 7 is fixed on metal perforated plate 5, composition current collector; Then on the hole of metal top cover, install sealed insulation ceramic member 6, by sealed insulation ceramic member 6, the top of metal electric current leading-off rods 7 and metal top cover are fastenedly connected;
3) negative material is heated to fusing, utilize the metal polyporous material 4 of current collector and the good wettability of negative material, current collector is made to absorb liquid negative material, cooling after absorption completes, then successively positive electrode 3 and electrolyte 2 are placed in battery compartment, electrolyte 2 is separated into upper and lower two parts by metal mesh opening separator 8, then in battery compartment, inert gas is filled with, again the metal top cover be fastenedly connected with current collector is welded on battery compartment, this assembling mode is called assembling of entirely charging, the battery assembled by this way is called full rechargeable battery,
Or at room temperature, successively positive electrode 3, negative material and electrolyte 2 is placed in battery compartment, electrolyte 2 is separated into upper and lower two parts by metal mesh opening separator 8, then in battery compartment, inert gas is filled with, again the cell cover be fastenedly connected with current collector is welded on battery compartment, this mode is called assembling of entirely discharging, and the battery assembled by this way is called full discharge battery.
In order to verify the concrete Practical Performance of liquid metal cell device provided by the invention, using this liquid metal cell device to assemble and a series of there is Different electrodes material and electrolytical battery, and electro-chemical test has been carried out to it, all achieving good effect.Below choose one of them example to illustrate stability and the practicality of this liquid metal cell device.
Find to have good runnability after the Li||Sb-Pb battery including metal mesh opening separator is assembled.First wire netting is welded in metal mesh opening supporting bracket, obtain metal mesh opening separator, again metal mesh opening separator is welded on the certain altitude of battery container inwall afterwards, again positive pole antimonial lead is put into bottom battery compartment, then electrolyte is added, electrolyte is divided into two-layer up and down by metal mesh opening separator, then the current collector being adsorbed with negative material is put into, finally be filled with high-purity argon gas and metal top cover be welded on the top of battery compartment, after completing the making of liquid metal cell, being heated operating temperature.This liquid metal cell successfully runs at higher current densities, and has extraordinary performance.As shown in Figure 3, this liquid metal cell still has very high coulombic efficiency (99%) more than 180 circulation times, higher energy efficiency (75%) and highly stable discharge capacity close.
The design of metal mesh opening separator is verified can prevent battery to lose efficacy prematurely effectively, thus makes battery obtain better more stable performance.This is the scheme of cheap, a feasible economically increase liquid metal cell service life.The design of this mesh separator also can be applied in other liquid state batteries systems as Na||Sb-Pb, Ca-Mg||Sb-Pb, Mg||Sb-Pb, and Sr||Pb-Sb etc.
Claims (10)
1. a liquid metal cell device, it is characterized in that: the battery container (1) comprising metal material, be disposed with positive electrode (3), electrolyte (2) and current collector in battery container (1) from top to bottom, and the metal mesh opening separator (8) that electrolyte (2) is arranged in battery container (1) is separated into upper and lower two parts; The metal electric current leading-off rods (7) that current collector comprises the metal polyporous material (4) being adsorbed with negative material, the metal perforated plate with some through holes (5) being fixed on metal polyporous material (4) top and is fixed on above metal perforated plate (5); The bottom of metal polyporous material (4) is immersed in electrolyte (2), the center at battery container (1) top is offered porose, hole is provided with sealed insulation ceramic member (6), the top of metal electric current leading-off rods (7) is stretched out outside hole, and be fastened on the upper surface of battery container (1) by sealed insulation ceramic member (6), and the top of the top of metal electric current leading-off rods (7) and battery container (1) is by sealed insulation ceramic member (6) sealing also mutual insulating; Wherein the top of metal electric current leading-off rods (7) is battery cathode, and battery container (1) is anode; Under battery operation state, positive electrode (3), electrolyte (2) and the negative material be adsorbed on metal polyporous material (4) are all in a liquid state, negative material infiltrates metal polyporous material (4), and the density of positive electrode (3) is greater than the density of electrolyte (2), the density of electrolyte (2) is greater than the density of negative material, objectionable intermingling between positive electrode (3), electrolyte (2), negative material.
2. liquid metal cell device according to claim 1, is characterized in that: the mixture that described positive electrode (3) is one or more in Al, Zn, Ga, Cd, In, Sn, Sb, Te, Hg, Ti, Pb, Bi; Negative material is one or more the mixture in Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba; Electrolyte (2) is one or more the mixture in halogen family inorganic salts corresponding to negative material.
3. liquid metal cell device according to claim 1 and 2, it is characterized in that: described metal mesh opening separator (8) is welded in battery container (1), the material of metal mesh opening separator (8) is stainless steel or titanium alloy; The wire netting that metal mesh opening separator (8) comprises metal mesh opening supporting bracket and is arranged in metal mesh opening supporting bracket; Wherein the mesh aperture of metal mesh opening supporting bracket is 3 ~ 6mm, and thickness is 3 ~ 5mm; The mesh aperture of wire netting is less than 1mm, and thickness is less than 1mm.
4. liquid metal cell device according to claim 1 and 2, it is characterized in that: the integral thickness of described electrolyte (2) is 1 ~ 3cm, electrolyte (2) is (1.5 ~ 2.5) by the upper and lower two-part Thickness Ratio that metal mesh opening separator (8) is separated into: 1.
5. liquid metal cell device according to claim 1 and 2, is characterized in that: the distance between the edge of described metal polyporous material (4) and the sidewall of battery container (1) is 8 ~ 15mm.
6. liquid metal cell device according to claim 1 and 2, it is characterized in that: the material of described metal polyporous material (4) is nickel, zirconium, titanium or its alloy, the average pore diameter of metal polyporous material (4) is less than 1mm, and porosity is 70 ~ 85%.
7. liquid metal cell device according to claim 1 and 2, is characterized in that: the material of described sealed insulation ceramic member (6) is aluminium oxide or zirconia.
8. liquid metal cell device according to claim 1 and 2, is characterized in that: the material of described battery container (1) is stainless steel or titanium alloy, and the shape of battery container (1) is square.
9. liquid metal cell device according to claim 1 and 2, is characterized in that: the material of described metal perforated plate (5) is stainless steel or titanium alloy;
The material of described metal electric current leading-off rods (7) is stainless steel or titanium alloy, and diameter is 1 ~ 2cm.
10. the assembly method of the liquid metal cell device in claim 1-9 described in any one, is characterized in that, comprise the following steps:
1) battery container (1) is made up of metal top cover with holes, metal tube and metal end, is welded in metal tube, then metal end is welded on metal mesh opening separator (8) bottom of metal tube, obtains battery compartment;
2) metal perforated plate (5) is fixed on metal polyporous material (4), then metal electric current leading-off rods (7) is fixed on metal perforated plate (5), composition current collector; Then on the hole of metal top cover, install sealed insulation ceramic member (6), by sealed insulation ceramic member (6), the top of metal electric current leading-off rods (7) and metal top cover are fastenedly connected;
3) negative material is heated to fusing, utilize the metal polyporous material (4) of current collector and the wettability of negative material, current collector is made to absorb liquid negative material, cooling after absorption completes, then successively positive electrode (3) and electrolyte (2) are placed in battery compartment, electrolyte (2) is separated into upper and lower two parts by metal mesh opening separator (8), then in battery compartment, inert gas is filled with, again the metal top cover be fastenedly connected with current collector is welded on battery compartment, be warming up to operating temperature and obtain full rechargeable battery,
Or at room temperature, successively positive electrode (3), negative material and electrolyte (2) are placed in battery compartment, electrolyte (2) is separated into upper and lower two parts by metal mesh opening separator (8), then in battery compartment, inert gas is filled with, again the cell cover be fastenedly connected with current collector is welded on battery compartment, is warming up to operating temperature and obtains full discharge battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410350077.1A CN104112865B (en) | 2014-07-22 | 2014-07-22 | A kind of liquid metal cell device and assembly method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410350077.1A CN104112865B (en) | 2014-07-22 | 2014-07-22 | A kind of liquid metal cell device and assembly method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104112865A CN104112865A (en) | 2014-10-22 |
| CN104112865B true CN104112865B (en) | 2015-08-05 |
Family
ID=51709575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410350077.1A Active CN104112865B (en) | 2014-07-22 | 2014-07-22 | A kind of liquid metal cell device and assembly method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104112865B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104505526B (en) * | 2014-12-15 | 2016-08-24 | 西安交通大学 | A kind of liquid metal cell and liquid metal cell multikilowatt module |
| CN105006601A (en) * | 2015-08-12 | 2015-10-28 | 王建平 | Liquid metal battery |
| CN105322240B (en) * | 2015-10-21 | 2017-10-13 | 中国科学院理化技术研究所 | Liquid metal flexible battery and preparation method thereof |
| CN106785105A (en) * | 2016-12-23 | 2017-05-31 | 东莞威胜储能技术有限公司 | A kind of liquid metal cell and its sealed insulation device |
| CN106532145A (en) * | 2016-12-23 | 2017-03-22 | 东莞威胜储能技术有限公司 | Liquid metal battery |
| CN106972174B (en) * | 2017-04-14 | 2019-06-28 | 华中科技大学 | A kind of double-deck negative current collector and preparation method thereof for liquid metal cell |
| CN107482209B (en) * | 2017-07-17 | 2020-10-16 | 华中科技大学 | Positive electrode material for liquid and semi-liquid metal batteries |
| CN107768680B (en) * | 2017-10-09 | 2020-09-01 | 中国西电电气股份有限公司 | Liquid metal battery negative current collector structure and assembling method thereof |
| CN110212255B (en) * | 2019-06-03 | 2021-06-08 | 西安西电电气研究院有限责任公司 | Liquid battery and preparation method thereof |
| CN111063909B (en) * | 2019-12-23 | 2021-05-25 | 北京科技大学 | Positive electrode stabilizing device for liquid metal battery |
| CN113745492B (en) * | 2021-08-26 | 2022-12-30 | 西安交通大学 | Liquid metal battery with prefabricated multi-pore structure positive electrode and preparation method thereof |
| CN114204139A (en) * | 2021-11-18 | 2022-03-18 | 清华大学 | Liquid metal battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8268471B2 (en) * | 2006-08-15 | 2012-09-18 | Massachusetts Institute Of Technology | High-amperage energy storage device with liquid metal negative electrode and methods |
| US9153803B2 (en) * | 2012-07-13 | 2015-10-06 | Massachusetts Institute Of Technology | High temperature sealed electrochemical cell |
| US9312522B2 (en) * | 2012-10-18 | 2016-04-12 | Ambri Inc. | Electrochemical energy storage devices |
| CN103715466A (en) * | 2013-12-11 | 2014-04-09 | 中国铝业股份有限公司 | Molten salt battery electrolyte |
-
2014
- 2014-07-22 CN CN201410350077.1A patent/CN104112865B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104112865A (en) | 2014-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104112865B (en) | A kind of liquid metal cell device and assembly method thereof | |
| CN104124459B (en) | A kind of square liquid metal cell device and assembly method thereof | |
| CN107403887B (en) | A kind of liquid metal cell device and its assembly method | |
| KR101822217B1 (en) | Molten salt battery | |
| CN103259004B (en) | Anode material for liquid-state and semi-liquid-state metal energy-storing batteries | |
| CN103280604B (en) | Liquid energy storage battery monomer structure with floating body electrolytes | |
| CN106654072B (en) | A kind of high-temperature fusant cell apparatus and its preparation process | |
| CN204289603U (en) | A kind of liquid metal cell device | |
| KR20160077063A (en) | Self healing liquid/solid state battery | |
| CN204230347U (en) | A kind of liquid metal cell device | |
| CN106972122B (en) | A kind of elevated-temperature seal electrode and preparation method thereof | |
| CN104505526A (en) | Liquid metal battery and KW-scale module of liquid metal battery | |
| CN110429350A (en) | A kind of reusable liquid metal cell device | |
| CN102780049B (en) | High-capacity sodium-nickel-chloride unit flat plate battery and battery pack thereof | |
| CN209843832U (en) | Liquid metal battery | |
| CN110148779B (en) | Application of LiI-KI eutectic salt in low-temperature liquid molten salt lithium battery, low-temperature liquid molten salt lithium battery and preparation method | |
| CN107394282B (en) | A kind of liquid metal cell and its packaging technology | |
| CN109841910A (en) | A kind of liquid metal cell | |
| CN113193179A (en) | Liquid metal battery and preparation method thereof | |
| CN106785105A (en) | A kind of liquid metal cell and its sealed insulation device | |
| CN104124444B (en) | A kind of positive electrode for liquid-solid metal battery | |
| KR20160060693A (en) | Intermediate temperature sodium-metal halide battery | |
| CN206497961U (en) | A kind of liquid metal cell and its sealed insulation device | |
| CN110620271A (en) | Low-temperature liquid and semi-liquid metal battery | |
| CN205882100U (en) | Monomer horizontal battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20141022 Assignee: XI'AN NEW BATTERY TECHNOLOGY CO., LTD. Assignor: Xi'an Jiaotong University Contract record no.: 2015610000102 Denomination of invention: Liquid metal battery device and assembly method thereof Granted publication date: 20150805 License type: Exclusive License Record date: 20151204 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |