CN106252747B - A kind of shell structure and preparation method thereof for liquid metal cell - Google Patents
A kind of shell structure and preparation method thereof for liquid metal cell Download PDFInfo
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- CN106252747B CN106252747B CN201610785391.1A CN201610785391A CN106252747B CN 106252747 B CN106252747 B CN 106252747B CN 201610785391 A CN201610785391 A CN 201610785391A CN 106252747 B CN106252747 B CN 106252747B
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- ceramic tube
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
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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
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- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Secondary Cells (AREA)
Abstract
The shell structure and preparation method thereof that the invention discloses a kind of for liquid metal cell, shell structure includes ceramic tube, as positive metab and as the casting coping of cathode, and the both ends of ceramic tube connect the battery case structure to form sealing with metab and casting coping respectively.The present invention solves the technical issues of chemical compatibility between the sealing of liquid metal cell shell, the insulation of positive and negative interpolar, shell and battery active material and physical and chemical stability in battery storing and temperature range of operation.
Description
Technical field
The invention belongs to liquid metal cell technical field, in particular to a kind of shell structure for liquid metal cell
And preparation process.
Background technique
Currently, China's power grid face renewable energy access accounting constantly expands, NETWORK STRUCTURE PRESERVING POWER SYSTEM increasingly complexity, power grid
Load peak-valley difference such as continues to increase at the lot of challenges.And high-quality, self-healing, safe and clean, economic, interaction are China's smart grids
Set target.The especially extensive energy storage technology of energy storage technology consumption renewable energy, improve stability of power system and
Meet power grid peak load shifting demand etc. to play a significant role, thus be the key that construct modern smart grid it is indispensable
Link.Power energy storage technology mainly includes two class of physics energy storage and chemical energy storage.Wherein, physics energy storage mainly includes flywheel storage
Energy, water-storage, compressed-air energy storage, double layer capacitor energy storage and super conductive magnetic storage energy.And chemical energy storage then mainly includes
Pseudo capacitance energy storage and all kinds of battery energy storages.The advantages such as battery energy storage has energy conversion rate high, and mounting condition is low, by
The extensive concern of people is arrived.
Liquid metal cell is the new secondary battery towards power grid grade stored energy application, monomer mainly by anode, cathode,
Electrolyte and battery case composition.Battery cathode is generally the simple substance or alloy of alkali or alkaline earth metal, and anode is generally
Energy and cathode form alloy and have the transition metal simple substance, alloy or other compounds of certain potential difference with cathode.Electrolyte is
Or mixtures thereof inorganic salts corresponding with negative metal.When battery operation, metal electrode and inorganic salt electrolyte are in high temperature
Lower melting is liquid, and according to density variation AUTOMATIC ZONING.When electric discharge, negative metal loses electronics, and is done work by external circuit.
Negative metal ionization after by fused salt move to anode and with cathode metal alloying.When charging, battery executes opposite mistake
Journey.By above-mentioned alloying and removal alloying process, liquid metal cell can complete the storage and release of electric energy, realize with
External energy exchange.
Liquid metal cell needs work at high temperature, the temperature being related to generally in environment temperature~700 DEG C or higher,
So that the active constituent in battery keeps liquid.At normal temperature, liquid metal cell can not work, and reason is electric at this time
The active constituent in pond is that there is not can be carried out the exchange of ion-electron in solid form.Only the temperature of battery improve to
More than its operating temperature it just can be carried out charge and discharge.In temperature changing process, active material is undergone phase transition, and bring is not only
The variation of object phase, while huge volume change can be generated.Therefore, entirety of the liquid metal cell under room temperature and hot conditions
Sealing, keeping active material not reveal, do not become flat is vital crucial technical problem.
Liquid metal cell works at high temperature, and to keep being dielectrically separated between positive and negative electrode layering, could be in its permission
In the case where, charge and discharge are carried out according to the path of regulation, therefore interelectrode insulation becomes crucial technical problem.
In battery storing and operational process, battery case cannot be with inside battery material, internal gas and battery ambient
Gas in environment chemically reacts.This is because, on the one hand, the corrosion that chemical reaction is likely to result in shell occurs, makes
At the leakage of inside battery active material, even jeopardize environment so as to cause battery failure；On the other hand, occur with internal material
Chemical reaction will cause the rotten of inside battery active material, and the decline for being likely to result in battery performance is even failed.Therefore it protects
It is vital for holding physical and chemical stability of the shell in storage and operational process.
New structural design is carried out for liquid metal cell, solves liquid metal cell at ambient and elevated temperatures close
Envelope insulate to keep the physics and chemistry in battery storing and operational process to stablize, and we have proposed new battery structure and sealed insulations
Technology.
Existing sealing technique mainly has compression seal technology and adhesive technology.Conventional compression seal technology passes through metal
Between be directly connected to or realized using the elastic material of air-tightness: it is intermetallic to be directly connected to difficult to realize be tightly connected two
Electrical insulating property between a component；The general thermal stability of the elastic material of air-tightness is poor, the tolerance of such as conventional silica gel sealing material
Temperature is usually no more than 200 DEG C.Bonding technology is generally using high temperature resistant, insulating ceramics as binder, but heat is swollen between ceramics and metal
Swollen coefficients match is poor, thus is difficult to meet the operation needs steady in a long-term of liquid metal cell.
Existing liquid metal cell uses Stainless Steel Shell, cannot directly solve being dielectrically separated from for electrode, need to increase
Insulating layer, structure is complicated.
Summary of the invention
The shell structure and preparation method thereof that the object of the present invention is to provide a kind of for liquid metal cell, solves liquid
Chemical compatibility between the sealing of state metal battery case, the insulation of positive and negative interpolar, shell and battery active material and in electricity
Pond storage and temperature range of operation in physical and chemical stability the technical issues of.
To solve the above problems, the technical scheme adopted by the invention is as follows:
A kind of shell structure for liquid metal cell including ceramic tube, the metab as anode and is used as negative
The casting coping of pole, the both ends of ceramic tube connect the battery case structure to form sealing with metab and casting coping respectively.
The positive electrode current exit of the metab forms groove, and the cathodal current exit of casting coping forms convex
It rises, the size of the protrusion and groove is mutually matched.
Ceramic tube, metab and the casting coping uses cylindrical body or rectangular parallelepiped structure；The groove setting
At the center of metab, the center of casting coping is arranged in protrusion；Ceramic tube, metab and casting coping coaxial arrangement.
When two liquid metal cells connect, the metab electric current exit of any battery is embedded in the gold of another battery
Belong to top cover electric current exit and carry out conduction, both ends battery current is directly led out.
Further include metal transfer component, passes through a metal respectively after the both ends ceramic metallization processing of the ceramic tube
Transition member and metab and casting coping weld.
The both ends of the ceramic tube pass through glass solder and metab and casting coping welds.
The material of the ceramic tube is C700 class aluminium oxide ceramics or βAl2O3 ceramics；Metab and casting coping
Material is stainless steel or copper.
A kind of preparation method of the shell structure for liquid metal cell, comprising the following steps:
1) ceramic tube both ends of the surface carry out ceramic metallization；
2) metal transfer component is welded on the ceramic tube both ends by ceramic metallization, metal transfer component and pottery respectively
Porcelain tube coaxial arrangement；
3) the metal transfer component sealing welding of metab and lower end, metab and ceramic tube are coaxially disposed；
4) after the charging of liquid metal cell active component, by casting coping and upper end metal transfer component sealing welding, gold
Belong to top cover and ceramic tube is coaxially disposed, forms the shell structure for being used for liquid metal cell.
A kind of preparation method of the shell structure for liquid metal cell, comprising the following steps:
1) using glass solder by metab and ceramic tube one end sealing welding, metab is coaxially set with ceramic tube
It sets；
2) after the charging of liquid metal cell active component, using glass solder by battery metal top cover and the ceramic tube other end
It is integrally welded, it is ensured that sealing forms the shell structure for being used for liquid metal cell.
Compared with the existing technology, the invention has the following advantages:
The battery case structure is sealed against each other by ceramic tube, the metab as anode and the casting coping as cathode
It connects and composes, solves the sealing problem of liquid metal cell shell；The exhausted of positive and negative electrode can directly be solved using ceramic tube
Edge isolation does not need to increase the complicated structure such as insulating layer, solves the Insulation Problems of positive and negative interpolar.And the resistance to height of ceramic tube
Temperature is had excellent performance, and operating temperature is able to bear 450 DEG C or more, and charge and discharge cycles are good, the change between shell and battery active material
It learns compatibility and the physical chemistry in battery storing and temperature range of operation is stablized.The structure can simplify liquid metal cell
Shell preparation process, reduce volume, be conducive to the thermal control in operational process, to save processing, space, energy cost.
Further, it is tightly connected between ceramic tube, metab and casting coping by welding procedure, the welding procedure energy
Physical and chemical stability in enough sealings for effectively solving liquid metal cell, positive and negative electrode insulation and battery storing and operational process
Equal crucial technical problems.
Further, the positive electrode current exit of metab forms groove, and the cathodal current exit of casting coping is formed
Protrusion can only need to carry out head and the tail insertion cooperation when the connection of multiple batteries, realize the current lead-through of positive and negative anodes.Reduce existing
Battery connected by conducting wire cabling the step of, battery connection it is simpler.
Preparation method of the invention using welding procedure be tightly connected, welding procedure be ceramic metallization welding procedure or
Welding procedure is carried out with glass solder, has prepared the liquid metal cell that can stablize charge and discharge.
Detailed description of the invention
Fig. 1 is liquid metal cell encapsulation schematic diagram；
Fig. 2 is Fig. 1 along A-A cross-sectional view；
Fig. 3 is ceramic tube schematic diagram；
Fig. 4 is battery metal pedestal (anode) schematic diagram；
Fig. 5 is battery metal top cover (cathode) schematic diagram；
Fig. 6 is metal transfer block diagram；
Fig. 7 is battery charging and discharging curve synoptic diagram.
Wherein: 1, ceramic tube；2, metab；3, casting coping；4, metal transfer component；5, raised；6, groove.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, respectively with apparatus structure and method, in the embodiment of the present invention
Technical solution is clearly and completely described.
First part: apparatus structure
As shown in Figures 1 to 6, a kind of liquid metal cell of the present invention contains ceramic tube 1,2 and of metab in shell mechanism
Casting coping 3.Metab 2 and casting coping 3 and ceramic tube 1 are coaxially disposed.The both ends of ceramic tube 1 respectively with metab 2
It is welded with casting coping 3.The electric current exit of metab 2 forms groove 6, and the electric current exit of casting coping forms convex
5 are played, and groove 6 must match each other with protrusion 5, it can be by the negative of positive and another battery of any battery when two batteries connect
Pole matching, it is ensured that well conducting.
Ceramic tube 1, metab 2, casting coping 3 can use cylindrical body or rectangular parallelepiped structure, but need to be consistent
And there is matching.
Wherein, ceramic matrix material is selected from C700 class aluminium oxide ceramics (being detailed in GB/T 8411.3-2009), βAl2O3 is made pottery
Porcelain and other refractory ceramicses etc..
The high temperature resistants high-conductive metal such as metab 2 and 3 material of casting coping selection stainless steel, copper.
Using battery structure of the invention, the positive and negative interpolar of battery has the ceramic tube with insulating properties to be separated by, and realizes just
The good insulation of cathode.Using ceramic metalizing process, one layer of metallic film is firmly adhered to by ceramic surface, makes to metallize
Ceramic surface afterwards can obtain the abundant wetting of solder, to realize that ceramics are reliably connected with intermetallic, reach sealing, resistance to
High temperature, etch-proof function.
Second part: preparation method
Welding procedure is ceramic metallization welding procedure or is welded with glass solder in preparation method of the invention
Technique.It is specific as follows:
Method one: please referring to Fig. 1-6, and liquid metal cell provided by the invention carries out component processing as illustrated, uses
Ceramic metalizing process welds together battery plus-negative plate with ceramic tube respectively；Firstly, by Fig. 3 cell ceramic tube both ends of the surface into
Row ceramic metallization；Fig. 6 metal transfer component 4 is welded on Fig. 3 battery for having carried out ceramic metallization by second step respectively
Ceramic tube both ends, it is coaxial with the cell ceramic tube of Fig. 3；Third step, by Fig. 4 battery metal pedestal (anode) and bottom metal transition
Component welds together, coaxial with Fig. 3 cell ceramic tube；4th step charges according to liquid metal cell active component；Finally,
Sealing welding at Fig. 5 battery metal top cover and upper end metal transfer component contact is integral, it is coaxial with Fig. 3 cell ceramic tube.
Complete the encapsulation of Fig. 1 liquid metal cell.
According to material therefor difference, comprising: molybdenum manganese method, gold-plated method, copper-plating method, tin plating method, LAP method (metal-plated after laser)
Etc. a variety of ceramic metalizing process；According to processing method difference, further comprise: thick film and cofiring method.
Method two: please referring to Fig. 1-6, and liquid metal cell provided by the invention carries out component processing as illustrated, uses
Glass solder welds together the positive and negative anodes of battery with ceramic cartridge respectively；Firstly, using glass solder by Fig. 4 battery metal
Pedestal (anode) and one end of Fig. 3 cell ceramic tube weld together, coaxial with Fig. 3 cell ceramic tube, it is ensured that sealing；Second
Step charges according to liquid metal cell active component；Third step, using glass solder by Fig. 5 battery metal top cover and Fig. 3 battery
The ceramic tube other end is integrally welded, it is ensured that sealing.Complete the encapsulation of Fig. 1 liquid metal cell.
It is welded with glass solder, which can be realized effective welding of ceramics with metal, can after welding
Sealing is kept in room temperature to operating temperature range, physicochemical property is stablized, and can be resistant to ceramics and intermetallic thermal stress, and keep
With the chemical compatibility between inside battery active material.
Part III:
Using battery structure of the present invention and welding procedure, performance is as shown in fig. 7, charge and discharge can be stablized by having prepared
The liquid metal cell of electricity.It can satisfy the parameters index of liquid metals battery.
Part IV:
It enumerates various embodiments and is shown in Table 1:
Table 1
As can be seen from the above table, the battery case structure that the present invention is prepared by two methods respectively, favorable sealing property,
Operating temperature can achieve 450 DEG C, and charging, discharge cycles are smooth.Meet indices requirement.Solve shell and battery-active
The technical issues of chemical compatibility of storeroom and physical and chemical stability in battery storing and temperature range of operation.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (7)
1. a kind of shell structure for liquid metal cell, it is characterised in that: including ceramic tube (1), the metal as anode
Pedestal (2) and casting coping (3) as cathode, the both ends of ceramic tube (1) respectively with metab (2) and casting coping (3)
Welding forms the battery case structure of sealing；The positive electrode current exit of the metab (2) forms groove (6), metal
The cathodal current exit of top cover (3) is formed raised (5), and the size of the protrusion (5) and groove (6) is mutually matched；It is described
The both ends of ceramic tube (1) pass through glass solder and metab (2) and casting coping (3) welding.
2. a kind of shell structure for liquid metal cell according to claim 1, it is characterised in that: the ceramics
It manages (1), metab (2) and casting coping (3) and uses cylindrical body or rectangular parallelepiped structure；The groove (6) is arranged in metal
The center of pedestal (2), center of raised (5) setting in casting coping (3)；Ceramic tube (1), metab (2) and casting coping
(3) it is coaxially disposed.
3. a kind of shell structure for liquid metal cell according to claim 2, it is characterised in that: when two liquid
When metal battery connects, the positive electrode current exit of the metab (2) of any battery is embedded in the casting coping (3) of another battery
Cathodal current exit carry out conductive, both ends battery current is directly led out.
4. a kind of shell structure for liquid metal cell according to claim 1 or 2 or 3, it is characterised in that: also wrap
It includes metal transfer component (4), passes through a metal transfer portion respectively after the both ends ceramic metallization processing of the ceramic tube (1)
Part (4) and metab (2) and casting coping (3) weld.
5. a kind of shell structure for liquid metal cell according to claim 1 or 2 or 3, it is characterised in that: described
Ceramic tube (1) material be C700 class aluminium oxide ceramics or βAl2O3 ceramics；Metab (2) and casting coping (3) material
For stainless steel or copper.
6. a kind of preparation method of the shell structure for liquid metal cell, which comprises the following steps:
1) ceramic tube (1) both ends of the surface carry out ceramic metallization；
2) metal transfer component (4) is welded on ceramic tube (1) both ends by ceramic metallization, metal transfer component respectively
(4) it is coaxially disposed with ceramic tube (1)；
3) by metal transfer component (4) sealing welding of metab (2) and lower end, metab (2) and ceramic tube (1) are coaxial
Setting；
4) after the charging of liquid metal cell active component, by casting coping (3) and upper end metal transfer component (4) sealing welding,
Casting coping (3) and ceramic tube (1) are coaxially disposed, and form the shell structure for being used for liquid metal cell.
7. a kind of preparation method of the shell structure for liquid metal cell, which comprises the following steps:
1) using glass solder by metab (2) and ceramic tube (1) one end sealing welding, metab (2) and ceramic tube (1)
Coaxial arrangement；
2) using glass solder that battery metal top cover (3) and ceramic tube (1) is another after the charging of liquid metal cell active component
It holds integrally welded, it is ensured that sealing forms the shell structure for being used for liquid metal cell.
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| CN201610785391.1A CN106252747B (en) | 2016-08-30 | 2016-08-30 | A kind of shell structure and preparation method thereof for liquid metal cell |
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| CN201610785391.1A CN106252747B (en) | 2016-08-30 | 2016-08-30 | A kind of shell structure and preparation method thereof for liquid metal cell |
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| CN106252747B true CN106252747B (en) | 2018-12-07 |
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| CN109449318A (en) * | 2018-10-15 | 2019-03-08 | 大连中比动力电池有限公司 | A kind of cylindrical battery configuration and preparation method of non-metal shell |
| CN113707952A (en) * | 2021-08-02 | 2021-11-26 | 大连理工大学 | Circular-section liquid metal battery with grid device for inhibiting fluid instability |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103259004A (en) * | 2013-04-16 | 2013-08-21 | 华中科技大学 | Anode material for liquid-state and semi-liquid-state metal energy-storing batteries |
| CN104124459A (en) * | 2014-07-22 | 2014-10-29 | 西安交通大学 | Square liquid metal battery device and assembling method thereof |
| CN204289603U (en) * | 2014-12-12 | 2015-04-22 | 芶富均 | A kind of liquid metal cell device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2013326877B2 (en) * | 2012-10-05 | 2017-07-27 | Massachusetts Institute Of Technology | Low-temperature liquid metal batteries for grid-scaled storage |
| WO2015042295A1 (en) * | 2013-09-18 | 2015-03-26 | Ambri Inc. | Unified structural and electrical interconnections for high temperature batteries |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103259004A (en) * | 2013-04-16 | 2013-08-21 | 华中科技大学 | Anode material for liquid-state and semi-liquid-state metal energy-storing batteries |
| CN104124459A (en) * | 2014-07-22 | 2014-10-29 | 西安交通大学 | Square liquid metal battery device and assembling method thereof |
| CN204289603U (en) * | 2014-12-12 | 2015-04-22 | 芶富均 | A kind of liquid metal cell device |
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Effective date of registration: 20210909 Address after: 710077 No. 18 West Second Ring Road, Shaanxi, Xi'an Patentee after: XI'AN HIGH VOLTAGE APPARATUS RESEARCH INSTITUTE Co.,Ltd. Address before: 710075 Shaanxi city of Xi'an Province Tang Hing Road No. 7 Patentee before: CHINA XD ELECTRIC Co.,Ltd. |
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Address after: 710077 No. 18 West Second Ring Road, Shaanxi, Xi'an Patentee after: Xi'an High Voltage Electrical Apparatus Research Institute Co.,Ltd. Address before: 710077 No. 18 West Second Ring Road, Shaanxi, Xi'an Patentee before: XI'AN HIGH VOLTAGE APPARATUS RESEARCH INSTITUTE Co.,Ltd. |