CN104701025B - A kind of high-power annular energy-storage battery - Google Patents
A kind of high-power annular energy-storage battery Download PDFInfo
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- CN104701025B CN104701025B CN201510079965.9A CN201510079965A CN104701025B CN 104701025 B CN104701025 B CN 104701025B CN 201510079965 A CN201510079965 A CN 201510079965A CN 104701025 B CN104701025 B CN 104701025B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
A kind of high-power annular energy-storage battery, if including the annular wall being made up of solid electrolyte dried layer coaxial package together, the two ends of annular wall are separately fixed on the cup dolly and circular upper cover of insulation, if all annular walls surround the airtight cavity that dried layer is set in together jointly with cup dolly and circular upper cover, interval is filled with positive electrode or negative material in adjacent airtight cavity, and positive and negative electrode material is liquid during battery operation；Positive and negative electrode electric current extraction pole is drawn respectively from airtight cavity bottom and assembles to form battery positive and negative electrode respectively.The battery that the present invention is provided has very big electrochemical reaction area and current flowing area, with excellent electronic conduction, it can reach sufficiently large current density, it ensure that sufficiently high charge-discharge velocity and power, and it is simple in construction, with low cost, dimensional parameters can be determined by different capacity requirements, it is easy to carry out popularization, can meet different capacity and space requirement.
Description
Technical field
The invention belongs to energy storage field, and in particular to be a kind of high-power annular energy-storage battery.
Background technology
With the rapid lifting of China's economic total volume, energy form is also increasingly severeer, how effectively to make good use of existing
Energy production capacity have become the important content of Energy restructuring.Building energetically under the background of intelligent grid, lifting electric energy
Quality is extremely urgent, and as an important indicator of the quality of power supply, the stability of mains frequency is related to the side of national product
Aspect face, more represents the adjustment capability that power network resists load impact.When there is significantly load variations, in order to stablize power network frequency
Rate, inputs to power network within the shortest time or absorbs big energy to offset big load fluctuation from power network, so that power network
Frequency stabilization in a controllable scope, that is, realize the frequency-modulating process of power network.During this, the most key be how
Export in the most short time or absorb substantial amounts of energy, this needs energy storage device powerful enough, usually flywheel energy storage
Or ultracapacitor.
On the other hand, with the fields such as military affairs, space flight high-new armament equipment appearance, such as magnetic artillery, it is desirable to have super
Level capacitor etc. can discharge the energy storage device of big energy in a short time as support.
However, limitation of the flywheel energy storage due to its physics energy storage mode, stored energy capacitance very little, energy loss can not be ignored；
Ultracapacitor etc. is high due to there is technology barriers, manufacturing cost.Then, using based on chemically reacting, scale easily opens up
Open up, respond rapid novel battery as the advantage of energy storage device it is clear that this needs the charge-discharge electric power of novel battery remote
Super existing all batteries, substantial amounts of energy can be discharged in a short period of time.On the other hand, from feature, this
Expansible, the with low cost ultracapacitor of another capacity can be can be regarded as completely by planting novel battery.But it yet there are no
There is the relevant report of the energy-storage battery of this super high power based on chemical reaction.
The content of the invention
It is an object of the invention to provide the high-power annular energy-storage battery of one kind, the battery has great charge and discharge electric work
Rate, can be used as ultracapacitor.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of high-power annular energy-storage battery, if including the ring being made up of solid electrolyte dried layer coaxial package together
Shape wall, the bottom of annular wall is fixed on cup dolly, and the top of annular wall is fixed on circular upper cover, cup dolly and circle
Upper lid is made by isolation material；If all annular walls surround what dried layer was set in together jointly with cup dolly and circular upper cover
Positive electrode or negative material are filled with airtight cavity, all airtight cavities, wherein the closed chamber filled with positive electrode
Body is positive electrode chamber, and the airtight cavity filled with negative material is negative material chamber, and positive electrode chamber and negative material chamber
It is spaced to set；The bottom of positive electrode chamber is provided with positive electrode current extraction pole, and positive electrode current extraction pole is stretched out outside cup dolly
And the integrated anode of meeting, the bottom of negative material chamber is provided with cathodal current extraction pole, cathodal current extraction pole stretching circular base
Seat is outer and can integrated GND；Wherein positive electrode be inert metal, negative material be active alkali metal or alkaline-earth metal,
Positive electrode and negative material are liquid under the running temperature of battery.
Described positive electrode is one kind or any several in Al, Zn, Ga, Cd, In, Sn, Sb, Te, Hg, Ti, Pb, Bi
Mixture；Negative material is one kind in Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba or any several mixture；Solid electricity
Solve good conductor of the matter for the metal cation of negative material.
Described positive electrode chamber and the filling rate of negative material chamber are respectively less than 50%.
The thickness of described annular wall is 3~5mm.
Described positive electrode current extraction pole and cathodal current extraction pole are stainless steel substrates.
The diameter of outermost annular wall is identical with the diameter of cup dolly and circular upper cover.
The height of the battery is less than 1 with the ratio of its diameter.
Relative to prior art, beneficial effects of the present invention are：
The invention provides a kind of charge-discharge electric power greatly, can be used as the high-power annular energy-storage battery of ultracapacitor,
The frequency modulation and military space technology of power network can be applied to.The battery designs for multi-layer annular, with very unique battery knot
Structure, in addition to outermost annular wall, the positive electrode and negative material of battery is distributed with the both sides of remaining annular wall respectively, because
This these annular wall (solid electrolyte) is all the reaction surface of electrochemical reaction, so the battery has sufficiently large electrochemistry anti-
Area is answered, this make it that the area of current flowing is very big.And electrode reaction is carried out at high temperature, both positive and negative polarity is liquid during operation
Metal, with very excellent electronic conduction, can reach sufficiently large current density, therefore the charge-discharge electric power of the battery can
With very big.The other battery can be determined many set dimensional parameters being distributed in proportion by different capacity requirements, it is easy to be carried out
Popularization, can meet different capacity and space requirement.The battery that the present invention is provided can either have larger current density again
There can be enough current flowing areas, it is ensured that sufficiently high charge-discharge velocity and power, and it is simple in construction, with low cost,
Used particularly suitable for the high energy weapon such as power grid frequency modulation and magnetic artillery.
Further, the filling of positive electrode chamber and negative material chamber in the high-power annular energy-storage battery that the present invention is provided
Rate is respectively less than 50%, and ensure that has enough spaces to accommodate life after positive and negative electrode material has reacted in positive and negative electrode materials chamber
Into product, it is to avoid due to caused in course of reaction material volume change caused by annular wall, cup dolly and circle
The extruding of upper lid, so that the battery capacity loss that damaged caused positive and negative electrode material is mutually mixed and brought after annular wall stress is avoided,
Battery generation bulge or the caused battery of positive and negative electrode material leakage is avoided to use safety and service life problem simultaneously.
Further, in the high-power annular energy-storage battery that the present invention is provided, ring is made on the premise of support strength is ensured
The thickness of shape wall is as small as possible, preferably 3~5mm, so as to ensure good ion conduction, during reduction battery operation
Polarization loss.
Brief description of the drawings
The structural representation for the annular energy-storage battery (Na ‖ Bi) that Fig. 1 provides for the present invention；
The schematic cross section for the annular energy-storage battery (Na ‖ Bi) that Fig. 2 provides for the present invention；
Fig. 3 is the alloy phase diagram of Na-Bi reaction systems；
The runnability curve map for the 3kW annular energy-storage batteries (Na ‖ Bi) that Fig. 4 provides for the present invention.
Embodiment
The present invention is described in further details below in conjunction with the accompanying drawings.
Participate in Fig. 1 and Fig. 2, the high-power annular energy-storage battery that provides of the present invention, if including dried layer coaxial package together
The annular wall 2 being made up of solid electrolyte, the bottom of annular wall 2 is fixed on cup dolly 3, and the top of annular wall 2 is fixed
On circular upper cover 1, the diameter of outermost annular wall 2 is identical with the diameter of cup dolly 3 and circular upper cover 1.Ensureing branch
Make the thickness of annular wall 2 as small as possible on the premise of support intensity, preferably 3~5mm.Cup dolly 3 and circular upper cover 1 are by exhausted
Edge material is made.Adjacent two layers annular wall 2 surrounds the airtight cavity of annular, the ring of innermost layer with cup dolly 3 and circular upper cover 1
Shape wall 2 is surrounded in the airtight cavity of cylinder, airtight cavity with cup dolly 3 and circular upper cover 1 filled with positive electrode or negative
Pole material, wherein the airtight cavity filled with positive electrode is positive electrode chamber 8, the airtight cavity filled with negative material is negative
Pole materials chamber 9, and positive electrode chamber 8 and negative material chamber 9 be arranged at intervals；The filling rate of positive electrode chamber 8 and negative material chamber 9
Less than 50%.The bottom of positive electrode chamber 8 is provided with positive electrode current extraction pole 4, and positive electrode current extraction pole 4 is stretched out outside cup dolly 3
And anode 5 is accumulated, the bottom of negative material chamber 9 is provided with cathodal current extraction pole 6, and cathodal current extraction pole 6 stretches out circle
Shape base 3 is outer and accumulates GND 7.Positive electrode current extraction pole 4 and cathodal current extraction pole 6 are stainless steel thin slice.Should
The height (height of annular wall 2) of battery is less than 1, i.e. annular wall 2 with the ratio of its diameter (diameter of outermost layer annular wall 2)
Highly it is less than the diameter of outermost layer annular wall 2.
The basic electrochemical reaction of the battery is the process of a kind of alloying and de- alloying, and positive electrode is inertia
One kind or any several mixture in metal, such as Al, Zn, Ga, Cd, In, Sn, Sb, Te, Hg, Ti, Pb, Bi；Negative material
For active alkali metal or alkaline-earth metal, one kind or any several mixing in such as Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba
Thing；Solid electrolyte is the good conductor of the metal cation of negative material, usually corresponds to the solid electrolyte of cation.Electrode
Reaction is carried out at high temperature, and positive electrode and negative material are liquid under the running temperature of battery, i.e. liquid metal, are had
Very excellent electronic conduction, it is allowed to have sufficiently large current density, by taking liquid metal lithium as an example, its electric current that can be reached
Density is up to 1.2A/cm2。
The battery designs for multi-layer circular, with sufficiently large electrochemical reaction area.Due to its unique structure, electrification
Response area is very big, and this make it that the area of current flowing is very big, it is contemplated that the high current density that electrode material can be reached,
The charge-discharge electric power of the battery can be very big.And the design of this cell apparatus can be determined to divide in proportion by different capacity requirements
Many set dimensional parameters of cloth, it is easy to carry out popularization, can meet different capacity and space requirement.
For the ease of being better understood from the present invention, below by taking Na ‖ Bi batteries as an example, the specific implementation of the present invention is provided
Example.
As shown in Figure 1, 2, the Na ‖ Bi batteries are annular Multi-layer design, have different-diameter by what solid electrolyte was constituted
, the annular wall 2 (being highly 20cm~50cm) of certain thickness and height is distributed in one piece of cup dolly 3 with one heart (diameter exists
30cm~60cm, identical with outermost annular wall outer circumference diameter) on, this cup dolly 3 is isolation material, with 5~10 not
With the fit sealing of annular wall 2 of diameter, generally it is sintered together with the material of ceramics, or realized in the gluing mode that insulate.Ring
The top of shape wall 2 and the fit sealing of circular upper cover 1, circular upper cover 1 are isolation material, are generally sintered in one with the material of ceramics
Rise, or realized in the gluing mode that insulate.Interval is full of positive electrode or negative material between two layers adjacent of annular wall, positive and negative
Positive and negative electrode electric current extraction pole is distributed with every cross-distribution, and in bottom in pole storeroom, usually stablizes erosion-resisting stainless steel
Thin slice, tightening seal is connected on cup dolly 3, and draws congregation, the as both positive and negative polarity of battery by both positive and negative polarity species.
The negative material of the battery is Na metal dusts, and positive electrode is Bi metal dusts, and solid electrolyte is sodium ion
Corresponding βAl2O3.Temperature that the running temperature of the battery is needed by electrode reaction (both positive and negative polarity electrode material need to be completely melt for
Liquid) and the optimum working temperature (ensure high ionic mobility) of the corresponding solid electrolyte of negative material cation it is common certainly
It is fixed.Such as Na-Bi reaction systems, Fig. 3 is seen.From phasor, when temperature is higher than 444 DEG C, Na and Bi react generation solid phase completely
Na3Bi, reaction equation is 3Na+Bi → Na3Bi；When temperature is higher than 271 DEG C (Bi fusing point) less than 444 DEG C, Na and Bi are completely anti-
Solid phase NaBi should be generated, reaction equation is Na+Bi → NaBi.In view of βAl2O3 solid electrolyte between 300 DEG C~350 DEG C
With optimal sodium ion conduction, on the other hand, higher than 444 DEG C at a high temperature of can bring under many hot environments sealing and absolutely
The problem of edge, therefore the running temperature of this cell apparatus is set to 300 DEG C~350 DEG C, electrochemical reaction is Na+Bi → NaBi.
In addition, the outer circumference diameter distribution of each annular wall 2 being distributed with one heart and height determine gap between them (just
Pole materials chamber and negative material chamber) volume, interstitial volume is the key parameter for the loading for determining positive and negative pole material again, is being ensured
Solid electrolyte thickness is small as far as possible on the premise of physical support intensity.Therefore the thickness of annular wall is preferably 3~5mm, with
Ensure good ion conduction, polarization loss during reduction battery operation.Such as Na-Bi reaction systems, it has been determined that both positive and negative polarity material
It is 1 to expect the mol ratio reacted completely:1, ideally, negative material sodium is completely migrating to where positive electrode Bi after reaction
In gap, and Bi generation NaBi solid phase alloys, now need ensure positive electrode chamber volume be large enough to hold pure Bi volume and
Maximum among NaBi volume, the volume of negative material chamber is large enough to hold pure Na volume.For certain interstitial volume,
After the annular wall height of battery is determined, the outer circumference diameter distribution of each annular wall being distributed with one heart can determine that, general electricity
The Ratio control of pond height and cell diameter is in the range of less than 1.Then, after certain battery capacity parameters are determined,
The specific dimensional parameters of battery can be determined by the consumption of electrode material.
In order to verify the specific practical performance of this large power energy storage battery, it has been made based on Na-Bi reaction systems
Cell apparatus, and put into operation.Cell diameter is 200mm~300mm, a height of 150mm~200mm；Output-current rating 200A,
Capacity 200Ah~400Ah, output voltage 0.6V, rated output power has reached 120W, is conventional monomer energy-storage battery output work
Tens times of rate arrive hundred times.As shown in figure 4, this large power energy storage battery is being undergone close to after 500 charge and discharge cycles still
Energy efficiency be higher than 75%, and discharge and recharge mean power almost without it is any decay stably runnability, this shows this
Battery has highly stable cycle performance while high-power discharge and recharge feature is possessed, and has very high cycle life.
Claims (4)
1. a kind of high-power annular energy-storage battery, it is characterised in that：If including dried layer coaxial package together by solid electrolytic
The annular wall (2) that matter is made, the bottom of annular wall (2) is fixed on cup dolly (3), and the top of annular wall (2) is fixed on circle
Covered in shape on (1), cup dolly (3) and circular upper cover (1) are made by isolation material；All annular walls (2) and cup dolly
(3) positive pole and circular upper cover (1) if surround the airtight cavity that dried layer is set in together jointly, is filled with all airtight cavities
Material or negative material, wherein the airtight cavity filled with positive electrode is positive electrode chamber (8), filled with the close of negative material
Closed chamber body be negative material chamber (9), and positive electrode chamber (8) and negative material chamber (9) it is spaced setting；Positive electrode chamber
(8) bottom is provided with positive electrode current extraction pole (4), and positive electrode current extraction pole (4) stretches out cup dolly (3) outside and can integrated battery
Positive pole (5), the bottom of negative material chamber (9) is provided with cathodal current extraction pole (6), and cathodal current extraction pole (6) stretches out circular base
Seat (3) is outside and can integrated GND (7)；Wherein positive electrode is inert metal, and negative material is active alkali metal or alkali
Earth metal, positive electrode and negative material are liquid under the running temperature of battery；Positive electrode chamber (8) and negative material chamber
(9) filling rate is respectively less than 50%, and the thickness of annular wall (2) is 3~5mm；The height of the battery is less than with the ratio of its diameter
1。
2. high-power annular energy-storage battery according to claim 1, it is characterised in that：Described positive electrode be Al, Zn,
One kind or any several mixture in Ga, Cd, In, Sn, Sb, Te, Hg, Ti, Pb, Bi；Negative material be Li, Na, K, Rb,
One kind or any several mixture in Cs, Mg, Ca, Sr, Ba；Solid electrolyte is good for the metal cation of negative material
Conductor.
3. high-power annular energy-storage battery according to claim 1, it is characterised in that：Described positive electrode current extraction pole
And cathodal current extraction pole (6) is stainless steel substrates (4).
4. high-power annular energy-storage battery according to claim 1, it is characterised in that：Outermost annular wall (2) it is straight
Footpath is identical with the diameter of cup dolly (3) and circular upper cover (1).
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| CN201510079965.9A CN104701025B (en) | 2015-02-13 | 2015-02-13 | A kind of high-power annular energy-storage battery |
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| CN201510079965.9A CN104701025B (en) | 2015-02-13 | 2015-02-13 | A kind of high-power annular energy-storage battery |
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| CN104701025B true CN104701025B (en) | 2017-08-15 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB794970A (en) * | 1953-12-24 | 1958-05-14 | Corson G & W H | Electric current-producing cell and method of producing current using the same |
| CN202395058U (en) * | 2011-12-16 | 2012-08-22 | 深圳市雄韬电源科技股份有限公司 | Annular battery |
| CN103872007A (en) * | 2012-12-17 | 2014-06-18 | 富士通半导体股份有限公司 | Capacitive element, capacitor array, and a/d converter |
| CN104124459A (en) * | 2014-07-22 | 2014-10-29 | 西安交通大学 | Square liquid metal battery device and assembling method thereof |
-
2015
- 2015-02-13 CN CN201510079965.9A patent/CN104701025B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB794970A (en) * | 1953-12-24 | 1958-05-14 | Corson G & W H | Electric current-producing cell and method of producing current using the same |
| CN202395058U (en) * | 2011-12-16 | 2012-08-22 | 深圳市雄韬电源科技股份有限公司 | Annular battery |
| CN103872007A (en) * | 2012-12-17 | 2014-06-18 | 富士通半导体股份有限公司 | Capacitive element, capacitor array, and a/d converter |
| CN104124459A (en) * | 2014-07-22 | 2014-10-29 | 西安交通大学 | Square liquid metal battery device and assembling method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Self-healing Li-Bi liquid metal battery for grid-scale energy storage;Xiaohui Ning等;《Journal of Power Sources》;20141029;第275卷;第370-376页 * |
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