CN106575786A - Air cathode battery using zinc slurry anode with carbon additives - Google Patents
Air cathode battery using zinc slurry anode with carbon additives Download PDFInfo
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- CN106575786A CN106575786A CN201580045193.5A CN201580045193A CN106575786A CN 106575786 A CN106575786 A CN 106575786A CN 201580045193 A CN201580045193 A CN 201580045193A CN 106575786 A CN106575786 A CN 106575786A
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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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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- 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
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Abstract
An air cathode battery is provided that uses a zinc slurry anode with carbon additives. The battery is made from an air cathode and a zinc slurry anode. The zinc slurry anode includes zinc particles, an alkaline electrolyte, with a complexing agent and carbon additives in the alkaline electrolyte. A water permeable ion-exchange membrane and electrolyte chamber separate the zinc slurry from the air cathode. The carbon additives may, for example, be graphite, carbon fiber, carbon black, or carbon nanoparticles. The proportion of carbon additives to zinc is in the range of 2.5 to 10% by weight. The proportion of alkaline electrolyte in the zinc slurry is in the range of 50 to 80% by volume.
Description
Technical field
This invention relates generally to electrochemical cell, more particularly, to using with carbonaceous additive, chelating agent and auxiliary
Circulation type (flow-through) the air cathode battery of the zinc slurry anode at water source.
Background technology
Flow-through cell has been for extensive energy storage use due to its long circulation life, flexible design and high reliability
Furtherd investigate and developed in way.Battery is a kind of electrochemical appliance, its intermediate ion (for example, metal ion, hydroxyl from
Son, proton etc.) travel to and fro between anode and negative electrode to realize energy stores and conversion.In conventional batteries, including anode material,
The all component of cathode material, barrier film, electrolyte and current collector is encased in the container of volume fixation.It is assembled in battery
Afterwards, its energy and capacity are immutable.Flow-through cell is constituted by the current collector (electrode) that film separates is ion exchanged, its sun
Pole and cathode material are stored in single holding tank.Anode and cathode material by wherein there is electrochemical reaction discharging and
The flow-through cell of storage energy is circulated.Therefore, battery capacity and energy are determined by the following：(1) electrode material (anode electricity
Solution matter and catholyte), the concentration of (2) anodolyte and catholyte, and (3) anodolyte and catholyte
The volume of holding tank.
Air cell is considered flow-through cathode battery, and wherein the oxygen in air is constantly through reactive metal
Electrode and as negative electrode.Electrolyte generally separates negative electrode with metal or metallic compound anode.Zinc is favourable metal, and
It can be in solid phase or in particulate forms realizing flow-through anode.Using the conventional batteries of circulation type zinc particles anode be subjected to for
Avoid the passivation around zinc particles and need the problem of a large amount of electrolyte.Additionally, zinc particles anode needs lasting pumping, and
Support that the viscosity needed for pumping causes low zinc concentration.
If there is the circulation type zinc anode battery using the low viscosity slurry with Treatment with High Concentration Zinc, it will be beneficial.
The content of the invention
It is disclosed herein for by air cathode is combined with inexpensive zinc slurry anode realize with scalable appearance
The zinc-air battery of amount.Slurry anode allows zinc-air battery mechanically to recharge.Zinc-air battery is used in Treatment with High Concentration Zinc
The anode of slurry form, the Treatment with High Concentration Zinc slurry has sufficiently low viscosity and does not solidify after discharge.After discharge, use
The slurry crossed can be replaced by the fresh slurry of pumping in the reservoir from connection so that realize mechanical charge.Slurry anode bag
Containing zinc particles, alkaline solution, chelating agent and carbonaceous additive.Some unique aspects of the battery include improving adding for viscosity
Plus agent (such as graphite or carbon fiber) and the use of chelating agent, make slurry be moved through system and use so as to be replaced with fresh slurry
The mechanism of the slurry (mechanically charge) crossed, and enough water content is kept in the slurry to prevent from being dried such that it is able to make chemistry
Reaction is carried out to the mechanism for completing.In such zinc-air battery, zinc slurry can realize deep discharge (80% with
On) and high-energy-density.Because slurry need not be pumped persistently, battery efficiency is improved.
Therefore it provides using the air cathode battery of the zinc slurry anode with carbonaceous additive.The battery is cloudy by air
Pole and zinc slurry anode are made.Zinc slurry anode includes zinc particles, alkaline electrolyte, has complexation in the alkaline electrolyte
Agent and carbonaceous additive.Electrolyte chamber with alkaline electrolyte is adjacent with air cathode, and water penetration ion exchange membrane is by electricity
Solution matter room separates with zinc slurry.Carbonaceous additive can be, for example, graphite, carbon fiber, white carbon black or carbon nano-particles.Carbonaceous additive pair
The ratio of zinc is in the range of 2.5 weight % to 10 weight %.Ratio of the alkaline electrolyte in zinc slurry in 50 volumes % extremely
In the range of 80 volumes %.
When battery (that is, zinc slurry is fresh) in the charge state, zinc slurry have less than 10 ohm resistance and
Zinc molar concentration more than 15 moles per liter.Under battery charging state, at 25 DEG C, zinc slurry have 10000 to
Viscosity in the range of 1000000 centipoises (cP).
Other details of above-mentioned zinc-air battery are provided below.
Description of the drawings
[Figure 1A] Figure 1A is the partial cross section view of the air cathode battery using the zinc slurry anode with carbonaceous additive,
And detailed view.
[Figure 1B] Figure 1B is the partial cross section view of the air cathode battery using the zinc slurry anode with carbonaceous additive,
And detailed view.
The relation that [Fig. 2A] Fig. 2A describes between slurry parameter.
The relation that [Fig. 2 B] Fig. 2 B describe between slurry parameter.
The relation that [Fig. 2 C] Fig. 2 C describe between slurry parameter.
The variant of [Fig. 3 A] Fig. 3 A depicted example anode collectors/flow channel.
The variant of [Fig. 3 B] Fig. 3 B depicted example anode collectors/flow channel.
The variant of [Fig. 3 C] Fig. 3 C depicted example anode collectors/flow channel.
[Fig. 4] Fig. 4 depicted examples anode chamber and cathode interface.
[Fig. 5] Fig. 5 is the local for describing the gravity feed air cathode battery for using rechargeable zinc slurry anode
Cross-sectional view.
[Fig. 6 A] Fig. 6 A are the cross-sectional view of the variant of the air cathode battery for describing Fig. 5.
The details of [Fig. 6 B] Fig. 6 B depictions 6A.
Specific embodiment
Figure 1A and 1B respectively uses the partial cross-section of the air cathode battery of the zinc slurry anode with carbonaceous additive
Figure, and detailed view.Battery 100 includes air cathode 102 and zinc slurry anode 104.Zinc slurry anode 104 includes current collector
106th, zinc particles 108, alkaline electrolyte 110, have carbonaceous additive 112 and chelating agent 113 in alkaline electrolyte 110.Zinc granule
Son 108, alkaline electrolyte 110, chelating agent 113 and carbonaceous additive 112 form together zinc slurry 105.Generally, zinc particles 108 have
There is the average-size (diameter) 114 in 1 micron to 500 micrometer ranges.It should be noted that：What figure was not drawn to scale.
Or, replacing Zn or in addition to Zn, the particle can be magnesium (Mg), aluminum (Al), ferrum (Fe), copper (Cu) or these metallics
Combination.Electrolyte chamber 115 comprising alkaline electrolyte 117 is adjacent with air cathode 102, and water penetration ion exchange membrane
119 are placed between electrolyte chamber and zinc slurry anode 104.
Carbonaceous additive 112 can be graphite, carbon fiber, white carbon black or carbon nano-particles.However, the carbon of other forms can
It is applicable.Alkaline electrolyte 110 and 117 can be, for example, potassium hydroxide (KOH) or sodium hydroxide (NaOH).It is well known, however, that
Many other alkaline electrolytes can be also applicable.In some aspects, electrolyte can comprising penetrating through IEM 119 in case
Only zinc slurry anode 104 be dried extra (excess) water.Chelating agent 113 can be ethylenediaminetetraacetic acid (EDTA), citric acid
And ammonium hydroxide.However, this is not the inventory of limit, those skilled in the art will know that other chelating agent are also applicable.
In the charge state, zinc slurry (that is, fresh zinc slurry) has the resistance for being less than 10 ohm and more than 15 moles
The zinc molar concentration of per liter (mol/L).As used herein, " charged state " is defined as battery active material and not yet experiences drive
Galvanic electricity (by external circuit, for example, loading) is from anode to movable cathode and the spontaneous oxidation reduction reaction that thus generates electricity." electric discharge
State " is defined herein as following state：Because anode material has been oxidized and cathode material is reduced, generate electricity
Spontaneous reaction stops.Fresh Zn or fresh Zn slurries refers to the zinc with neutral charge or in metal form.It is used
Zn or used Zn slurries refer to zinc that is oxidized and being converted into ZnO.Zn in ZnO is that 2 electricity are lost to O atom
The ion with 2+ electric charges of son.Because ZnO is closely knit not as Zn, used slurry has larger volume.
Carbonaceous additive 112 is to the ratio of zinc 108 in the range of by weight 2.5% to 10% (weight %).Alkalescence
Ratio of the electrolyte 110 in zinc slurry is in the range of 50 volumes % to 80 volumes %.Under battery charging state, at 25 DEG C
Under, zinc slurry has the viscosity in the range of 10000 to 1000000 centipoises (cP).
Air cathode 102 includes membrane electrode assembly (MEA) 116 and current collector 118.As shown in fig. 1b, MEA 116 can be with
Comprising catalyst layer 130 and gas diffusion layers (GDL) 132.Film 133 separates catalyst layer 130 with electrolyte 117.Catalyst
Reagent can be the platinum particles in the conductive layer of embedded carbon.GDL can be comprising carbon-coating and platinum particles and some water-repelling agents such as spy
Fluon.GDL 132 allows air to be externally entering, but prevents water and electrolyte leakage from preventing drying.
Generally, current collector 118 and 106 is the material with carbon element that high-conductivity metal or metal are coated.The quilt of current collector 106 and 118
It is shown as being electrically connected with load 120.As known in the art, MEA is widely used in sharing some spies with flow-through cell
In the fuel cell of property.
Anode chamber houses anode collector 106, and with input flow port 124 and output flow port 126.Anode slurry is stored up
Pond 128 is connected with the input flow port 124 and output flow port 126 of anode chamber.In one aspect, battery 100 includes water reservoir
134, and electrolyte chamber 115 has the input port 136 being connected with the water reservoir.
Slurry maximizes battery capacity used in zinc-air system, because the zinc in the slurry of disclosed battery
Concentration is far above conventional mechanical rechargeable battery (conventional mechanically rechargeable
Batteries the zinc concentration in).For example, the slurry with 30 moles per liter of zinc has been illustrated.
Another unique aspect is the use of the carbonaceous additive (for example, graphite or carbon fiber) in slurry and chelating agent.
In the case of chelating agent, the slurry of high concentration will be hardened after discharge, and extremely difficult will remove from battery.Because
When Zn is converted into ZnO, following two pieces thing can occur, so there is being hardened or cementation for slurry.First, because zinc particles become
It is porous to obtain Zinc Oxide that is less and being formed, so the effective surface area of pulp particle increases.This causes interparticle strong
Adhesion.Second, water is trapped in porous zinc bloom and becomes cannot function as the medium that ion may move through, so that
Chemical reaction stops.Chelating agent is generally to interact to form the molecule of metal complex, in the metal with metal ion
Metal is surrounded by the molecule in complex.Generally, as a result it is that metal ion is isolated, this can prevent metal ion with other gold
Category ion aggregation.The formation of metal complex is also the means for making these metallic ion passivations, and otherwise these metal ions will be with
Other compound reactions near them.That is, chelating agent be used to prevent Zn2+It is precipitated as ZnO.
With regard to material with carbon element, it was observed that the amount of the electrolyte (liquid) that can be added in slurry mix highly depends on
In the amount of carbon.In the case of without carbon, the volume of electrolyte is no more than by the capillary force institute in the space between zinc particles
The volume of holding.As a result the amount produces and behaves like damp sand and be very difficult to close to the amount for commercially available zinc-air battery
The slurry of pumping.Addition can produce the mixing being clearly separated that zinc particles are deposited to bottom more than more liquid results of the amount
Thing.Such mixture is mechanically unstable, i.e. under high pressure excessive liquid is with different from the speed of heavier zinc particles
Degree movement.However, in the case where a small amount of material with carbon element is added, the electrolyte of significantly greater amount can be added, because the electrolyte
Can be by the carbon adsorption of high surface.Gained slurry is relatively low, the more smooth and more stable suspension of viscosity.Additionally, carbon addition
Agent also prevents solidification, the solidification from sending out in the only slurry containing zinc (zinc-only slurry) generally after deep discharge
It is raw.During discharging, zinc particles are converted into Zinc Oxide by following Zn/ZnO redox reaction：
Zinc particles before the volume ratio electric discharge of Zinc Oxide are high by up to 20%.Such expansion causes the only slurry containing zinc
Electric discharge when solidify so that it is very difficult by slurry pumping by the system.As observed in practice, when to fresh normal
Rule zinc slurry discharged (to 76% capacity) when, cause slurry volume to expand and solidify to the conversion of ZnO.
The relation that Fig. 2A to Fig. 2 C describes between slurry parameter.It is apparent that expect the amount for reducing carbon and electrolyte as far as possible,
The stable suspension with the range of viscosities for allowing slurry to be pumped through the system is still kept simultaneously.Slurry optimization according to
According to be slurry composition and the mechanical/electrical parameter of slurry between relation.For example, the DC resistance (R of slurrySlurry) carbon is depended on to zinc
Ratio (Fig. 2A), and liquid electrolyte accounts for the percentage ratio (Fig. 2 B) of the cumulative volume of slurry.Dotted line in Fig. 2 B is represented in zinc granule
The maximum of the liquid that the precipitation of son can add before occurring, thus provides a constraints.Slurry viscosity also depends on carbon
Ratio to zinc, as shown in FIG. 2 C.Dotted line A and B determine that the amount of the pumping and carbon that can wherein carry out slurry will not excessively extremely
Cause the range of viscosities of high DC resistance.It is also required to consider the size of zinc particles.When zinc particles are too little, self discharge is probably obvious
's.When zinc particles are too big, utilization rate reduces, precipitation occurs and increases with the friction of conduit wall.Self discharge be by due to
The OH that the decomposition of the water in electrolyte is produced-And the low rate of the zinc for carrying out, parasiticss spontaneous oxidation (low-rate,
Parasitic, spontaneous oxidation), the decomposition of water occurs because of following reaction：2H2O+2e-→H2+2OH-.Example
Such as, the test that composition is associated with slurry resistance shows that zinc concentration can be up to 36 moles per liter (Mol/L).Such slurry shows
Show in 30 milliamperes of (mA/cm every square centimeter2) electric current density under after 10 circulations up to 95% coulombic efficiency, 63%
Utilization rate and 95% capability retention.
[table 1]
| Sample | C/Zn (weight %) | Zn concentration (mol/L) | KOH (volume %) | The slurry resistance (Ω) of calculating |
| A | 10.7 | 22 | 67 | 19.9 |
| B | 5.3 | 29 | 65 | 90.3 |
| C | 4.5 | 34 | 59 | 8.5 |
| D | 2.8 | 36 | 57 | 9.8 |
The variant of Fig. 3 A to 3C depicted example anode collectors/flow channel.Fig. 3 A describe have 3.3 milliliters (mL)/
8cm2The two-pass anode current collector 106 of/3700 MAHs (mAh) ability.Fig. 3 B describe with 3.6mL/8.7cm2/4100mAh
The U anode collector 106 of ability, and Fig. 3 C descriptions have 4.6mL/11.2cm2The snakelike of/3200mAh abilities is led to
Road anode collector 106.For example, current collector can be made up of the graphite material for being coated with metal such as stannum.The volume (mL) of slurry
With measure (mAh) direct correlation of electron stream.Effective area (cm between anode and negative electrode2) to producing, how many electric currents (electronics
Stream) also have an impact.
Fig. 4 depicted examples anode chamber and cathode interface.The example uses the serpentine channel anode collector 106 of Fig. 3 C.
MEA 116 is also show, the MEA 116 can be included and is fixed on the charcoal on being forced into ion exchange membrane or barrier film substrate
The platinum catalyst composition that can't see on cloth or carbon paper.Charcoal cloth/the carbon paper of MEA 116 and the interfaces of cathode collector 118.Electrolysis
Matter room 115 and MEA 116 interfaces on a surface, and the water penetration IEM (not shown) in back surface starches with zinc
Material interfaces.Current collector 118 can be netted so that most of area of MEA 116 and air contact.Carbon paper be it is conductive,
Therefore electronics can pass through from the MEA/ Air Interfaces that redox reaction occurs.
Fig. 5 is the partial cross-section for describing the gravity feed air cathode battery for using rechargeable zinc slurry anode
Figure.Battery 500 includes air cathode 502 and zinc slurry anode architectures 504.Zinc slurry anode architectures 504 include zinc slurry 506,
The zinc slurry 506 includes zinc particles, alkaline electrolyte, has chelating agent and carbonaceous additive (not in the alkaline electrolyte
Illustrate).Electrolyte chamber 115 is adjacent with air cathode 502, and water penetration IEM 516 is by zinc slurry 506a and electrolyte chamber
Alkaline electrolyte separate.Generally, zinc particles have the average-size in the range of 1 micron to 500 microns.Big particle tendency
In increasing viscosity, and less particle is more mechanical stability (less easily from slurry sediment out), but chemically not
It is too stable (being easier to be subjected to self discharge).Fresh zinc slurry 506a has the resistance less than 10 ohm and more than 15 moles per liter
Zinc molar concentration.
Zinc slurry anode architectures 504 are also comprising slurry charging reservoir 508, slurry collection reservoir 510 and with cloudy with air
The anode collector 512 of the adjacent rechargeable effective coverage 514 in pole 502.Effective coverage 514 connects from slurry charging reservoir 508
By the fresh zinc slurry 506a of charged state, and the used slurry of discharge condition is provided to slurry collection reservoir 510
506b.Air cathode 502 includes membrane electrode assembly (MEA) 116 and current collector 118.
As described above, another key feature of the battery is to keep enough water content in the slurry to prevent drying
Such that it is able to make chemical reaction carry out to the means for completing.The water dissolution for playing solvent in the electrolyte provides chemical reaction
Needed for the salt of ion, alkali or acid.Additionally, water is the medium that these ions can be moved back and forth by it.Without foot
In the case of enough water, even if before active material exhausts, chemical reaction also stops and battery is out of service.In other words,
Battery will be with poor efficiency.When the water in slurry is consumed, the volume of the electrolyte between slurry and air cathode
Semipermeable membrane that can be between electrolyte and slurry automatically feeds water.As it was previously stated, without in slurry supplement water this
In the case of the ability of kind, slurry drying.
Fig. 6 A are the cross-sectional view of the variant of the air cathode battery for describing Fig. 5.The details of Fig. 6 B depictions 6A.At one
Aspect, battery 600 to feed reservoir 508 from slurry comprising receiving to be realized in the way of the conveyer belt 602 of fresh zinc slurry 506a
Anode collector.Conveyer belt 602 for example can be made up of the metal forming of such as nickel.Conveyer belt current collector 602 is used as rechargeable
Electric effective coverage 604 to air cathode 502 provides fresh zinc slurry 506a, and by from the used of effective coverage 604
Slurry 506b is stored in slurry collection reservoir 510.Slurry feed reservoir 508 by fresh zinc slurry 506a gravity feeds extremely
Anode collector conveyer belt 602, and anode collector conveyer belt by used slurry 506b gravity feeds to slurry receive
In collection reservoir 510.
In shown one side, water penetration ion exchange membrane 606 is the synchronization adjacent with anode collector conveyer belt 602
Mobile conveyer belt.Gap between ion exchange membrane 606 and conveyer belt current collector 602 affects the speed of internal resistance and electric discharge.
There is low-angle between conveyer belt current collector 602 and vertical axises, the low-angle is by the flow behavior of zinc slurry 506a and used
Slurry 506b electric discharge when volumetric expansion determine.For example, the gap between conveyer belt 602 and ion exchange membrane is fresh
Slurry reservoir 508 nearby can be more narrower than used slurry reservoir 510 near, so as to limit the angle of deviation vertical axises.
The gap or angle can be adjustable to prevent the excessive thickening of slurry and be easy to remove slurry from conveyer belt 602.Electricity
Pond 600 can continuously work, as long as to its mechanical charge (the fresh zinc slurry of supply).
Optional auxiliary water reservoir 608 can be used for by the gravity feed of water 610 to ion exchange membrane conveyer belt 606 with
In electrolyte chamber 115 between air cathode 502.Challenge is the mobile zinc slurry with quite coarse solid, while in slurry
Produce close contact between material/IEM/ air cathodes to promote to produce low internal resistance and continuous Ion paths.In one aspect,
Optional auxiliary water reservoir 608 can be auxiliary electrolyte reservoir and water 610 can be alkaline electrolyte.
As another option, except promoting by gravity and control in addition to the flowing of fresh zinc slurry 506a, can be with
Using piston 612.It is mounted horizontally rather than vertically arranged unshowned other aspect in battery, piston could be for making
Unique power of fresh zinc pulp flow.
As the battery of Fig. 1, the carbonaceous additive in the zinc slurry 506 of the battery described in Fig. 5, Fig. 6 A and Fig. 6 B can
Think graphite, carbon fiber, white carbon black or carbon nano-particles.Carbonaceous additive to the ratio of zinc 2.5 weight % to 10 weight % model
In enclosing, and ratio of the alkaline electrolyte in zinc slurry is in the range of 50 volumes % to 80 volumes %.
Alkaline electrolyte in fresh zinc slurry 506a (or used slurry 506b) can be potassium hydroxide (KOH)
Or sodium hydroxide (NaOH).Assisted electrolysis matter 117 can be and the identical or different electrolyte used in zinc slurry.
Together provide flow-through cell together with the correlation technique for being used to generate voltage potential.Have been presented for material
With the example of pulp flow construction illustrating the present invention.However, the present invention is not limited only to these examples.Those skilled in the art will
Expect other variants and embodiment of the present invention.
(other explanations)
This application claims enjoying the priority of the continuation in part application based on following patent application：It is entitled to hand over ion
The circulation type metal battery of film is changed, is invented by Yuhao Lu etc., serial number 14/042264, be filed in September in 2013 30, generation
Reason people's Reference Number SLA3294；It is the continuation in part application of following patent application：It is entitled with low-temperature molten salt (LTMS) negative electrode
Battery, is invented, serial number 13/564015 by Yuhao Lu etc., is filed in August in 2012 1, attorney docket SLA3165.This
Two applications are all incorporated herein by way of reference.
Claims (22)
1. a kind of use has the air cathode battery of the zinc slurry anode of carbonaceous additive, and the battery bag contains：
Air cathode；
Zinc slurry anode, the zinc slurry anode is included：Current collector；Zinc slurry, the zinc slurry includes zinc particles, alkaline electrolysises
Matter and carbonaceous additive and chelating agent in the alkaline electrolyte；
Electrolyte chamber, the electrolyte chamber is comprising alkaline electrolyte and adjacent with the air cathode；With
The water penetration ion exchange membrane (IEM) that the zinc slurry anode is separated with the electrolyte chamber.
2. battery according to claim 1, wherein,
The group that the carbonaceous additive is constituted selected from graphite, carbon fiber, white carbon black and carbon nano-particles.
3. battery according to claim 1 and 2, wherein,
Under battery charging state, the zinc slurry has resistance and the zinc mole more than 15 moles per liter less than 10 ohm dense
Degree；Wherein described carbonaceous additive is to the ratio of the zinc particles in the range of 2.5 weight % to 10 weight %；And wherein institute
Ratio of the alkaline electrolyte in the zinc slurry is stated in the range of 50 volumes % to 80 volumes %.
4. battery according to any one of claim 1 to 3, wherein,
The zinc particles have the average-size in the range of 1 micron to 500 microns.
5. battery according to any one of claim 1 to 4, wherein,
The group that the alkaline electrolyte is constituted selected from potassium hydroxide (KOH) and sodium hydroxide (NaOH).
6. battery according to any one of claim 1 to 5, wherein,
The air cathode is included：Membrane electrode assembly (MEA)；And current collector.
7. battery according to any one of claim 1 to 6, it is also included：Anode chamber, the anode chamber has current collection
Device, input flow port and output flow port；And anode slurry reservoir, the anode slurry reservoir with described in the anode chamber
Input flow port and output flow port connection.
8. battery according to any one of claim 1 to 7, wherein,
Under battery charging state, at 25 DEG C, the zinc slurry has in the range of 10000 to 1000000 centipoises (cP)
Viscosity.
9. battery according to any one of claim 1 to 8, wherein,
The group that the chelating agent is constituted selected from ethylenediaminetetraacetic acid (EDTA), citric acid and ammonium hydroxide.
10. battery according to any one of claim 1 to 9, it also includes water reservoir, and wherein described electrolyte chamber
With the input port being connected with the water reservoir.
A kind of 11. air cathode batteries of use rechargeable zinc slurry anode, the battery bag contains：
Air cathode；
Zinc slurry anode architectures, the zinc slurry anode architectures are included：Zinc slurry, the zinc slurry includes zinc particles, alkaline electro
Xie Zhi, the chelating agent in the alkaline electrolyte and carbonaceous additive；Slurry feeds reservoir；Slurry collection reservoir；With with institute
The anode collector of the adjacent rechargeable effective coverage of air cathode is stated, the effective coverage connects from slurry charging reservoir
By the fresh zinc slurry of charged state, and the used slurry of discharge condition is provided to the slurry collection reservoir；
Electrolyte chamber, the electrolyte chamber is comprising alkaline electrolyte and adjacent with the air cathode；With
The water penetration ion exchange membrane (IEM) being placed between the electrolyte chamber and the zinc slurry anode.
12. batteries according to claim 11, wherein,
The anode collector is conveyer belt, and the conveyer belt feeds reservoir and receives fresh zinc slurry, conduct from the slurry
The rechargeable effective coverage provides the fresh zinc slurry and by from the use of effective coverage to the air cathode
The slurry crossed is stored in the slurry collection reservoir.
13. batteries according to claim 12, wherein,
The slurry feeds reservoir by fresh zinc slurry gravity feed to the anode collector conveyer belt, and wherein
The anode collector conveyer belt is by used slurry gravity feed to the slurry collection reservoir.
14. batteries according to claim 13, wherein,
The water penetration ion exchange membrane is the synchronization-moving conveyer belt adjacent with the anode collector conveyer belt.
15. batteries according to claim 14, it is also included：Alkaline electrolyte gravity feed is made to the electrolyte
Assisted electrolysis matter reservoir in room.
16. batteries according to any one of claim 11 to 15, wherein,
The group that the carbonaceous additive is constituted selected from graphite, carbon fiber, white carbon black and carbon nano-particles.
17. batteries according to any one of claim 11 to 16, wherein,
The fresh zinc slurry has the resistance and the zinc molar concentration more than 15 moles per liter less than 10 ohm.
18. batteries according to claim 17, wherein,
The carbonaceous additive is to the ratio of the zinc particles in the range of 2.5 weight % to 10 weight %；Wherein described alkalescence
Ratio of the electrolyte in the zinc slurry is in the range of 50 volumes % to 80 volumes %；And wherein described zinc particles have
Average-size in the range of 1 micron to 500 microns.
19. batteries according to any one of claim 11 to 18, wherein,
The group that the alkaline electrolyte is constituted selected from potassium hydroxide (KOH) and sodium hydroxide (NaOH).
20. batteries according to any one of claim 11 to 19, wherein,
The air cathode is included：Membrane electrode assembly (MEA)；And current collector.
21. batteries according to any one of claim 11 to 20, wherein,
At 25 DEG C, the fresh zinc slurry has the viscosity in the range of 10000 to 1000000 centipoises (cP).
22. batteries according to any one of claim 11 to 21, wherein,
The group that the chelating agent is constituted selected from ethylenediaminetetraacetic acid (EDTA), citric acid and ammonium hydroxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/473,713 US9608264B2 (en) | 2012-08-01 | 2014-08-29 | Air cathode battery using zinc slurry anode with carbon additive |
| US14/473,713 | 2014-08-29 | ||
| PCT/JP2015/004177 WO2016031201A1 (en) | 2014-08-29 | 2015-08-20 | Air cathode battery using zinc slurry anode with carbon additives |
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| CN106575786A true CN106575786A (en) | 2017-04-19 |
| CN106575786B CN106575786B (en) | 2019-06-28 |
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| JP (1) | JP6290509B2 (en) |
| CN (1) | CN106575786B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112643193A (en) * | 2020-12-11 | 2021-04-13 | 北京工业大学 | Preparation method of zinc with composite microstructure of zinc-air battery |
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| JP6346913B2 (en) * | 2016-04-19 | 2018-06-20 | 株式会社ギャラキシー | Vanadium air battery |
| WO2022237990A1 (en) | 2020-05-14 | 2022-11-17 | Media Lario S.R.L. | Metal-air rechargeable flow battery with zn-based nanoelectrofuel and process for obtaining an air cathode for such metal-air flow battery |
| US20240222744A1 (en) | 2021-05-14 | 2024-07-04 | Media Lario S.R.L. | Metal-Air Rechargeable Flow Battery |
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| US20130285597A1 (en) * | 2009-12-14 | 2013-10-31 | Jonathan Russell Goldstein | Zinc-Air Battery |
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| JPS4727859Y1 (en) * | 1971-09-09 | 1972-08-24 | ||
| FR2319982A1 (en) * | 1975-08-01 | 1977-02-25 | ELECTROCHEMICAL GENERATOR | |
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| JP6290509B2 (en) | 2018-03-07 |
| WO2016031201A1 (en) | 2016-03-03 |
| JP2017532724A (en) | 2017-11-02 |
| CN106575786B (en) | 2019-06-28 |
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