CN105449240A - Flow battery system - Google Patents
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- CN105449240A CN105449240A CN201410508445.0A CN201410508445A CN105449240A CN 105449240 A CN105449240 A CN 105449240A CN 201410508445 A CN201410508445 A CN 201410508445A CN 105449240 A CN105449240 A CN 105449240A
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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
Abstract
The invention discloses a flow battery system, which comprises a plurality of reaction units, a storage unit, conveying pipelines and power pumps. The storage unit is in connection with the reaction units through the conveying pipelines. According to the invention, the battery charge-discharge units (reaction units) and the energy storage unit are arranged separately, so that the power and capacity of a battery can be independent, the battery power depends on the number of the reaction units connected in parallel or in series in a battery stack, and the battery capacity depends on the content of electrode active materials in an electrolyte solution. The flow battery system provided by the invention has high energy density, long cycle life and high safety performance, and has the advantages of simple making process, low cost and easy integration systematization, thus having very considerable application prospects in electric automobiles, large energy storage equipment like wind energy, solar energy device and power grid peak regulation devices.
Description
Technical field
The invention belongs to electrochemical energy storage field, concrete, relate to a kind of flow battery system.
Background technology
The mankind, to the extensive utilization of new forms of energy, result in the expansion rapidly in secondary cell market.Ubiquitous to the requirement of secondary cell in current new forms of energy system, no matter be electric automobile, wind energy, solar grid-connected or peak load regulation network, is all badly in need of a kind of cheap, reliably, the secondary cell of safety and life-span length.How to design high energy storage, low cost, high security battery thus ensure that the sustainable development of regenerative resource becomes one of field of batteries important subject.
As the prototype of current most of battery, voltaic element is very low for the utilization ratio of battery active material, even can obtain the lithium rechargeable battery of highest energy density at present, its utilization ratio does not reach 50% (volume ratio) yet.The battery of the type makes its energy density significantly reduce owing to employing some non-active materials (as collector plate, barrier film, binders for electrodes, electrolyte etc.) simultaneously, and in the process of this battery from monocell to integrated system, energy density can reduce half again.
In order to more effectively promote the energy density of integrated system, scientific research personnel have devised energy storage units and the separable flow battery of charge/discharge unit.Be different from common storage battery, the active material of flow battery exists in liquid form, and the active material of these stored energys can be placed in external memory storage, and can be pumped to Blast Furnace Top Gas Recovery Turbine Unit (TRT) when reaction.The advantage of flow battery design is that it easily forms the system battery of different scales, and when power system capacity increases, its energy density approaches the energy density of living solution.
As typical flow battery, aqueous reaction flow battery has stable, easily extensible and the high feature of cost performance.But employ the active material (40Wh/L) of low energy densities due to aqueous phase flow battery and need to consume a large amount of mechanical energy for pumping into the lower concentrations of active material be stored in external memory storage, cause the design advantage of flow battery also offset by these deficiencies.
Therefore, prior art is real is necessary to further develop.
Summary of the invention
The present invention aim to provide a kind of energy density high, have extended cycle life and the flow battery system of easy of integrationization.
The invention provides a kind of flow battery system, comprising: some reaction members, described reaction member comprises plus plate current-collecting body, negative current collector and the barrier film be arranged between described plus plate current-collecting body and negative current collector; Described reaction member is divided into the positive pole reaction zone near described plus plate current-collecting body and the negative reaction district near described negative current collector by described barrier film; Memory cell, described memory cell comprises positive pole memory cell and negative pole memory cell, and described positive pole memory cell stores anode electrolyte, and described negative pole memory cell stores electrolyte liquid; Conveyance conduit, described memory cell is connected with described some reaction members by described conveyance conduit; Kinetic pump, described anode electrolyte circulates between described positive pole memory cell and described positive pole reaction zone via described conveyance conduit under described kinetic pump promotes; Described electrolyte liquid circulates between described negative pole memory cell and described negative reaction district via described conveyance conduit under described kinetic pump promotes; Described anode electrolyte comprises positive active material, and described positive active material is suspended in described anode electrolyte with particulate form, comprise can reversible deviate from-material of embedded ion; Described electrolyte liquid comprises at least one and can dissolve electrolyte and make the solvent that described electrolyte ionizes; Described electrolyte can ionize out at least one charge and discharge process and reduce-deposit and be oxidized-the active ion that dissolves in described negative reaction district.
Preferably, described positive active material is micron order, submicron order or nano level particle.
Preferably, also comprise the additive being selected from carbon-based material in described anode electrolyte, described carbon-based material comprises at least one be selected from section's qin carbon black, acetylene black, activated carbon, carbon fiber, graphite or carbon nano-tube.
Preferably, described active ion comprises metal ion, and described metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni.
Preferably, described metal ion is present in described electrolyte liquid with at least one form in hydrochloride, sulfate, nitrate, acetate, formates, phosphate.
Preferably, the concentration range of described active ion is 0.5-15mol/L.
Preferably, described negative current collector does not participate in electrochemical reaction.
Preferably, material selected from metal Ni, Cu, Ag, Pb, Sn, Fe, Al of described negative current collector or the one in the above-mentioned metal of Passivation Treatment.
Preferably, the material of described negative current collector is selected from carbon-based material, stainless steel or has the metal of plating/coating, and described plating/coating contains at least one in the simple substance of C, Sn, In, Ag, Pb, Co, Zn, alloy or oxide.
Preferably, the thickness range of described plating/coating is between 1-1000nm.
Preferably, described negative pole currect collecting surface is formed with porous layer, and described porous layer has micron order or submicron order or nano level hole.
Preferably, described negative pole currect collecting surface forms graphene layer.
Preferably, described reaction member also comprises negative electrode active material, and described negative electrode active material is formed on described negative current collector, and described negative electrode active material can be oxidized-be dissolved as described active ion when described flow battery system electric discharge.
Preferably, described negative electrode active material surface is formed with porous layer, and described porous layer has micron order or submicron order or nano level hole.
Preferably, described negative electrode active material surface is formed with graphene layer.
Preferably, the thickness range of described porous layer is 0.05-1mm.
Preferably, described porous layer comprises carbon-based material.
Preferably, described carbon-based material is selected from least one in section's qin carbon black, acetylene black, activated carbon, carbon nano-tube, carbon fiber, graphite.
Preferably, described porous layer comprises the mixture of activated carbon powder and binding agent, and the weight percentage ranges that described activated carbon powder accounts for described porous layer is 20-99%.
Preferably, described activated carbon is activated carbon-fiber felt or activated carbon fiber cloth.
Preferably, described positive active material comprises at least one in the reversible material deviating from-embed lithium ion, sodium ion or magnesium ion.
Preferably, described positive active material meets general formula Li
1+xmn
ym
zo
kcan the reversible material deviating from-embed the spinel structure of lithium ion, wherein ,-1<x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M is selected from least one in Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al.
Preferably, described positive active material meets general formula Li
1+xm
ym '
zm "
co
2+ncan the reversible material deviating from-embed the layer structure of lithium ion, wherein ,-1<x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1 ,-0.2≤n≤0.2, M, M ', M " is selected from the middle at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al respectively.
Preferably, described positive active material meets general formula Li
xm
1-ym '
y(XO
4)
ncan the reversible material deviating from-embed the olivine structural of lithium ion, wherein, 0<x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, M ' is selected from least one in Mg, Ti, Cr, V or Al, and X is selected from least one in S, P or Si.
Preferably, described positive active material comprises NaVPO
4f.
Preferably, the basis material of described plus plate current-collecting body is selected from carbon-based material, the one in metal or alloy.
Preferably, described carbon-based material comprises vitreous carbon, graphite, carbon cloth, foamy carbon, carbon felt or has the electric conducting material of 3D bicontinuous structure.
Preferably, described metal comprises Al, Ni, Fe, Cu, Pt, Pd, Pb, Ti, Ta, Nb, Zr, Cr, Mo, Zn, V, W, the Be through transpassivation.
Preferably, described alloy comprises through the stainless steel of transpassivation, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy or Pt-Rh alloy.
Preferably, described stainless steel comprises stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.
Preferably, described anode electrolyte also comprises can the reversible ion deviate from-embed, and the described reversible ion deviate from-embed reversiblely can embed-deviate from described positive active material.
Preferably, the concentration range of the described reversible ion deviate from-embed is 0.1-30mol/L.
Preferably, described reaction member connects with in parallel or series system.
Preferably, described anode electrolyte and described solvent comprise at least one in the aqueous solution or alcoholic solution.
Preferably, the pH value range of described anode electrolyte and described electrolyte liquid is 4-7.
Flow battery system provided by the invention, charge/discharge unit (reaction member) and energy storage units (memory cell) are provided separately, the power of battery and capacity is made to be independently, watt level depends on the quantity of reaction member, the size of capacity depends on the content of electrode active material in electrolyte, battery capacity can be increased by increasing the amount of electrode active material in electrolyte, thus construct energy density high, have extended cycle life and the flow battery system of easy of integrationization.Flow battery system is at electric automobile, and such as the application on the peak adjusting device of wind energy, solar energy and electrical network of large-scale energy storage device has very considerable prospect.
Accompanying drawing explanation
Below in conjunction with drawings and embodiments, the invention will be further described.
Fig. 1 is the structural representation of flow battery system in the present invention;
Fig. 2 is the structural representation of reaction member in the present invention;
Fig. 3 is the structural representation of reaction member in the present invention, and wherein negative pole currect collecting surface forms negative pole
Active material.
Wherein:
1. flow battery system 14. plus plate current-collecting body 24. positive pole memory cell
6. conveyance conduit 16. negative current collector 26. negative pole memory cell
8. kinetic pump 18. barrier film 28. negative electrode active material
10. reaction member 20. positive pole reaction zone
12. package casing 22. negative reaction districts
Embodiment
Refer to shown in Fig. 1, flow battery system 1, comprise some reaction members 10, memory cell, conveyance conduit 6 and kinetic pump 8.
See also shown in Fig. 1 and Fig. 2, reaction member 10 comprises plus plate current-collecting body 14, negative current collector 16 and the barrier film 18 be arranged between plus plate current-collecting body 14 and negative current collector 16.Reaction member 10 is divided into the positive pole reaction zone 20 near plus plate current-collecting body 14 and the negative reaction district 22 near negative current collector 16 by barrier film 18.
Plus plate current-collecting body 14 does not participate in electrochemical reaction, mainly as the carrier of electrical conductivity and collection.The material of plus plate current-collecting body 14 is selected from the one in carbon-based material, metal or alloy.
Carbon-based material comprises vitreous carbon, graphite, carbon cloth, foamy carbon, carbon felt, carbon fiber or has the electric conducting material of 3D bicontinuous structure.
Metal comprises Al, Ni, Fe, Cu, Pt, Pd, Pb, Ti, Ta, Nb, Zr, Cr, Mo, Zn, V, W, Be through transpassivation.Preferably, plus plate current-collecting body 14 is selected from the Al of Passivation Treatment.
The main purpose of metallic aluminium being carried out Passivation Treatment makes the surface of aluminium form one deck passivating film, when flow battery system 1 works, aluminium can stable play to be collected and the effect of conduction electron, and can not participate in the reaction of positive pole reaction zone 20, thus the performance of guarantee flow battery system 1.
Alloy comprises through the stainless steel of transpassivation, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy or Pt-Rh alloy.Stainless steel includes but are not limited to the one in stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.Preferably, plus plate current-collecting body 14 is selected from through transpassivation stainless steel.
Same, stainless steel is carried out Passivation Treatment be also can be stable play and collect and the effect of conduction electron, and the reaction of positive pole reaction zone 20 can not be participated in, the performance of guarantee flow battery system 1.In a specific embodiment, the stainless detailed process of passivation is: at 50 DEG C, stainless steel is inserted half an hour in the nitric acid of 20%, makes stainless steel surfaces form one deck passivating film, and then is used as plus plate current-collecting body 12 by stainless steel.
Negative current collector 16 can as the carrier of electrical conductivity and collection.Negative current collector 16 can be any conductive metal or alloy that can be made its electrochemicaUy inert by passivation.Concrete, material selected from metal Ni, Cu, Ag, Pb, Sn, Fe, Al of negative current collector 16 or a kind of in the above-mentioned metal of Passivation Treatment or carbon-based material or stainless steel or have the metal of plating/coating, plating/coating is selected from least one in simple substance, alloy or the oxide containing C, Sn, In, Ag, Pb, Co, Zn.Wherein, carbon class electric conducting material comprises graphite material, and the paper tinsel of such as business-like graphite compacting, the part by weight scope wherein shared by graphite is 90-100%.Stainless steel material comprises the one in stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.
Preferably, plating/coating is selected from the higher material of hydrogen-evolution overpotential, and to reduce the generation of negative reaction district 22 side reaction, the thickness of plating/coating is between 1-1000nm.Such as tin on negative current collector 16 plated surface of copper or graphite foil, plumbous or silver-colored.
Reaction member 10 is divided into positive pole reaction zone 20 and negative reaction district 22 by barrier film 18, the product that barrier film 18 will stop one of them electrode reaction to generate on the one hand passes through, with the reaction avoiding it to participate in another opposite polarity electrode reaction district, the ion of balancing charge also to be allowed to pass through on the other hand.Barrier film 18 is selected from the one in permoselective membrane, common porous film, cation-exchange membrane or anion-exchange membrane.In a specific embodiment, barrier film 18 is selected from Celgard2500.
Reaction member 10 is connected by parallel or series system, then is encapsulated by package casing 12.
Memory cell comprises positive pole memory cell 24 and negative pole memory cell 26.Store anode electrolyte in positive pole memory cell 24, containing positive active material in anode electrolyte, positive active material is suspended in anode electrolyte with solid particles, makes anode electrolyte be suspension containing positive active material.Preferably, positive active material is micron or sub-micron or nano level particle.Anode electrolyte is with at least one in water or alcoholic solution for solvent, and alcoholic solution includes but are not limited to methyl alcohol and ethanol.The volume range that positive active material accounts for anode electrolyte is 10-40%.
Positive active material comprise can reversible deviate from-material of embedded ion.Concrete, positive active material comprises at least one can the reversible material deviating from-embed lithium ion or sodium ion or magnesium ion.
In a specific embodiment, positive active material meets general formula Li
1+xmn
ym
zo
kcan the reversible material deviating from-embed the spinel structure of lithium ion, wherein ,-1<x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M is selected from least one in Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al.Preferably, positive active material contains LiMn
2o
4.Preferred, positive active material contains the LiMn through doping or coating modification
2o
4.
In a specific embodiment, positive active material meets general formula Li
1+xm
ym '
zm "
co
2+ncan the reversible material deviating from-embed the layer structure of lithium ion, wherein ,-1<x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1 ,-0.2≤n≤0.2, M, M ', M " is selected from the middle at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al respectively.Preferably, positive active material contains LiCoO
2.
In a specific embodiment, positive active material meets general formula Li
xm
1-ym '
y(XO
4)
ncan the reversible material deviating from-embed the olivine structural of lithium ion, wherein, 0<x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, M ' is selected from the middle at least one of Mg, Ti, Cr, V or Al, and X is selected from the one in S, P or Si.Preferably, positive active material contains LiFePO
4.
In current Lithium Battery Industry, nearly all positive active material all can through overdoping, the modification such as coated.But doping, it is complicated that the means such as coating modification cause the chemical general formula of material to express, as LiMn
2o
4can not represent the general formula of now widely used " LiMn2O4 ", and should with general formula Li
1+xmn
ym
zo
kbe as the criterion, comprise the LiMn through various modification widely
2o
4positive active material.Same, LiFePO
4and LiCoO
2also should be interpreted as widely and comprise through various doping, the modification such as coated, general formula meets Li respectively
xm
1-ym '
y(XO
4)
nand Li
1+xm
ym '
zm "
co
2+npositive active material.
Positive active material of the present invention be lithium ion deviate from-inlaid scheme time, can select as LiMn
2o
4, LiFePO
4, LiCoO
2, LiM
xpO
4, LiM
xsiO
ycompounds such as (wherein M are a kind of variable valency metal).In addition, the compound N aVPO of sodium ion can be deviate from-embed
4f, can deviate from-embed the compound Mg M of magnesium ion
xo
y(wherein M is a kind of metal, 0.5<x<3,2<y<6) and there is similar functions, can deviate from-compound of embedded ion or functional group can as the positive active material of battery of the present invention.
As optimization, also comprise the reversible ion deviate from-embed in anode electrolyte, the reversible ion deviate from-embed reversiblely can embed-deviate from positive active material, thus improves the exchange velocity of positive active material and anode electrolyte intermediate ion.Concrete, positive active material is can the reversible compound deviating from-embeds lithium ion, and in anode electrolyte, correspondence also comprises lithium ion.The reversible ion deviate from-embed comprises lithium ion or sodium ion or magnesium ion, and the concentration range of the reversible ion deviate from-embed in anode electrolyte is 0.1-30mol/L.In a specific embodiment, anode electrolyte comprises lithium acetate.
Electrolyte liquid is stored in negative pole memory cell 26, electrolyte liquid comprises at least one can dissolve electrolyte and the solvent that electrolyte is ionized, and electrolyte can ionize out at least one charge and discharge process and reduce-deposit and be oxidized-the active ion that dissolves in negative reaction district 22.Solvent is at least one in the aqueous solution or alcoholic solution, and alcoholic solution includes but are not limited to methyl alcohol and ethanol.
The concentration range of active ion is 0.5-15mol/L.In a particular embodiment, active ion comprises metal ion.Metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni.Preferably, metal is Zn.
Metal ion is present in electrolyte liquid with forms such as hydrochloride, sulfate, nitrate, acetate, formates, phosphate.At concrete execution mode, metal ion exists with the form of nitrate; In a preferred embodiment, metal ion exists with the form of sulfate; In preferred execution mode, metal ion exists with the form of acetate.
In a specific embodiment, when plus plate current-collecting body 14 is the stainless steel of Passivation Treatment, preferably, metal ion is present in electrolyte liquid with the form of sulfate or nitrate or acetate; When plus plate current-collecting body 14 is the metallic aluminium of Passivation Treatment, preferably, metal ion is present in electrolyte liquid with the form of sulfate or acetate.
In order to ensure the battery capacity of flow battery system 1, the concentration of the active ion in electrolyte liquid must reach certain limit, when electrolyte liquid crosses alkali, can affect the solubility of active ion in electrolyte liquid; When electrolyte liquid peracid, then there will be the problems such as proton embeds altogether in electrode material corrosion and charge and discharge process, therefore, in the present invention, the pH value range of anode electrolyte and electrolyte liquid is 4-7.
Flow battery system 1 also comprises conveyance conduit 6 and kinetic pump 8.Memory cell is connected with reaction member 10 by conveyance conduit 6, and anode electrolyte circulates between positive pole memory cell 24 and positive pole reaction zone 20 via conveyance conduit 6 under kinetic pump 8 promotes, electrolyte liquid circulates between negative pole memory cell 26 and negative reaction district 22 via conveyance conduit 6 under kinetic pump 8 promotes.
The anode electrolyte carrying positive active material and the electrolyte liquid carrying negative electrode active ion drive respectively by kinetic pump 8 and flow into reaction member 10 through conveyance conduit 6 circulation, and there is electrochemical reaction at positive pole reaction zone 20 and negative reaction district 22 respectively, in reaction member 10, positive pole reaction zone 20 and negative reaction district 22 are separated by barrier film 18, flow battery system 1 external load or charge power supply.In flow battery system 1, charge/discharge unit (reaction member 10) and energy storage units (positive pole memory cell 24, negative pole memory cell 26) be provided separately, therefore the power of flow battery system 1 and energy are independently, watt level depends on the quantity of reaction member 10, the size of energy depends on the content of electrode active material in electrolyte, can be reached the object increasing the energy content of battery by the content increasing electrode active material in electrolyte.
The charge-discharge principle of the flow battery system 1 in the present invention is: during charging, electrolyte is pushed into reaction member 10 by the pump 8 that turns on the power, at positive pole reaction zone 20, anode electrolyte carries positive active material and flows through plus plate current-collecting body 14, at plus plate current-collecting body 14 place, the reversible ion deviate from-embed is deviate from positive active material, simultaneously oxidized with variable valency metal in active material, and ejected electron.Electronics arrives battery cathode collector 16 via plus plate current-collecting body 14 and external circuits, and the active ion simultaneously in electrolyte liquid obtains electronics in negative reaction district 22 and is reduced, and is deposited on negative reaction district 22.Discharge process is be then the inverse process of charging process.
The execution mode that of flow battery system 1 is concrete, negative current collector 16 does not participate in electrochemical reaction, carrier when only reducing as the active ion in electrical conductivity and collection and electrolyte liquid-deposit.Flow battery system 1 works first and reduces-be deposited on the charging process on negative current collector 16 surface in negative reaction district 22 for deviating from reversible ion, the active ion in electrolyte liquid deviate from-embed in positive active material.
Refer to shown in Fig. 3, preferably, reaction member 10 also comprises negative electrode active material 28, negative electrode active material 28 in any suitable manner, such as plating or coating, be formed on negative current collector 16, negative electrode active material 28 can be oxidized when flow battery system 1 discharge process-be dissolved as the active ion in electrolyte liquid.Same, negative current collector 16 does not participate in electrochemical reaction, only as the carrier of electrical conductivity and collection.Flow battery system 1 works first, both can be deviate from reversible ion, the active ion in electrolyte liquid deviate from-embed in positive active material to reduce in negative reaction district 22, being deposited on the charging process that negative electrode active material 28 surface forms active ion sedimentary deposit, also can be the discharge process that the reversible ion deviate from-embed is embedded in positive active material, negative electrode active material 28 is oxidized-is dissolved as the active ion in electrolyte liquid in anode electrolyte.Preferred, flow battery system 1 works as the reversible ion deviate from-embed is deviate from from positive active material first, and the active ion in electrolyte liquid reduces in negative reaction district 22-be deposited on the charging process on negative electrode active material 28 surface.
Specific to this preferred embodiment in, positive active material is LiMn
2o
4, plus plate current-collecting body 14 is graphite foil, and negative electrode active material 28 is Zn, and negative current collector 16 is graphite foil, comprises lithium acetate in anode electrolyte, comprises zinc acetate in electrolyte liquid.As the Zn of negative electrode active material 28 when flow battery system 1 discharges, be oxidized-be dissolved as Zn
2+, be present in electrolyte liquid, with this simultaneously, at positive pole reaction zone 20, the Li contained in anode electrolyte
+be embedded into positive active material, therefore, the mode of operation first of flow battery system 1 is discharge process; In addition, positive active material LiMn
2o
4in be rich in Li, and Li can from LiMn
2o
4in deviate from, the Zn in electrolyte liquid
2+the negative electrode active material 28 that can reduce-be deposited into during charging is surperficial, and therefore, the mode of operation first of flow battery system 1 can also be charging process.
In another concrete execution mode of flow battery system 1, carrier when negative current collector 16 not only reduces as the active ion in electrical conductivity and collection and electrolyte liquid-deposits, can be oxidized-dissolve when flow battery system 1 discharge process the active ion become in electrolyte liquid simultaneously.In like manner, flow battery system 1 works first, both can be deviate from reversible ion, the active ion in electrolyte liquid deviate from-embed in positive active material to reduce-be deposited on negative current collector 15 surface in negative reaction district 22 and become the charging process of active ion sedimentary deposit, also can be the discharge process that the reversible ion deviate from-embed is embedded into positive active material, negative current collector 16 is oxidized-is dissolved as the active ion in electrolyte liquid in anode electrolyte.Preferably, flow battery system 1 works first as charging process.
Specific in present embodiment, positive active material is LiMn
2o
4, plus plate current-collecting body is graphite foil, and negative current collector 16 is Zn, comprises lithium acetate in anode electrolyte, comprises zinc acetate in electrolyte liquid.Therefore, flow battery system 1 first mode of operation can be electric discharge, the Li namely in anode electrolyte
+be embedded into positive active material LiMn
2o
4, Zn is oxidized-is dissolved as Zn
2+; Flow battery system 1 first mode of operation can also be charging, i.e. positive active material LiMn
2o
4in deviate from Li
+, the Zn in electrolyte liquid
2+reduce-be deposited into negative current collector 16.Therefore, flow battery system 1 works first and has two kinds of patterns, facilitates user to carry out choice for use in conjunction with self needing.
In addition, electrochemical reaction can be participated in when negative current collector 16 being provided with negative electrode active material 28 or negative current collector 16 discharges in flow battery system 1, it can be discharge process or charging process that flow battery system 1 works first, therefore need not limit positive active material when flow battery system 1 works first simultaneously and contain in the reversible ion deviating from-embed and anode electrolyte containing the reversible ion deviate from-embed.When flow battery system 1 works first, positive active material does not comprise the reversible ion deviate from-embed, so the flow battery system 1 reversible ion deviate from-embed be in anode electrolyte that works first is embedded into positive active material, and negative electrode active material 28 or negative current collector 16 are oxidized-are dissolved as the discharge process of the active ion in electrolyte liquid.The reversible ion deviate from-embed is not contained in anode electrolyte when flow battery system 1 works first, so flow battery system 1 works first and is the reversible ion deviate from-embed and deviates from from positive active material, and active ion reduces in negative reaction district 22-be deposited as the charging process of active ion sedimentary deposit.
When flow battery system 1 works first, as long as meet positive active material can reversible deviate from-embedded ion and contain the reversible ion deviate from-embed containing in this reversible ion deviating from-embeds or anode electrolyte, all can ensure the use of flow battery system 1 as power supply or energy storage device.And, flow battery system 1 in the present invention is when working first, there is the pattern of different discharge and recharges, the producer can according to the application scenario of user, select the collocation participating in the material of electrochemical reaction in flow battery system 1, produce the flow battery system 1 with different charge and discharge mode.Flow battery system 1 is simple to operate simultaneously, and safe easy care, function admirable, is applicable to being applied in large-scale energy storage field, as the storage of solar energy, wind energy very much.
Flow battery system 1 provided by the invention, electrolyte is in flow regime in charge and discharge process, increases the speed of the material Transfer in collector-electrolyte interface solution, thus reduces the concentration polarization in electrode reaction district.In addition, except reaction member 10, flow battery system 1 further comprises positive pole memory cell 24 external separately and negative pole memory cell 26, not only increase the stored energy capacitance of battery, and electrolyte can be changed on demand or take away, electrolyte after charging can save backup, and is pumped in some reaction members 10 when need discharge again.Therefore, this energy storage units and the separable flow battery system 1 of charge/discharge unit, be easy to make reaction member 10 form integrated system, thus the convenient power and the energy that design battery according to the application of battery.
At positive pole reaction zone 20, in order to make the exchange realizing effective charge be more prone between positive active material and plus plate current-collecting body 14, the additive of carbon-based material is also comprised in anode electrolyte, concrete, carbon-based material is micron order or submicron order or nano-scale particle, and carbon-based material is selected from least one in section's qin carbon black (KB), acetylene black, activated carbon, carbon fiber, graphite, Graphene or carbon nano-tube.The volume range that carbon-based material accounts for anode electrolyte is 0.5-5%.Graphite includes but are not limited to mineral ore graphite (Veingraphite).In a particular embodiment, carbon-based material is selected from KB, the electric conductivity of the adsorption capacity that KB is strong and excellence, the speed of charge-exchange between positive active material and plus plate current-collecting body 14 can not only be improved, the reunion of positive active material in anode electrolyte and depositional phenomenon can also be prevented simultaneously, thus make positive active material evenly be dispersed in the anode electrolyte of flowable state.
In negative reaction district 22, more even in order to what make active ion deposit in negative reaction district 22, in a specific embodiment, can be formed with the porous layer with micron order or submicron order or nanoscale hole on negative current collector 16 surface, the thickness range of porous layer is 0.05-1mm.
In a preferred embodiment, when reaction member 10 comprises negative electrode active material 28, be formed with the porous layer with micron or submicron order or nanoscale hole on negative electrode active material 28 surface, described porous layer thickness scope is 0.05-1mm.
Micron order or submicron order hole account for the 50-95% of porous layer volume range.Preferably, negative current collector 16 is provided with the porous layer of nanoaperture, and nanoaperture accounts for the 10-99% of porous layer volume range, and the scope of the average diameter of nanoaperture is 1 to 999nm.Preferred, the scope of the average diameter of nanoaperture is 1 to 150nm.
Porous layer does not participate in the electrochemical reaction in negative reaction district 22, porous layer has very large specific area, can be in discharge and recharge course of reaction the active ion that deposition reduction and oxidation dissolution occur and larger deposition rate surface area is provided, make active ion negative current collector 16 or negative electrode active material 28 surface deposition ground more even, the effective generation reducing negative reaction district 22 dendrite.In addition, by being formed at the porous layer on negative current collector 16 or negative electrode active material 28 surface, migration distance in active ion charge and discharge process can also be shortened, active ion only needs to spread shorter distance just can complete charge and discharge process, solves the problem that in active ion course of reaction, diffusional resistance is large.Simultaneously, owing to being provided with porous layer, thinner barrier film 18 can being used when preparing battery, making in battery charging process, especially the oxygen that during overcharge, positive pole reaction zone 20 produces more easily can move to negative reaction district 22 and reduce, and strengthens the invertibity of battery.
In a specific embodiment, the material of porous layer mainly comprises active carbon material.
Porous layer comprises the mixture of activated carbon powder and binding agent.The specific area of activated carbon is at 200-3000m
2between/g, the weight range that activated carbon accounts for porous layer is 20-99%.Preferably, by commercialization activated carbon powder (particle size range is between 1-200mm) and PVDF (Kynoar) Homogeneous phase mixing, add NMP (1-METHYLPYRROLIDONE) and be dissolved into pasty state, be coated on negative current collector 16 or negative electrode active material 28 surface.Porous layer thickness is between 0.1-0.2mm, and the weight range that NMP accounts for porous layer mixture is 50-70%.
In another concrete execution mode, porous layer is activated carbon-fiber felt or activated carbon fiber cloth, and the specific area of activated carbon-fiber felt or activated carbon fiber cloth is at 100-2200m
2between/g.
Another preferred embodiment in, active carbon particle is mixed with electrically conductive graphite, then with PVDF, NMP Homogeneous phase mixing, be coated in negative current collector 16 or negative electrode active material 28 surface.The thickness of porous layer is between 0.1-0.2mm.The effect of electrically conductive graphite is the electronic conduction ability increasing porous layer.In the present embodiment, the weight range that activated carbon accounts for porous layer is 20-80%, and the weight range that electrically conductive graphite accounts for porous layer is 5-20%, and the weight range that bonding agent PVDF accounts for porous layer is 5-15%.Active carbon material has loose structure and larger specific area, and price is also cheap relative to the carbon-based material of carbon nano-tube class.And the technique specifically making the negative current collector 16 or negative electrode active material 28 containing porous layer is also relatively simple, easy industrialization.
In a particular embodiment, the material of porous layer is selected from carbon black, preferred, and the material of porous layer is selected from KB, and KB has very large specific area and very strong adsorption capacity, and active ion can be made to deposit more even in negative reaction district 22.
In more preferably execution mode, what deposit in negative reaction district 22 to make the active ion in electrolyte liquid is more even, forms graphene layer on negative current collector 16 surface.In preferred execution mode, reaction member 10 comprises negative electrode active material 28, is formed with graphene layer on negative electrode active material 28 surface.The theoretical specific surface area of Graphene is up to 2600m
2/ g, there is outstanding heat conductivility and mechanical property, and electron mobility at a high speed under room temperature, therefore, the graphene layer being formed at negative current collector 16 or negative electrode active material 28 surface can not only provide larger surface area for the deposition of active ion 28, that can also improve negative reaction district 22 further leads electronic capability simultaneously, thus improves the chemical property of battery big current.
Flow battery system 1 provided by the invention, has gathered the feature of lithium rechargeable battery and flow battery.In contrast to traditional lithium rechargeable battery, can reversible deviate from-positive active material of embedded ion suspend with particulate form be stored in anode electrolyte, plus plate current-collecting body 14 only as conduction and the carrier collecting electronics, makes the content of the positive active material of high power capacity be no longer changeless, in contrast to the vanadium flow battery that in flow battery, technology is comparatively ripe, adopt in the present invention energy density high can reversible deviate from-positive active material of embedded ion replaces the liquid electrolyte of the low energy densities of the vanadium ion containing different valence state, in addition, electrode reaction district and the memory cell containing electrode active material are provided separately, make the positive active material of electrochemical reaction and negative electrode active ion storage to occur in the outside of reaction member 10 at plus plate current-collecting body 14 and negative current collector 16, and in charge and discharge process, electrolyte is pumped into reaction member 10 via conveyance conduit 6 by kinetic pump 8, the effective charge realized between electrode active material and collector exchanges.The battery structure of this uniqueness, the power of battery and capacity is made to be independently, watt level depends on the quantity of reaction member 10, and the size of capacity depends on the content of electrode active material in electrolyte, can increase battery capacity by the amount increasing electrode active material in electrolyte.In addition, the electrolyte in flow battery system 1 is water or alcoholic solution, and relative to the conventional lithium ion secondary cell adopting organic electrolyte, security performance is higher, is easier to safeguard that cost is also less simultaneously.Therefore, the flow battery system 1 in the present invention has high-energy-density, high safety performance, long-life feature, and the battery process of industrialization is simultaneously simple and easy to safeguard, cost is low.
Flow battery system 1 is except having high-energy-density, the flow battery with independent energy memory cell also may change the concept of people for traditional secondary battery, because can realize being different from the quick charge of traditional approach by " replacing " stored energy solid active material (mode of similar " oiling ").This battery structure is also the long-life simultaneously, the battery design of integrated system, easy care opens new road, make flow battery system 1 at electric automobile, such as the application on the peak adjusting device of wind energy, solar energy and electrical network of large-scale energy storage device has very considerable prospect.
Below in conjunction with better embodiment, set forth the present invention further.Should be understood that these execution modes are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in following embodiments, the usually conveniently conditioned disjunction condition of advising according to manufacturer.Unless otherwise indicated, otherwise all percentage, ratio, ratio or number by weight.
Unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as, refer to the weight of solute in the solution of 100 milliliters.Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the meaning be familiar with identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Execution mode one
Flow battery system comprises some reaction members, memory cell, conveyance conduit and kinetic pump.
Reaction member comprises plus plate current-collecting body, negative current collector and the barrier film be arranged between plus plate current-collecting body and negative current collector.Plus plate current-collecting body and negative current collector all adopt thickness to be the graphite foil of 0.1mm, and wherein, negative pole currect collecting surface is formed with porous layer.Concrete, porous layer preparation process is: by activated carbon powder, (coconut husk is fired, and specific area is 1500m
2g
-1), conductive carbon black, PVDF mixes with the ratio of 90:5:5, adds NMP and is dissolved, and be evenly coated in obtained porous layer in negative current collector graphite foil, the thickness of porous layer is 0.1mm.Barrier film is Celgard2500, and reaction member is divided into the positive pole reaction zone near plus plate current-collecting body and the negative reaction district near negative current collector by barrier film.
Memory cell comprises positive pole memory cell and negative pole memory cell, and positive pole memory cell stores anode electrolyte, and anode electrolyte is the aqueous solution containing 1.3MLiCl, and positive active material is LiMn
2o
4, the carbon back additive in anode electrolyte is section's qin carbon black (KB), concrete, LiMn
2o
420% and 1% is respectively with the volume ratio of KB in anode electrolyte.LiMn
2o
4be present in anode electrolyte with micron particles state, KB is present in anode electrolyte with nano-scale particle, makes anode electrolyte be suspension.Negative pole memory cell stores electrolyte liquid, and electrolyte liquid is for containing 4MZnCl
2the aqueous solution, wherein Zn
2+it is the active ion that reduction deposition, oxidation dissolution occur in negative reaction district.
Memory cell is connected with some reaction members by conveyance conduit, and anode electrolyte circulates between positive pole memory cell and positive pole reaction zone via conveyance conduit under kinetic pump promotes; Electrolyte liquid circulates between negative pole memory cell and negative reaction district via conveyance conduit under kinetic pump promotes.
Execution mode two
In execution mode two, negative current collector adopts Copper Foil zinc-plated, and all the other batteries form identical with execution mode one.
Execution mode three
With LiCoO
2for positive active material, the carbon back additive in anode electrolyte is section's qin carbon black (KB), and wherein, the volume ratio that positive active material and carbon back additive account for anode electrolyte is respectively 26% and 0.8%.
All the other batteries form identical with execution mode one.
Execution mode four
With LiFePO
4for positive active material, the carbon back additive in anode electrolyte is section's qin carbon black (KB), and wherein, the volume ratio that positive active material and carbon back additive account for anode electrolyte is respectively 20% and 1%.
All the other batteries form identical with execution mode one.
The foregoing is only better embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
Claims (10)
1. a flow battery system, comprising:
Some reaction members, described reaction member comprises plus plate current-collecting body, negative current collector and the barrier film be arranged between described plus plate current-collecting body and negative current collector; Described reaction member is divided into the positive pole reaction zone near described plus plate current-collecting body and the negative reaction district near described negative current collector by described barrier film; Memory cell, described memory cell comprises positive pole memory cell and negative pole memory cell, and described positive pole memory cell stores anode electrolyte, and described negative pole memory cell stores electrolyte liquid;
Conveyance conduit, described memory cell is connected with described some reaction members by described conveyance conduit; Kinetic pump, described anode electrolyte circulates between described positive pole memory cell and described positive pole reaction zone via described conveyance conduit under described kinetic pump promotes; Described electrolyte liquid circulates between described negative pole memory cell and described negative reaction district via described conveyance conduit under described kinetic pump promotes;
It is characterized in that: described anode electrolyte comprises positive active material, described positive active material is suspended in described anode electrolyte with particulate form, comprise can reversible deviate from-material of embedded ion; Described electrolyte liquid comprises at least one and can dissolve electrolyte and make the solvent that described electrolyte ionizes; Described electrolyte can ionize out at least one charge and discharge process and reduce-deposit and be oxidized-the active ion that dissolves in described negative reaction district.
2. flow battery system according to claim 1, it is characterized in that: also comprise the additive being selected from carbon-based material in described anode electrolyte, described carbon-based material comprises at least one in section's qin carbon black, acetylene black, activated carbon, carbon fiber, graphite, Graphene or carbon nano-tube.
3. flow battery system according to claim 1, is characterized in that: described active ion comprises metal ion, and described metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni.
4. flow battery system according to claim 3, is characterized in that: described metal ion is present in described electrolyte liquid with the form of at least one in hydrochloride, sulfate, nitrate, acetate, formates, phosphate.
5. flow battery system according to claim 1, is characterized in that: described negative current collector does not participate in electrochemical reaction.
6. flow battery system according to claim 1, it is characterized in that: described reaction member also comprises negative electrode active material, described negative electrode active material is formed on described negative current collector, and described negative electrode active material can be oxidized-be dissolved as described active ion when described flow battery system electric discharge.
7. flow battery system according to claim 1, is characterized in that: described positive active material comprises at least one can the reversible material deviating from-embed lithium ion or sodium ion or magnesium ion.
8. flow battery system according to claim 1, is characterized in that: described anode electrolyte also comprises can the reversible ion deviate from-embed, and the described reversible ion deviate from-embed reversiblely can embed-deviate from described positive active material.
9. flow battery system according to claim 1, is characterized in that: described reaction member connects with in parallel or series system.
10. flow battery system according to claim 1, is characterized in that: described anode electrolyte and described solvent comprise at least one in the aqueous solution or alcoholic solution.
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| CN201410508445.0A CN105449240A (en) | 2014-09-28 | 2014-09-28 | Flow battery system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107871861A (en) * | 2017-05-15 | 2018-04-03 | 中国科学院金属研究所 | A kind of water system sodium ion electrochemical energy storage device |
| CN116031424A (en) * | 2023-03-24 | 2023-04-28 | 南方科技大学 | Flow battery composite electrode, preparation method thereof and flow battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903924A (en) * | 2011-06-03 | 2013-01-30 | 苏州宝时得电动工具有限公司 | Battery |
| CN103094627A (en) * | 2011-11-03 | 2013-05-08 | 苏州宝时得电动工具有限公司 | Battery |
| CN103872370A (en) * | 2012-12-11 | 2014-06-18 | 苏州宝时得电动工具有限公司 | Flow battery |
-
2014
- 2014-09-28 CN CN201410508445.0A patent/CN105449240A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903924A (en) * | 2011-06-03 | 2013-01-30 | 苏州宝时得电动工具有限公司 | Battery |
| CN103094627A (en) * | 2011-11-03 | 2013-05-08 | 苏州宝时得电动工具有限公司 | Battery |
| CN103872370A (en) * | 2012-12-11 | 2014-06-18 | 苏州宝时得电动工具有限公司 | Flow battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107871861A (en) * | 2017-05-15 | 2018-04-03 | 中国科学院金属研究所 | A kind of water system sodium ion electrochemical energy storage device |
| CN116031424A (en) * | 2023-03-24 | 2023-04-28 | 南方科技大学 | Flow battery composite electrode, preparation method thereof and flow battery |
| CN116031424B (en) * | 2023-03-24 | 2023-06-23 | 南方科技大学 | Flow battery composite electrode, preparation method thereof and flow battery |
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Application publication date: 20160330 |