CN105765780A - High capacity alkali/oxidant battery - Google Patents
High capacity alkali/oxidant battery Download PDFInfo
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- CN105765780A CN105765780A CN201480064329.2A CN201480064329A CN105765780A CN 105765780 A CN105765780 A CN 105765780A CN 201480064329 A CN201480064329 A CN 201480064329A CN 105765780 A CN105765780 A CN 105765780A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide electrodes
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
An alkali/oxidant battery is provided with an associated method of creating battery capacity. The battery is made from an anode including a reduced first alkali metal such as lithium (Li), sodium (Na), and potassium (K), when the battery is charged. The catholyte of battery includes an element, in the battery charged state, such as nickel oxyhydroxide (NiOOH), magnesium(IV) (oxide Mn(4+)O2), or iron(III) oxyhydroxide (Fe(3+)(OH)3), with the alkali metal hydroxide. An alkali metal ion permeable separator is interposed between the anolyte and the catholyte. For example, if the catholyte includes nickel(II) hydroxide (Ni(OH)2) in a battery discharged state, then it includes NiOOH in a battery charged state. To continue the example, the anolyte may include dissolved lithium ions (Li+) in a discharged state, with solid phase reduced Li formed on the anode in the battery charged state.
Description
Technical field
The present invention relates generally to electrochemical cell, and relates more particularly to the battery formed by alkali metal negative pole with the positive pole comprising nickel, magnesium (manganese) or ferrum.
Background technology
Battery is that wherein electronics and ion come and go the electrochemical appliance to realize electrochemical reaction between negative pole and positive pole.Voltage and the capacity of battery are determined by electrode material.In conventional batteries, all parts including negative material, positive electrode, barrier film, electrolyte and current collector are loaded in the container that volume is fixing.As long as battery is assembled, its energy and capacity are exactly unmodifiable.Flow-thru cell is formed by being ion exchanged the current collector (electrode) that film separates, and its negative pole and positive electrode are stored in independent holding vessel simultaneously.Negative pole and positive electrode circulate in flow-thru cell, wherein occur electrochemical reaction with release and to store energy.Therefore, battery capacity and energy are determined by the following: (1) electrode material (negative electrode solution (anolyte) and positive pole liquid (catholyte)), (2) concentration of negative electrode solution and positive pole liquid, and the volume of (3) negative electrode solution and positive pole liquid holding vessel.Conventional prior art negative pole and positive electrode generally react with the aqueous containing some redox couples or non-aqueous solution (electrolyte).
In general, metal being used as negative material and can obtain high voltage in the battery, their low-molecular-weight provides big capacity simultaneously.Such as, lithium has relative to H2/H+Peak capacity for the most nagative potential of-3.04 volts (V) and 3860 MAHs every gram (mAh/g).High voltage and Large Copacity cause the overall high-energy of battery.It addition, in metal ion battery, sodium, potassium, magnesium, nickel, zinc, calcium, aluminum etc. are the good candidate as negative material.
Prior art positive electrode focuses on metal ion host compound (hostcompounds).Metal ion can be extracted from the clearance space of electrode material in charging process and is inserted in material during discharge process.It should be noted, however, that the lattice of charge and discharge process serious distortion material, this substantially destroys their structure after some circulations.Additionally, these positive electrodes are only provided that the capacity less than metal negative electrode material 1/10th.Accordingly, it would be desirable to develop new positive electrode to mate the more high power capacity of negative material and the long circulation life of (2) displaying metal ion battery with (1).
In 1996, Abraham and Jiang reported wherein oxygen and is used as the polymer dielectric system rechargeable lithium/oxygen cell of positive electrode [non-patent literature 1].Oxygen in air constantly flows into battery and provides the very high ratio energy of 5200 watt-hour every kilogram (Wh/kg).But, oxygen is just having some shortcomings.First, expensive eelctro-catalyst is used in battery to drop the aerodynamic blockage of hypoxic effect.Second, the blunt electrochemical reaction of oxygen has manufactured big overpotential in lithium/air cell.3rd, lithium/air cell must keep the positive pole opened to allow air into.Similarly, oxygen positive pole is also used in zinc-air battery [patent documentation 1].
In 2011, Lu and Goodenough disclosed the aqueous positive-pole [non-patent literature 2] for lithium ion battery.They use water soluble, redox to such as Fe (CN)6 3/Fe(CN)6 4Aqueous solution as positive pole.Around in environment, lithium/aqueous positive-pole battery works under about 3.4 volts.This battery shows little overpotential, high coulombic efficiency and long circulation life.But, water is inert material in electrochemical system, and it reduces the specific capacity of positive pole.Although the design of lithium/circulation positive battery can increase capacity and energy, but its volume must be big.
Utilize similar battery structure, Ni (OH)2It is used as positive pole to mate cathode of lithium [non-patent literature 3].Li/Ni(OH)2Battery must be charged so that Ni (OH)2Following reaction can be passed through and be oxidized to NiOOH:
Ni(OH)2+OH-=NiOOH+H2O+e-。
Meanwhile, there is following reaction:
Li++e-=Li
Wherein lithium ion derives from electrolyte.
Therefore, although Ni (OH)2Experimentally show the high power capacity of 260mAh/g, but battery capacity is limited by the Li ion concentration in electrolyte.The capacity advantage of Li/Ni is limited by the Li ion concentration in electrolyte.
Reference listing
Patent documentation
Patent documentation 1:PhilipN.Ross, Jr., zinc electrode and rechargeable zinc-air battery (Zincelectrodeandrechargeablezinc-airbattery), US4842963.
Patent documentation 2:WilliamC.Carter, Yet-MingChiang, high energy density redox flow device (Highenergydensityredoxflowdevice), US2011/0189520.
Non-patent literature
Non-patent literature 1:K.M.Abraham, Z.Jiang, polymer dielectric system rechargeable lithium/oxygen cell (Apolymerelectrolyte-basedrechargeablelithium/oxygenbatte ry), ECS's will (JournaloftheElectrochemicalSociety), 143 (1996) 1-5.
Non-patent literature 2:YuhaoLu, johnB.Goodenough, YoungsikKim, aqueous positive-pole (Aqueouscathodefornextgenerationalkali-ionbatteries) for alkali metal-ion battery of future generation, JACS (JournaloftheAmericanChemicalSociety), 133 (2011), 5756-5759.
Non-patent literature 3:H.Li, Y.Wang, H.Na, H.Liu, H.Zhou, incorporate the rechargeable Ni-Li battery (RechargeableNi-Libatteryintegratedaqueous/nonaqueoussyst em) of aqueous/nonaqueous systems, JACS (J.Am.Chem.Soc), 131 (2009) 15098-15099.
Summary of the invention
Technical problem
Will advantageously, NiOOH can be used as positive electrode in the battery have cathode of lithium so that the capacity of Li/Ni battery is determined by the amount of NiOOH in positive pole during fabrication.
Technical scheme
According to an aspect of the present invention, it is a kind of comprise following alkali metal/oxidant cell: negative pole, it comprises the first alkali metal of reduction under battery charging state；Negative electrode solution；Positive pole, it comprises selected from hydroxy nickel oxide (NiOOH), magnesium oxide (IV) (Mn under battery charging state(4+)O2) and FeOOH (III) (Fe(3+)(OH)3) in composition (element)；Positive pole liquid, it comprises the first alkali metal hydroxide；With the first permeable barrier film of alkali metal ion, it is placed between described negative electrode solution and described positive pole liquid.
According to another aspect of the present invention, it it is a kind of method for producing alkali metal/oxidant cell capacity, described method includes: form battery in the charge state, described battery has the first alkali metal negative pole, negative electrode solution, the first permeable barrier film of alkali metal ion, and comprise selected from hydroxy nickel oxide (NiOOH), magnesium oxide (IV) (Mn(4+)O2) and FeOOH (III) (Fe(3+)(OH)3) in the positive pole of oxidizing component, and comprise the positive pole liquid of the first alkali metal hydroxide；Producing the first battery capacity, wherein said first battery capacity is corresponding to the first alkali-metal amount of the oxidizing component in positive pole and the reduction at negative pole place.
According to another aspect of the present invention, it is a kind of comprise following lithium (Li)/nickel (Ni) battery: negative pole, it comprises the Li of reduction under battery charging state；Negative electrode solution；Positive pole, it comprises hydroxyl oxidize Ni (Ni (OH) under battery discharge status2) and under battery charging state, comprise hydroxy nickel oxide (NiOOH)；Positive pole liquid, it comprises LiOH；With lithium ion (Li+) permeable barrier film, it is placed between described negative electrode solution and described positive pole liquid.
Accompanying drawing explanation
[Fig. 1] Fig. 1 is the partial cross sectional view of the alkali metal/oxidant cell of charging.
[Fig. 2] Fig. 2 is the partial cross sectional view of alkali metal/oxidant cell in the discharged condition.
[Fig. 3 A] Fig. 3 A is the partial cross sectional view describing alkali metal/oxidant cell that wherein negative pole is the material being dissolved in negative electrode solution.
[Fig. 3 B] Fig. 3 B is the partial cross sectional view describing alkali metal/oxidant cell that wherein negative pole is the material being dissolved in negative electrode solution.
[Fig. 4 A] Fig. 4 A is the partial cross sectional view of alkali metal/oxidant cell, wherein positive pole liquid and just extremely comprise the identical component of anode sizing agent.
[Fig. 4 B] Fig. 4 B is the partial cross sectional view of alkali metal/oxidant cell, wherein positive pole liquid and just extremely comprise the identical component of anode sizing agent.
[Fig. 5] Fig. 5 is the partial cross sectional view of alternative (alternative) alkali metal/oxidant cell using anode sizing agent.
[Fig. 6] Fig. 6 is the partial cross sectional view of the alternative alkali metal/oxidant cell using anode sizing agent.
[Fig. 7] Fig. 7 is the schematic block diagram describing multiple monocells.
[Fig. 8] Fig. 8 is the partial cross sectional schematic block diagram describing alkali metal/oxidant cell with different view.
[Fig. 9] Fig. 9 is the partial cross sectional schematic block diagram describing to have the flow-thru cell of anode sizing agent.
[Figure 10] Figure 10 is the partial cross sectional schematic block diagram of several battery blocks being connected to slurry pool by pipeline.
[Figure 11] Figure 11 is the flow chart illustrating the method for producing alkali metal/oxidant cell capacity.
Detailed description of the invention
Disclosed herein is cathode of lithium battery, and it uses hydroxy nickel oxide (NiOOH), magnesium oxide (IV) (Mn(4+)O2) or FeOOH (III) (Fe(3+)(OH)3) as the positive electrode in alkali metal negative battery.Positive electrode can be fixed on current collector as solid, and can also be made into following slurry positive pole liquid, and it flows through the side of the positive electrode of battery, it is allowed to uses machinery (contrary with electricity/chemistry) method to quickly charging battery.
Therefore it provides a kind of alkali metal/oxidant cell.When battery is electrically charged, this battery is made up of the negative pole of the first alkali metal lithium (Li) comprising reduction, sodium (Na) and potassium (K).Under battery charging state, the positive pole of battery comprises composition such as NiOOH, Mn(4+)O2Or Fe(3+)(OH)3, and the alkali metal hydroxide in positive pole liquid.The permeable barrier film of alkali metal ion is placed between negative electrode solution and positive pole liquid.Such as, if under battery discharge status, positive pole comprises nickel hydroxide (II) (Ni (OH)2), then under battery charging state, it comprises NiOOH.Continuing this example, negative electrode solution can comprise the lithium ion (Li dissolved under discharge condition+), and the Li of the solid phase reduction formed on negative pole under battery charging state.
In one aspect, positive pole and positive pole liquid are identical composition, form anode sizing agent, and cathode collector is immersed in anode sizing agent.In this aspect, monocell comprises negative pole, negative electrode solution and barrier film and anode sizing agent pond, and it is connected to monocell input and delivery outlet, when battery charging or electric discharge under a load for the anode sizing agent of oxidizing, and the anode sizing agent that supply is reduced when battery charges.Additionally, multiple monocells can connect in the way of serial or parallel connection electrical connection.
Provide below above-mentioned battery and for producing the other details of the method for alkali metal/oxidant cell capacity.
Fig. 1 is the partial cross sectional view of the alkali metal/oxidant cell of charging.Battery 100 comprises negative pole 102 and negative electrode solution 106, and described negative pole 102 comprises the first alkali metal 104 of reduction under battery charging state.Battery 100 also comprises positive pole 110 and the positive pole liquid 111 comprising the first alkali metal hydroxide 108, and described positive pole 110 comprises the material 113 such as hydroxy nickel oxide (NiOOH), magnesium oxide (IV) (Mn of oxidation under battery charging state(4+)O2) or FeOOH (III) (Fe(3+)(OH)3).At this, for simplicity, the first alkali metal hydroxide is schematically represented as in positive pole liquid 111 oval composition.These positive electrodes are water insoluble, to promote stable circulation.They have the clearly defined current potential being associated with redox couple, and low-molecular-weight is to promote high-energy-density.Positive pole liquid can be aqueous, because under the current potential that oxidoreduction occurs, water is not because reacting or decomposing and meet requirement.Additionally, different from organic bath, water is cheap and nonflammable.The first permeable barrier film 112 of alkali metal ion is placed between negative electrode solution 106 and positive pole liquid 111.Negative electrode solution generally comprises organic solvent such as ethylene carbonate, diethyl carbonate or the mixture of both.Such as, when dissolving in a solvent, lithium salts is LiPF such as6It is dissociated into Li+PF6 -。
Barrier film 112 is following permeable membrane, and it is placed between negative pole 102 and positive pole 110 to keep two electrodes to separate, thus preventing electrical short, allows the transmission of ionic charge carrier needed for Guan Bi circuit in battery 100 during current flowing simultaneously.Barrier film 112 can be the polymeric membrane forming microporous layers.Relative to negative electrode solution and positive pole liquid material, it is usually chemical and electrochemically stable.
Fig. 2 is the partial cross sectional view of alkali metal/oxidant cell in the discharged condition.As used in this article, when the electrochemical active material in positive pole is the state of oxidation and the electrochemical material in negative pole is reducing condition, battery is charged state.When battery is discharge condition, the electrochemical active material in positive pole is reducing condition and the electrochemical material in negative pole is the state of oxidation.In other words, when providing external connection between a positive electrode and a negative electrode by load, occurring self power generation chemical reaction to make electric current flow to negative pole (or electronics flows to positive pole from negative pole) from positive pole, now battery is charged.Simultaneous, these react induced positive electrode active materials and aoxidize negative active core-shell material.Similarly, when providing external connection by load between a positive electrode and a negative electrode, it does not have self power generation chemical reaction occurring and does not have electric current to flow to negative pole (or electronics flows to positive pole from negative pole) from positive pole, now battery has put electricity.On the contrary, it is necessary to external power source with force electric current from negative pole flow to positive pole (or electronics flows to negative pole from positive pole) with reverse otherwise can charging battery occur spontaneous reaction.
In general, battery 100 works as the result of redox reaction, and redox reaction relates to: oxidation, and it is by molecule, atom or losses of ions electronics or increases oxidation state, and relating to reduction, it obtains electronics by molecule, atom or ion or reduces oxidation state.In one case, seeing figures.1.and.2 the two, positive pole 110 comprises the composition 200 such as nickel hydroxide (II) (Ni (OH) of reduction under battery discharge status2), and under battery charging state, comprise the composition 113 such as NiOOH of oxidation.Continuing this example, under battery discharge status, negative electrode solution 106 can comprise alkali metal ion 202, such as lithium ion (Li+).More generally, under battery discharge status, negative electrode solution 106 comprises alkali metal ion 202 such as lithium ion (Li+), sodium ion (Na+) or potassium ion (K+).Under battery charging state, negative pole 102 comprises the alkali metal 104 of solid phase reduction, respectively Li, Na or K.
In other embodiments, positive pole 110 comprises magnesium oxide (IV) (Mn under battery charging state(4+)O2) 113, under battery discharge status, comprise hydroxyl oxidize magnesium (III) (Mn(+3)OOH)200.Or, positive pole 110 comprises Fe under battery charging state(3+)(OH)3113, and under battery discharge status, comprise FeOOH (II) (Fe(2+)(OH)2)200。
When the positive pole 110 under battery charging state is NiOOH, it utilizes following reaction to develop into battery discharge status from battery charging state:
NiOOH+H2O+e-=Ni (OH)2+OH-。
When the positive pole 110 under battery charging state is Mn(4+)O2Time, it utilizes following reaction to develop into battery discharge status from battery charging state:
Mn(4+)O2+H2O+e-→Mn(3+)OOH+OH-。
When the positive pole 110 under battery charging state is Fe(3+)(OH)3Time, it utilizes following reaction to develop into battery discharge status from battery charging state:
Fe(3+)(OH)3+e-→Fe(2+)(OH)2+OH-。
Fig. 1 and Fig. 2 describes the alkali metal/oxidant cell of active material solid phase negative pole and active material positive pole.For active material, it means that negative pole 102 and positive pole 110 react with negative electrode solution 106 and positive pole liquid 111 respectively in the redox reaction that can make battery charging and discharging.Although being not explicitly depicted, but negative pole 102 and positive pole 110 are likely in the way of covering current collector to be formed.In this example, when battery in the charge state time, negative pole 102 be reduction solid alkali metal 104 such as Li, Na or K.Additionally, positive pole 110 comprises Mn under battery charging state(4+)O2113, and comprise Mn under battery discharge status(+3)OOH200.Or, positive pole 110 comprises Fe under battery charging state(3+)(OH)3113, and comprise Fe under battery discharge status2+(OH)2200.In yet another aspect, under battery charging state, positive pole 110 is NiOOH113, and under battery discharge status, it is Ni (OH)2200.For example, it is possible to by Ni (OH) in water2Powder and binding agent (a kind of polymer) and conductive carbon (white carbon black or graphite or carbon fiber) mix the thickener being applied to current collector (nickel foil or nickel foaming body) with formation.This positive pole is suppressed and heats so that water becomes dry.In this article positive pole 110 is called solid, but it has positive pole liquid 111 and penetrates into microcosmic hole therein by capillary force.
Fig. 3 A and 3B is the partial cross sectional view describing alkali metal/oxidant cell that wherein negative pole is the material being dissolved in negative electrode solution.Positive pole 110 and positive pole liquid 111 described in the explanation of Fig. 1 and 2, are different in that cathode collector 300 is explicitly shown as above.In this aspect, under battery charging state, negative pole (Fig. 3 A) comprises the alkali metal 104 (that is, Li, Na or K) of the reduction formed on current collector 302.Under battery discharge status, alkali metal ion 202 (that is, Li+、Na+Or K+) be dissolved in negative electrode solution 106.Under battery discharge status, it does not have alkali metal is necessarily attached on current collector 302.
Fig. 4 A and 4B is the partial cross sectional view of alkali metal/oxidant cell, wherein positive pole liquid and just extremely comprise the identical component of anode sizing agent.Cathode collector 300 is dipped in anode sizing agent 110/111.In these figures, negative pole 102 and negative electrode solution 106 and above identical described in the explanation of Fig. 1 and 2, for brevity, this explanation is not repeated.Monocell 400 comprises negative pole 102, negative electrode solution 106, the first permeable barrier film 112 of alkali metal ion, input port 402 and delivery outlet 404.Anode sizing agent pond 406 is connected to monocell input port 402 and delivery outlet 404 and supplies the anode sizing agent 113 of oxidizing with under battery charging state (Fig. 4 A), or under electric loading, keep charging, or when battery is under discharge condition (Fig. 4 B) or when charging when it, the anode sizing agent 200 of supply reduction.For simplicity, in anode sizing agent 110/111, the anode sizing agent 113 of oxidation and the anode sizing agent 200 of reduction are schematically represented as ellipse.
Fig. 5 and 6 are the partial cross sectional view of the alternative alkali metal/oxidant cell using anode sizing agent.In these figures, negative pole 102 and negative electrode solution 106 and above identical described in the explanation of Fig. 3 A and 3B, and for brevity, this explanation is not repeated.Monocell 400 comprises negative pole 102, negative electrode solution 106, the first permeable barrier film 112 of alkali metal ion, input port 402 and delivery outlet 404.Anode sizing agent pond 406 is connected to monocell input port 402 and delivery outlet 404 and supplies the anode sizing agent 113 of oxidizing with under battery charging state (Fig. 5), to keep charging under electric loading, or when battery is under discharge condition (Fig. 6) or when charging when it, the anode sizing agent 200 of supply reduction.
Fig. 7 is the schematic block diagram describing multiple monocells.Being illustrated that monocell 700-0 to 700-n, wherein n is greater than the integer of 1, but is not additionally limited to any particular value.Monocell 700-0 to 700-n is shown as being electrically connected in series, but alternatively (not shown), and they can be electrical connection in parallel.In one aspect, as it can be seen, anode sizing agent pond 406 and multiple monocell 700-0 to 700-n are connected in parallel to carry anode sizing agent 110/111.Alternatively but not shown, monocell can be connected in series with slurry pool.
Fig. 8 is the partial cross sectional schematic block diagram describing alkali metal/oxidant cell with different view.In one aspect, as it can be seen, NiOOH is used as the positive electrode 802 in lithium/nickel-based battery 800.Battery 800 comprises the lithium an-ode 804 and NiOOH positive pole 802 that are separated by Li ion-permeable barrier film 806, and described Li ion-permeable barrier film 806 transports Li ion 808 between negative pole 804 side and positive pole 802 side.Lithium/NiOOH battery 800 must discharge with following electrochemical reaction after initial assembling:
Negative side: Li=Li++e-；
Side of the positive electrode: NiOOH+H2O+e-=Ni (OH)2+OH-；
Overall reaction: Li+NiOOH+H2O=Ni (OH)2+LiOH。
Lithium/Ni (OH) that capacity that is that associate with non-patent literature 3 (H.Li etc.) and that describe in the background section above is limited by the Li ion concentration in electrolyte2Battery is different, and the capacity of the Li/NiOOH battery of Fig. 8 is only determined by the active material in electrode.Specifically, for non-patent literature 3, negative pole is Li, just extremely Ni (OH)2, and electrolyte has LiOH.The first reaction after battery assembling must be the process to battery charging.During charging process, LiOH in the electrolyte dissociates, Li+Moving to negative side and becoming is plated on lithium an-ode, OH-Ion and Ni (OH)2Reaction, generates NiOOH and H2O.The capacity of battery is determined by the amount of the LiOH being added into liquid electrolyte.
In battery 800, negative pole is Li metal and just extremely NiOOH.Different from above-mentioned prior art battery (non-patent literature 3), the first reaction after battery assembles is that battery 800 is discharged.Li+It is dissolved in negative electrode solution in negative side and moves to side of the positive electrode.Positive electrode NiOOH reacts and produces Ni (OH)2.Battery capacity is limited by the primary quantity of Li or NiOOH existed when battery manufactures.Because Li has very big the capacity (> 3000mAh/g more than LiOOH positive pole (261mAh/g)), so Li/NiOOH battery capacity is determined by the primary quantity of the NiOOH at positive pole.Therefore, the battery with NiOOH positive pole of initial charge has ratio and utilizes Ni (OH) in non-patent literature 32Electrode and LiOH liquid electrolyte carry out the capacity that the battery of initial discharge is much higher.
Fig. 9 is the partial cross sectional schematic block diagram describing to have the flow-thru cell of anode sizing agent.Once be attached on current collector at the NiOOH assembling battery 800, battery capacity is exactly fixing.In order to increase battery capacity further, the slurry positive pole liquid 902 that NiOOH is formed as being fed in cathode collector 904 by the flow-thru cell of Fig. 9 is to mate the high power capacity of cathode of lithium 804.Carter and Chiang (patent documentation 2, referring to background section) discloses and uses flowable slurry as electrode material in the battery.But, they have LiCoO2The battery of slurry positive pole liquid is shown, 0.36Li ion reversibly inserts LiCoO between 2V and 4.5V2In molecule/from LiCoO2Releasing in molecule, this is corresponding to the capacity of 99mAh/g, and the capacity than the 261mAh/g of NiOOH is much smaller.Circulation Li/NiOOH battery 900 is by cathode of lithium 804, and the positive compartment barrier film composition of Li ion-permeable film or Li ion conducting solid electrolyte 806.During discharging, NiOOH is reduced to Ni (OH)2.If being mechanically charged (utilize and recover anode sizing agent from the oxidation slurry in pond), battery 900 can be continuously generated electric power.Similarly, for the negative pole to replace, negative compartment can also be easily removable, thus realizing mechanical charge.In some respects, current collector 904 can additionally comprise the wall of the compartment containing slurry.
Figure 10 is the partial cross sectional schematic block diagram of several battery blocks being connected to slurry pool by pipeline.Each block 1002 comprises multiple flow-thru cells 900 of electrical connection in parallel.In order to obtain high voltage and high-energy, as shown, block 1002 can be electrically connected in series to form battery pile 1000.Several blocks 1002 can be connected in parallel (as shown in the figure) or be connected in series to circulate NiOOH slurry positive pole liquid by pipeline.The same with the circulation Li/NiOOH battery of Fig. 9, heap 1000 can also carry out mechanical charge when Li negative pole is replaced and supplements with NiOOH slurry positive pole liquid.
The following is the summary of battery structure described in Fig. 1 to Fig. 6:
1. slurry positive pole/solid, metal negative electrode；
2. solid positive pole/solid, metal negative electrode；
3. slurry positive pole/be dissolved in the negative material in negative electrode solution；
4. solid positive pole/be dissolved in the negative material in negative electrode solution.
Along with slurry or solid positive pole develop into oxidation state (and developing into reduction-state from oxidation state) from reduction-state, they do not have phase transformation.For the battery (that is, together with positive pole place, redox reaction occurring at negative pole) to discharge or to charge, the oxidation state of positive pole and negative pole must be contrary.
Table 1
There is the battery (1) of Ni slurry positive pole/solid, metal Li negative pole
During discharging, slurry positive pole enters oxidation state (NiOOH) and negative pole is metal Li (being in reduction-state).Slurry is with reduction-state (Ni (OH)2Leave.Subsequently, by the flowing of the slurry that reverses, i.e. Ni (OH)2Enter with reduction-state and leave with oxidation state (NiOOH), it is possible to battery is charged.Dissolve when metal Li is oxidized, i.e. Li+Aqueous electrolyte is solvable.Battery has the high power capacity (contrary with the much smaller concentration of alkali metal ion in the electrolytic solution) determined by the amount of solid metal negative pole.
Table 2
There is the battery (3) of the negative material of Ni slurry positive pole/be dissolved in negative electrode solution.
As previously mentioned, dissolve when metal Li is reduced, i.e. Li+Aqueous electrolyte is solvable.Therefore, it can foundation and there is no solid negative pole, only there is the battery of the current collector of suitable material.Metal ion (oxidation) is dissolved in negative electrode solution solution.During charging, along with the oxidized slurry positive pole of negative pole enters reduction-state (Ni (OH)2).Slurry leaves with oxidation state (NiOOH).Subsequently, by the flowing of the slurry that reverses, i.e. NiOOH enters oxidation state and with reduction-state (Ni (OH)2) leave, can to battery discharge.When metal Li is reduced, it is plated on current collector.Battery capacity is determined by the concentration of metal ion in electrolyte.
Figure 11 is the flow chart illustrating the method for producing alkali metal/oxidant cell capacity.Although the method is depicted as in order to know the step of a series of numbering, but numbering be not necessarily indicative to the order of step.Should be appreciated that some in these steps can be skipped, parallel carry out, or carry out when not maintaining strict order.But, in general, the method follows the numerical order of the step described.The method starts in step 1100.
Step 1102 forms battery in the charge state, and this battery has the first alkali metal negative pole, negative electrode solution, the first permeable barrier film of alkali metal ion and the positive pole comprising oxidizing component.The composition of oxidation can be hydroxy nickel oxide (NiOOH), magnesium oxide (IV) (Mn(4+)O2), or FeOOH (III) (Fe(3+)(OH)3).Battery also comprises the positive pole liquid containing the first alkali metal hydroxide.In one aspect, positive pole and positive pole liquid are anode sizing agent.Step 1104 produces the first battery capacity, and wherein the first battery capacity is in response to the first alkali-metal amount of the composition aoxidized in positive pole and the reduction of negative pole place.
In one aspect, step 1102 forms battery in the charge state, and this battery has the first alkali metal (X) negative pole of NiOOH positive pole and reduction, and wherein X is lithium (Li), sodium (Na) or potassium (K).Then, by carrying out following reaction, step 1006 is to battery discharge:
Negative pole: X=X++e-And,
Positive pole: NiOOH+H2O+e-=Ni (OH)2+OH-。
In yet another aspect, step 1102 forms battery in the charge state, and this battery has Mn(4+)O2First alkali metal (X) negative pole of positive pole and reduction, wherein X is Li, Na or K.Then, include battery discharge in a step 1106 carrying out following reaction:
Negative pole: X=X++e-, and
Positive pole: Mn(4+)O2+H2O+e-→Mn(3+)OOH+OH-。
In yet another aspect, step 1102 forms battery in the charge state, and this battery has Fe(3+)(OH)3First alkali metal (X) negative pole of positive pole and reduction, wherein X is Li, Na or K.Then, include battery discharge in a step 1106 carrying out following reaction:
Negative pole: X=X++e-, and
Positive pole: Fe(3+)(OH)3+e-→Fe(2+)(OH)2+OH-。
In one aspect, battery discharge includes being formed have the lithium ion (Li being dissolved in negative electrode solution in a step 1106+), sodium ion (Na+) or potassium ion (K+) negative electrode solution.
Alkali metal/oxidant cell is together provided with the correlation technique being used for producing battery capacity.Illustrate the embodiment of material and pulp flow structure with this invention of example.But, the present invention is not limited only to these embodiments.For those skilled in the art, will appear from other variant of the present invention and embodiment.
nullAll applications described below are with reference to being incorporated herein: (1) has the circulation metal battery (FLOW-THROUGHMETALBATTERYWITHIONEXCHANGEMEMBRANE) of ion exchange membrane，Invented by YuhaoLu etc.，Serial number 14/042264，Within 30th, submit to JIUYUE in 2013，Attorney Docket Number SLA3294 (2) has the battery (BatterywithLowTemperatureMoltenSalt (LTMS) Cathode) of low temperature molten salt (LTMS) positive pole，Invented by YuhaoLu etc.，Serial number 13/564015，Submit on August 1st, 2012，Attorney Docket Number SLA3165.
Claims (21)
1. alkali metal/oxidant cell, described battery comprises:
Negative pole, it comprises the first alkali metal of reduction under battery charging state；
Negative electrode solution；
Positive pole, it comprises selected from hydroxy nickel oxide (NiOOH), magnesium oxide (IV) (Mn under battery charging state(4+)O2) and FeOOH (III) (Fe(3+)(OH)3) in composition；
Positive pole liquid, it comprises the first alkali metal hydroxide；With
The first permeable barrier film of alkali metal ion, it is placed between described negative electrode solution and described positive pole liquid.
2. alkali metal/oxidant cell according to claim 1, wherein said positive pole comprises nickel hydroxide (II) (Ni (OH) under battery discharge status2), and comprise NiOOH under battery charging state.
3. alkali metal/oxidant cell according to claim 2, wherein said negative electrode solution comprises lithium ion (Li under battery discharge status+)。
4. alkali metal/oxidant cell according to claim 1, wherein said positive pole liquid and just extremely comprise the identical component of anode sizing agent；And
Described positive pole also comprises the cathode collector immersing described anode sizing agent.
5. alkali metal/oxidant cell according to claim 4, also comprises:
Monocell, it comprises described negative pole, described negative electrode solution, the described first permeable barrier film of alkali metal ion, input port and delivery outlet；
Anode sizing agent pond, it is connected to the input of described monocell and delivery outlet, thus when described battery discharges under a load for the anode sizing agent of oxidizing, the anode sizing agent of supply reduction when described battery charges.
6. alkali metal/oxidant cell according to claim 5, also comprises:
Multiple monocells that structure to be selected from series connection and electrical connection in parallel connects.
7. alkali metal/oxidant cell according to claim 6, wherein said anode sizing agent pond and the plurality of monocell are connected in parallel to carry described anode sizing agent.
8. alkali metal/oxidant cell according to claim 1, wherein said negative electrode solution comprises selected from lithium ion (Li under battery discharge status+), sodium ion (Na+) and potassium ion (K+) in alkali metal ion；And
Wherein under battery charging state, described negative pole comprises the alkali metal of the solid phase reduction covering current collector being respectively selected from Li, Na and K.
9. alkali metal/oxidant cell according to claim 1, wherein said positive pole comprises Mn under battery charging state(4+)O2, under battery discharge status, comprise hydroxyl oxidize magnesium (III) (Mn(+3)OOH)。
10. alkali metal/oxidant cell according to claim 1, wherein said positive pole comprises (Fe under battery charging state(3+)(OH)3), under battery discharge status, comprise FeOOH (II) (Fe(2+)(OH)2)。
11. alkali metal/oxidant cell according to claim 1, wherein said positive pole is NiOOH under battery charging state, and utilizes following reaction to develop into battery discharge status from battery charging state:
NiOOH+H2O+e-=Ni (OH)2+OH-。
12. alkali metal/oxidant cell according to claim 1, wherein said positive pole is Mn under battery charging state(4+)O2, and utilize following reaction to develop into battery discharge status from battery charging state:
Mn(4+)O2+H2O+e-→Mn(3+)OOH+OH-。
13. alkali metal/oxidant cell according to claim 1, wherein said positive pole is Fe under battery charging state(3+)(OH)3, and utilize following reaction to develop into battery discharge status from battery charging state:
Fe(3+)(OH)3+e-→Fe(2+)(OH)2+OH-。
14. alkali metal/oxidant cell according to claim 1, wherein said negative pole is selected from the first alkali metal of solid phase reduction and the first alkali metal of the solid phase reduction of covering current collector under battery charging state.
15. for the method producing alkali metal/oxidant cell capacity, described method includes:
Forming battery in the charge state, described battery has the first alkali metal negative pole, negative electrode solution, the first permeable barrier film of alkali metal ion, and comprises selected from hydroxy nickel oxide (NiOOH), magnesium oxide (IV) (Mn(4+)O2) and FeOOH (III) (Fe(3+)(OH)3) in the positive pole of oxidizing component, and comprise the positive pole liquid of the first alkali metal hydroxide；
Producing the first battery capacity, wherein said first battery capacity is in response to the first alkali-metal amount of the oxidizing component in described positive pole and the reduction at described negative pole place.
16. method according to claim 15, being formed with described battery and include being formed when rechargeable battery the first alkali metal (X) negative pole of NiOOH positive pole and reduction, wherein X is selected from lithium (Li), sodium (Na) and potassium (K)；Further,
Described method also includes:
By carrying out following reaction to described battery discharge:
Negative pole: X=X++e-, and
Positive pole: NiOOH+H2O+e-=Ni (OH)2+OH-。
17. method according to claim 15, it is formed with described battery and includes being formed in the charge state Mn(4+)O2First alkali metal (X) negative pole of positive pole and reduction, wherein X is selected from Li, Na and K；Further,
Described method also includes:
By carrying out following reaction to described battery discharge:
Negative pole: X=X++e-, and
Positive pole: Mn(4+)O2+H2O+e-→Mn(3+)OOH+OH-。
18. method according to claim 15, it is formed with described battery and includes being formed in the charge state Fe(3+)(OH)3First alkali metal (X) negative pole of positive pole and reduction, wherein X is selected from Li, Na and K；Further,
Described method also includes:
By carrying out following reaction to described battery discharge:
Negative pole: X=X++e-, and
Positive pole: Fe(3+)(OH)3+e-→Fe(2+)(OH)2+OH-。
19. method according to claim 15, also include:
By forming described negative electrode solution, described battery being discharged, described negative electrode solution comprises the free lithium ion (Li of the choosing being dissolved in described negative electrode solution+), sodium ion (Na+) and potassium ion (K+) ion in form first alkali-metal group.
20. method according to claim 15, it is formed with described battery and includes described positive pole and positive pole liquid becomes anode sizing agent.
21. lithium (Li)/nickel (Ni) battery, described battery comprises:
Negative pole, it comprises the Li of reduction under battery charging state；
Negative electrode solution；
Positive pole, it comprises hydroxyl oxidize Ni (Ni (OH) under battery discharge status2) and under battery charging state, comprise hydroxy nickel oxide (NiOOH)；
Positive pole liquid, it comprises LiOH；With
Lithium ion (Li+) permeable barrier film, it is placed between described negative electrode solution and described positive pole liquid.
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| US14/092,048 | 2013-11-27 | ||
| US14/092,048 US20140075745A1 (en) | 2012-08-01 | 2013-11-27 | High Capacity Alkali/Oxidant Battery |
| PCT/JP2014/005924 WO2015079689A1 (en) | 2013-11-27 | 2014-11-26 | High capacity alkali/oxidant battery |
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| CN109428134A (en) * | 2017-09-01 | 2019-03-05 | 丰田自动车株式会社 | The reuse method and secondary battery system of secondary cell |
| CN112952172A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Alkaline iron-nickel flow battery |
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| KR101865383B1 (en) * | 2016-06-03 | 2018-06-07 | 울산과학기술원 | Rechargeable battery module and method for manufacturing the same |
| JPWO2022102032A1 (en) * | 2020-11-11 | 2022-05-19 |
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