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WO2015064069A1 - Électrode de pile au fer (ii)-hexacyanoferrate (ii) de sodium et procédé de synthèse - Google Patents

Électrode de pile au fer (ii)-hexacyanoferrate (ii) de sodium et procédé de synthèse Download PDF

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WO2015064069A1
WO2015064069A1 PCT/JP2014/005394 JP2014005394W WO2015064069A1 WO 2015064069 A1 WO2015064069 A1 WO 2015064069A1 JP 2014005394 W JP2014005394 W JP 2014005394W WO 2015064069 A1 WO2015064069 A1 WO 2015064069A1
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ions
sodium
solution
hexacyanoferrate
group
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Yuhao Lu
Sean Andrew VAIL
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Sharp Corp
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Sharp Corp
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Priority claimed from US14/067,038 external-priority patent/US9450224B2/en
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Priority to CN201480051249.3A priority Critical patent/CN105555712B/zh
Publication of WO2015064069A1 publication Critical patent/WO2015064069A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • C01C3/12—Simple or complex iron cyanides
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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

Definitions

  • This invention generally relates to electrochemical cells and, more particularly, to a sodium iron(II)-hexacyanoferrate(II) material, iron(II)-hexacyanoferrate(II) battery electrode, and associated fabrication processes.
  • a battery is an electrochemical cell through which chemical energy and electric energy can be converted back and forth. Overall, the energy density of a battery is determined by its voltage and charge capacity. Lithium has the most negative potential (-3.04 V vs. H 2 /H + ), and exhibits the highest gravimetric capacity corresponding to 3860 milliamp-hours per gram (mAh/g). Due to their high energy densities, lithium-ion batteries (LIBs) have triggered the portable electronics revolution. However, both the high cost of lithium metal and the strain on natural resources render doubtful the commercialization of LIBs as large scale energy storage devices. In general, LIBs employ lithium storage compounds as the positive (cathode) and negative (anode) electrode materials.
  • the positive electrode (cathode) material is conventionally a metal oxide with a layered structure, such as lithium cobalt oxide (LiCoO 2 ), or a material having a tunneled structure, such as lithium manganese oxide (LiMn 2 O 4 ) on an aluminum current collector.
  • the negative electrode (anode) typically consists of graphitic carbon, also a layered material, on a copper current collector.
  • metal-ion batteries employ metal-ion host compounds as their electrode materials into which metal-ions can migrate both easily and reversibly. Since Li + has one of the smallest radii among metal ions, it is easily accommodated within the interstitial spaces of various materials including layered LiCoO 2 , olivine-structured LiFePO 4 , spinel-structured LiMn 2 O 4 , and so on.
  • Fig. 1 is a diagram depicting the crystal structure of a transition metal hexacyanoferrate (TMHCF) in the form of A x M1M2(CN) 6 (prior art).
  • Transition metals are defined as elements whose atoms possess an incomplete d sub-shell or can give rise to cations (transition metal ions) with an incomplete d shell and include Groups 3 to 12 of the Periodic Table.
  • the crystal structure of TMHCFs exhibits an open framework and is analogous to that of the ABX 3 perovskite, as shown.
  • M 1 and M 2 are transition metal ions in an ordered arrangement on the B sites.
  • the large, tetrahedrally coordinated A sites can host both alkali and alkaline earth ions (A x ) in addition to species such as H 2 O.
  • the open framework structure of the TMHCFs facilitates both rapid and reversible intercalation processes for alkali and alkaline earth ions (A x ).
  • Transition metal hexacyanoferrates with large interstitial spaces have been investigated as cathode materials for rechargeable lithium-ion batteries [NPL 1,2], sodium-ion batteries [NPL 3,4], and potassium-ion batteries [NPL 5].
  • NPL 1,2 lithium-ion batteries
  • NPL 3,4 sodium-ion batteries
  • NPL 5 potassium-ion batteries
  • a method for synthesizing sodium iron(II)-hexacyanoferrate(II) comprising: preparing a first solution including sodium ions; mixing a Fe(CN) 6 material with the first solution and a first element selected from a group consisting of an anti-oxidant and a reducing agent; forming sodium iron(II)-hexacyanoferrate(II) (Na1+XFe[Fe(CN)6] Z .mH 2 O), where x and z are each less than or equal to 1; and, where m is in a range between 0 and 7.
  • a sodium iron(II)-hexacyanoferrate(II) battery electrode comprising: a current collector; sodium iron(II)-hexacyanoferrate(II) (Na 1+X Fe[Fe(CN) 6 ] Z .mH 2 O) overlying the current collector, where x and z are each less than or equal to 1; and, where m is in a range of 0 to 7.
  • a sodium iron(II)-hexacyanoferrate(II) battery comprising: a cathode comprising: a current collector; sodium iron(II)-hexacyanoferrate(II) (Na 1+X Fe[Fe(CN) 6 ] Z .mH 2 O) overlying the current collector, where x and z are each less than or equal to 1; where m is in a range of 0 to 7; an anode; an electrolyte; and, an ion-permeable membrane.
  • Fig. 1 is a diagram depicting the crystal structure of a transition metal hexacyanoferrate (TMHCF) in the form of A x M1M2(CN) 6 (prior art).
  • Fig. 2 is a partial cross-sectional view of a sodium iron(II)-hexacyanoferrate(II) battery electrode.
  • Fig. 3A is schematic drawings of Na 1+X Fe[Fe(CN) 6 ] Z .MH 2 O.
  • Fig. 3B is schematic drawings of Na 1+X A Y Fe[Fe(CN) 6 ] Z .MH 2 O.
  • Fig. 4 is a partial cross-sectional view of a battery employing the battery electrode of Fig. 2.
  • Fig. 1 is a diagram depicting the crystal structure of a transition metal hexacyanoferrate (TMHCF) in the form of A x M1M2(CN) 6 (prior art).
  • Fig. 2 is a partial cross-sectional view
  • FIG. 5 is a graph representing the electrochemical behavior of Na 1+X Fe[Fe(CN) 6 ] Z synthesized by a conventional precipitation method that mixes a Fe 2+ solution and a ferrocyanide solution.
  • Fig. 6 is an x-ray diffraction (XRD) pattern of a NaFe 2 (CN) 6 sample prepared using a method purportedly able to produce K 2 Fe 2 (CN) 6 .
  • Fig. 7 is a schematic diagram depicting the structure of ascorbic acid, which is a common anti-oxidant.
  • Fig. 8 is a XRD pattern for Na 1+X Fe[Fe(CN) 6 ] Z synthesized using a hydrothermal process including ascorbic acid in the reaction solution.
  • Fig 10 is a flowchart illustrating method for synthesizing sodium iron(II)-hexacyanoferrate(II).
  • Described herein is a hydrothermal reaction process for directly synthesizing sodium iron (II)-hexacyanoferrate(II) ( Na 1+X Fe[Fe 2 (CN) 6 ]).
  • reducing agents and/or anti-oxidants are integrated into the reaction solutions.
  • Fe (II) in the reaction solution is protected from oxidization by the presence of reducing agents/anti-oxidants.
  • Na 1+X Fe[Fe 2 (CN) 6 ] can be directly used as a cathode in sodium-ion batteries with a non-sodium anode to achieve high capacity.
  • Reducing agents or anti-oxidants are included within the hydrothermal reaction solutions to protect iron (II) from oxidization, which allows more sodium-ions to be retained in the Fe-HCF structure.
  • reaction solution can be weakly acidic, although it is not necessary.
  • Na 1+X Fe[Fe(CN) 6 ] can be directly employed as a cathode material in sodium-ion batteries with a non-sodium metal anode.
  • a method for synthesizing sodium iron(II)-hexacyanoferrate(II).
  • the method prepares a first solution including sodium ions, where the sodium ions are derived from a material such as sodium nitrite, sodium nitrate, sodium chloride, sodium carbonate, sodium acetate, sodium phosphate, sodium thiosulfate, sodium iodide, sodium bisulfite, sodium sulfite, sodium bromide, sodium fluoride, or combinations thereof.
  • the first solution may include an aqueous solvent, non-aqueous solvent, or a combination thereof.
  • a Fe(CN) 6 material is mixed with the first solution and either an anti-oxidant or a reducing agent.
  • the Fe(CN) 6 material may be either ferrocyanide ([Fe(CN) 6 ] 4- ) or ferricyanide ([Fe(CN) 6 ] 3- ).
  • Potential anti-oxidants and reducing agents include monosaccharides, disaccharides, glucose, ascorbic acid, formic acid, alcohols, oxalic acid, aldehydes, ketones, organic compounds having reducing properties, inorganic compounds having reducing properties, or combinations thereof.
  • the first solution including includes A ions, such as alkali metal ions, alkaline earth metal ions, or combinations thereof, resulting in the formation of Na 1+X A Y Fe[Fe(CN) 6 ] Z .mH 2 O, where y is less than or equal to 1.
  • Fig. 2 is a partial cross-sectional view of a sodium iron(II)-hexacyanoferrate(II) battery electrode.
  • the battery electrode 200 comprises a current collector 202 and sodium iron(II)-hexacyanoferrate(II) (Na 1+X Fe[Fe(CN) 6 ] Z .mH 2 O) 204 overlying the current collector, where x and z are each less than or equal to 1; and, where m is in a range of 0 to 7.
  • the sodium iron(II)-hexacyanoferrate(II) 204 additionally comprises A ions such as alkali metal ions, alkaline earth metal ions, or combinations thereof, forming Na 1+X A Y Fe[Fe(CN) 6 ] Z .mH 2 O, where y is less than or equal to 1.
  • the A ions may be lithium ions (Li + ), sodium ions (Na + ), potassium ions (K + ), rubidium ions (Rb + ), cesium ions (Cs + ), beryllium ions (Be + ), magnesium ions (Mg + ), calcium ions (Ca + ), strontium ions (Sr + ), or barium ions (Ba + ).
  • alkali metal refers to elements in Group 1 of the Periodic Table which exhibit a tendency to form ions with a single positive charge (alkali metal ions) through loss of an electron.
  • Alkaline earth metals include those elements in Group 2 of the Periodic Table which readily lose two electrons to form species with a 2+ charge (alkaline earth metal ions).
  • the battery electrode 200 may also include a conductor (not shown), such as a carbonaceous material including carbon black, carbon nanotubes, carbon fibers, etc., to improve electrical conductivity between the sodium iron(II)-hexacyanoferrate(II) 204, and between the sodium iron(II)-hexacyanoferrate(II) 204 and the current collector 202.
  • the battery electrode 200 may also include a polymeric binder (not shown), such as polytetrafluoroethylene (PTFE) or polyvinylidene difluoride (PVDF) to provide adhesion between electrode components/current collector and improve the overall physical stability and form of the battery electrode.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene difluoride
  • Figs. 3A and 3B are, respectively, schematic drawings of Na 1+X Fe[Fe(CN) 6 ] Z .mH 2 O and Na 1+X A Y Fe[Fe(CN) 6 ] Z .mH 2 O.
  • Fig. 4 is a partial cross-sectional view of a battery employing the battery electrode of Fig. 2.
  • the battery 400 comprises a cathode (positive) battery electrode 401, an electrolyte 402, and an anode (negative) battery electrode 406.
  • Either the cathode battery electrode 401 or the anode battery electrode 406 is made from sodium iron(II)-hexacyanoferrate(II) overlying a current collector , as described above in the explanation of Fig 2.
  • the cathode 401 can be made from a sodium iron(II)hexacyanoferrate(II) material while the anode 406 is made with a TMHCF material other than sodium iron(II)-hexacyanoferrate(II).
  • the designation of an electrode as an anode or a cathode is arbitrary, based upon the relative potentials of the two TMHCF materials.
  • the electrolyte 402 may be non-aqueous, such as an organic liquid electrolyte, or alternatively, gel electrolyte, polymer electrolyte, solid (inorganic) electrolyte, etc.
  • non-aqueous (liquid) electrolytes include organic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), etc., although many other organic carbonates and alternatives to organic carbonates exist.
  • gel electrolytes consist of polymeric materials which have been swelled in the presence of liquid electrolytes.
  • polymers employed as gel electrolytes include, but are not limited to, poly(ethylene)oxide (PEO) and fluorinated polymers such as poly(vinylidene) fluoride (PVDF)-based polymers and copolymers, etc.
  • (solid) polymer electrolytes may be prepared using the same classes of polymers for forming gel electrolytes although swelling of the polymer in liquid electrolytes is excluded.
  • solid inorganic (or ceramic) materials may be considered as electrolytes, which may be employed in combination with liquid electrolytes.
  • the appropriate electrolyte system may consist of combinations (hybrid) of the above classes of materials in a variety of configurations. Otherwise, an aqueous electrolyte compatible with the sodium iron(II)-hexacyanoferrate(II) may be used.
  • An ion-permeable membrane 404 is interposed between the cathode 200a and the anode 200b. In some instances not shown, the ion-permeable membrane and the electrolyte can be the same material, as may be the case for polymer gel, polymer, and solid electrolytes.
  • the cathode battery electrode 401 is made from sodium iron(II)-hexacyanoferrate(II), as described above, the anode battery electrode 406 may be made from a sodium metal, a metal (other than sodium), metal alloy, non-metal material, and/or a polymer material.
  • the electrodes described above are the result of an improved hydrothermal reaction strategy to synthesize sodium iron(II)-hexacyanoferrate (Na 1+X Fe[Fe(CN) 6 ] Z ).
  • metal hexacyanoferrates can be synthesized in a straightforward method using a standard precipitation method. Briefly, a solution containing metal-ions is dropped (added) into a ferrocyanide/ferricyanide solution to afford the metal hexacyanometallate material.
  • the precipitation method is not readily applicable to the preparation of Fe(II) hexacyanoferrate (II) (Fe-HCF) synthesis since Fe(II) is readily oxidized in the solution even under inert (nitrogen) atmosphere.
  • Fig. 5 is a graph representing the electrochemical behavior of Na 1+X Fe[Fe 2 (CN) 6 ] Z synthesized by a conventional precipitation method that mixes a Fe 2+ solution and a ferrocyanide solution.
  • the material demonstrated a capacity of 40.85 mAh/g, which corresponds to 0.52 Na + -ions per formula.
  • thermogravimetric analysis (TGA) analysis confirmed the presence of 2.79 water molecules per formula.
  • the molecular formula can be calculated to be Na 0.52 Fe III [Fe II (CN) 6 ] 1-y 2.79H 2 O (y ⁇ 1).
  • TGA thermogravimetric analysis
  • Fig. 6 is an x-ray diffraction (XRD) pattern of a NaFe 2 (CN) 6 sample prepared using a method purportedly able to produce K 2 Fe 2 (CN) 6 .
  • XRD x-ray diffraction
  • the product was determined to be a mixture of NaFe 2 (CN) 6 , Fe 3 O 4 , and iron(III) oxide (Fe 2 O 3 ), although all peaks of Fe 2 O 3 exhibited a small displacement to the low angles.
  • Some displacement is normal in XRD experiments, due to instrument accuracy and calibration, sample surface irregularities, and changes in the size of the crystal under examination.
  • the XRD pattern of the synthesized NaFe 2 (CN) 6 sample (top) showing peaks and peak locations
  • the standard (known) peak locations for Fe 3 O 4 (middle) and Fe 2 O 3 (bottom) are shown.
  • Fig. 7 is a schematic diagram depicting the structure of ascorbic acid, which is a common anti-oxidant.
  • ascorbic acid was added into the hydrothermal reaction solution.
  • oxygen radicals O .
  • ascorbic acid ions react with oxygen radicals (O . ) to effectively remove oxidizing species from the reaction solution according to the following:
  • Fig. 8 is a XRD pattern for sodium Fe(II)-HCF(II) synthesized using a hydrothermal process including ascorbic acid in the reaction solution. Accordingly, Fe(II) was protected from oxidation and sodium Fe(II)-HCF(II) was formed. Unlike NaFe 2 (CN) 6 , with a cubic structure, sodium Fe(II)-CHF(II) exhibits a rhombohedral structure.
  • Fig. 9 is a graph depicting the charge/discharge curves for batteries using Na 1+X Fe[Fe(CN) 6 ] Z material synthesized using a hydrothermal process including ascorbic acid in the reaction solution. Based upon a first charge capacity of 135 mAh/g, the number of sodium could be calculated to be ⁇ 1.6 per formula. In other words, the formula of sodium Fe(II)-HCF(II) could be designated as Na 1.6 Fe[Fe(CN) 6 ]mH 2 O.
  • Fig 10 is a flowchart illustrating method for synthesizing sodium iron(II)-hexacyanoferrate(II). Although the method is depicted as a sequence of numbered steps for clarity, the numbering does not necessarily dictate the order of the steps. It should be understood that some of these steps may be skipped, performed in parallel, or performed without the requirement of maintaining a strict order of sequence. Generally however, the method follows the numeric order of the depicted steps. The method starts at Step 1000.
  • Step 1002 prepares a first solution including sodium ions.
  • the sodium ions may be derived from materials such as sodium nitrite, sodium nitrate, sodium chloride, sodium carbonate, sodium acetate, sodium phosphate, sodium thiosulfate, sodium iodide, sodium bisulfite, sodium sulfite, sodium bromide, sodium fluoride, or combinations thereof.
  • Step 1004 mixes a Fe(CN) 6 material with the first solution and a first element, which is either an anti-oxidant or a reducing agent.
  • the Fe(CN) 6 material may be either ferrocyanide ([Fe(CN) 6 ] 4- ) or ferricyanide ([Fe(CN) 6 ] 3- ).
  • an anti-oxidant is defined as a material that inhibits oxidation. Anti-oxidants function to remove free radical intermediates generated during oxidation processes as well as inhibit other oxidation reactions.
  • a reducing agent is defined as a species that donates an electron to another species in an oxidation-reduction (redox) reaction. Consequently, the reducing agent is itself oxidized in the process since electron(s) have been forfeited.
  • agents that can function as anti-oxidants and/or reducing agents including monosaccharides (glucose, glyceraldehyde, galactose), disaccharides (lactose, maltose), starch, ascorbic acid, formic acid, alcohols, oxalic acid, aldehydes, ketones, organic compounds having reducing properties, and inorganic compounds having reducing properties.
  • reducing sugars reducing mono- and di-saccharides
  • reducing mono- and di-saccharides are characterized by ⁇ open-chain ⁇ forms containing an aldehyde group or, alternatively, containing a ketone group that can provide an aldehyde group via isomerization.
  • the aldehyde group of the reducing sugar can be oxidized via a redox reaction through which a separate material is reduced in the process.
  • Starches are glucose polymers that may contain an abundance of aldehyde groups.
  • Ascorbic acid is a naturally occurring anti-oxidant that represents a form of Vitamin C. Since formic acid in a deprotonated form breaks into hydride and carbon dioxide, it can function as a reducing agent.
  • Oxalic acid can function as a reducing agent by donating electrons during which process it is transformed (oxidized) to carbon dioxide.
  • Step 1006 forms sodium iron(II)-hexacyanoferrate(II) (Na 1+X Fe[Fe(CN) 6 ] Z .mH 2 O), where x and z are each less than or equal to 1; and, where m is in a range between 0 and 7.
  • preparing the first solution in Step 1002 includes the first solution comprising a solvent such as an aqueous solvent, non-aqueous solvent, or combinations thereof.
  • mixing the Fe(CN) 6 material with the first solution and the first element in Step 1004 includes heating at a temperature in a range between about 20 and 1000 degrees centigrade, forming an intermediate product. The mixing of the Fe(CN) 6 material with the first solution and the first element may occur for a duration in the range of 1 hour to 1 month. Further, the mixing may performed by stirring, agitating, or shaking.
  • Step 1005a subsequent to forming the intermediate product, Step 1005a washes the intermediate product in a solution such as an aqueous solution, non-aqueous solution, or combinations thereof.
  • Step 1005b dries the intermediate product at a temperature in a range between about 20 and 200 degrees centigrade. In one aspect, Step 1005b dries the intermediate product under vacuum at a pressure in a range between 0.001 mTorr and 30 Torr.
  • the separation of the intermediate product from the wash solution prior to drying may be performed using a number of conventional processes including, but not limited to, filtration and centrifugation.
  • preparing the first solution in Step 1002 includes the first solution comprising A ions such as alkali metal ions, alkaline earth metal ions, or combinations thereof.
  • Step 1006 forms Na 1+X A Y Fe[Fe(CN) 6 ] Z .mH 2 O, where y is less than or equal to 1.
  • the A ions may be lithium ions (Li + ), sodium ions (Na + ), potassium ions (K + ), rubidium ions (Rb + ), cesium ions (Cs + ), beryllium ions (Be + ), magnesium ions (Mg + ), calcium ions (Ca + ), strontium ions (Sr + ), or barium ions (Ba + ).
  • TRANSITION METAL HEXACYANOMETALLATE-CONDUCTIVE POLYMER COMPOSITE invented by Sean Vail et al., Serial No. 14/059,599, filed October 22, 2013, attorney docket No. SLA3336.
  • METAL-DOPED TRANSITION METAL HEXACYANOFERRATE (TMHCF) BATTERY ELECTRODE invented by Yuhao Lu et al., Serial No. 13/907,892, filed June 1, 2013, attorney docket No. SLA3287.
  • TRANSITION METAL HEXACYANOFERRATE BATTERY CATHODE WITH SINGLE PLATEAU CHARGE/DISCHARGE CURVE invented by Yuhao Lu et al., Serial No. 13/752,930, filed January 29, 2013, attorney docket No. SLA3265.
  • SUPERCAPACITOR WITH HEXACYANOMETALLATE CATHODE, ACTIVATED CARBON ANODE, AND AQUEOUS ELECTROLYTE invented by Yuhao Lu et al., Serial No. 13/603,322, filed September 4, 2012, attorney docket No. SLA3212.

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Abstract

L'invention concerne un procédé pour synthétiser du fer (II)-hexacyanoferrate (II) de sodium. Un matériau de type Fe(CN)6 est mélangé avec une première solution et soit avec un antioxydant, soit avec un agent de réduction. Le matériau de type Fe(CN)6 peut être soit le ferrocyanure ([Fe(CN)6]4-), soit le ferricyanure ([Fe(CN)6]3-). Il s'ensuit que du fer (II)-hexacyanoferrate (II) de sodium (Na1+XFe[Fe(CN)6]Z.mH2O se forme, x étant inférieur ou égal à 1 et m se situant dans une plage entre 0 et 7. Dans un aspect, la première solution comprend des ions A, tels que des ions de métal alcalin, de métal alcalino-terreux ou des combinaisons correspondantes, ce qui entraîne la formation de Na1+XAYFe[Fe(CN)6]Z.mH2O, y étant inférieur ou égal à 1. Une pile au Na1+XFe[Fe(CN)6]Z.mH2O et une électrode de pile au Na1+XFe[Fe(CN)6]Z.mH2O sont également décrites.
PCT/JP2014/005394 2013-10-30 2014-10-23 Électrode de pile au fer (ii)-hexacyanoferrate (ii) de sodium et procédé de synthèse Ceased WO2015064069A1 (fr)

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US14/067,038 US9450224B2 (en) 2012-03-28 2013-10-30 Sodium iron(II)-hexacyanoferrate(II) battery electrode and synthesis method

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CN112786828A (zh) * 2021-02-22 2021-05-11 宁波容百新能源科技股份有限公司 一种高压实密度高倍率性能的普鲁士类正极片、其制备方法及钠离子电池
CN115188607A (zh) * 2022-06-20 2022-10-14 浙江师范大学 一种缺陷型Fe3O4@Fe电极材料及其制备方法
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CN112786828A (zh) * 2021-02-22 2021-05-11 宁波容百新能源科技股份有限公司 一种高压实密度高倍率性能的普鲁士类正极片、其制备方法及钠离子电池
CN115188607A (zh) * 2022-06-20 2022-10-14 浙江师范大学 一种缺陷型Fe3O4@Fe电极材料及其制备方法
WO2024119235A1 (fr) * 2022-12-07 2024-06-13 Proton Systems Pty Limited Cathode pour batteries à protons et procédé de fabrication
CN118895539A (zh) * 2024-06-24 2024-11-05 合肥国轩高科动力能源有限公司 一种铁氰化锌钾/碳布复合电极材料的制备方法及应用

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