[go: up one dir, main page]

WO2014178171A1 - Électrode de batterie d'hexacyanoferrate modifiée par des ferrocyanures ou des ferricyanures - Google Patents

Électrode de batterie d'hexacyanoferrate modifiée par des ferrocyanures ou des ferricyanures Download PDF

Info

Publication number
WO2014178171A1
WO2014178171A1 PCT/JP2014/002195 JP2014002195W WO2014178171A1 WO 2014178171 A1 WO2014178171 A1 WO 2014178171A1 JP 2014002195 W JP2014002195 W JP 2014002195W WO 2014178171 A1 WO2014178171 A1 WO 2014178171A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
battery
group
tmhcf
additive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/002195
Other languages
English (en)
Inventor
Yuhao Lu
Jong-Jan Lee
David Evans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sharp Corp
Original Assignee
Sharp Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/872,673 external-priority patent/US9246164B2/en
Priority claimed from US13/897,492 external-priority patent/US9099719B2/en
Application filed by Sharp Corp filed Critical Sharp Corp
Priority to EP14792239.7A priority Critical patent/EP2992563A4/fr
Priority to CN201480024742.6A priority patent/CN105164833B/zh
Publication of WO2014178171A1 publication Critical patent/WO2014178171A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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

Definitions

  • This invention generally relates to electrochemical cells and, more particularly, to a transition-metal hexacyanoferrate (TMHCF) battery electrode with Fe(CN) 6 additives, and associated fabrication processes.
  • THCF transition-metal hexacyanoferrate
  • a battery is an electrochemical cell through which chemical energy and electric energy can be converted back and forth.
  • the energy density of a battery is determined by its voltage and charge capacity.
  • Lithium has the most negative potential of -3.04 V vs. H 2 /H + , and has the highest gravimetric capacity of 3860 milliamp-hours per gram (mAh/g). Due to their high energy densities, lithium-ion batteries have led the portable electronics revolution. However, the high cost of lithium metal renders doubtful the commercialization of lithium batteries as large scale energy storage devices. Further, the demand for lithium and its reserve as a mineral have raised the need to build other types metal-ion batteries as an alternative.
  • Lithium-ion (Li-ion) batteries employ lithium storage compounds as the positive (cathode) and negative (anode) electrode materials. As a battery is cycled, lithium ions (Li + ) are exchanged between the positive and negative electrodes. Li-ion batteries have been referred to as rocking chair batteries because the lithium ions "rock" back and forth between the positive and negative electrodes as the cells are charged and discharged.
  • the positive electrode (cathode) material is typically 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) material is typically a graphitic carbon, also a layered material, on a copper current collector. In the charge-discharge process, lithium ions are inserted into, or extracted from interstitial spaces of the active materials.
  • metal-ion batteries use the metal-ion host compounds as their electrode materials in which metal-ions can move easily and reversibly.
  • a Li + -ion it has one of the smallest radii of all metal ions and is compatible with the interstitial spaces of many materials, such as the layered LiCoO 2 , olivine-structured LiFePO 4 , spinel-structured LiMn 2 O 4 , and so on.
  • Other metal ions such as Na + , K + , Mg 2+ , Al 3+ , Zn 2+ , etc., with large sizes, severely distort Li-based intercalation compounds and ruin their structures in several charge/discharge cycles. Therefore, new materials with large interstitial spaces would have to be used to host such metal-ions in a metal-ion battery.
  • 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).
  • TMHCF transition metal hexacyanoferrate
  • NPL1,2 lithium-ion batteries
  • NPL3,4 sodium-ion batteries
  • NPL5 potassium-ion batteries
  • Mn-HCF manganese hexacyanoferrate
  • Fe-HCF iron hexacyanoferrate
  • TMHCF has demonstrated high capacity and energy density with a non-aqueous electrolyte, its cycling life is short, especially for a paste-type Mn-HCF electrode [NPL11].
  • TMHCF can be expressed as A x M y Fe z (CN) n .mH 2 O, in which A is alkali-ion or alkaline-ion, and M indicates one or several transition metals. Due to large interstitial spaces, it is inevitable that water molecules exist in the TMHCF formulation.
  • M y Fe z (CN) n .mH 2 O constitutes the TMHCF framework into/from which "A" can be easily inserted/extracted.
  • the stability of the framework determines the TMHCF cycling life.
  • solid state TMHCF has the following dynamic equilibrium with a liquid electrolyte:
  • a x M y Fe z (CN) n .mH 2 O xA a+ + yM b- + [Fe z (CN) n ] c- + mH 2 O.
  • TMHCF has a tendency to dissolve into the electrolyte, which changes the surface structures of TMHCF.
  • alkali-ions or alkaline-ions are extracted from TMHCF, the dissolution of TMHCF can be aggravated and the cycling life shortened.
  • TMHCF cathode could be treated or modified in such a manner as to support the lattice structure through multiple cycles of charge and discharge.
  • a transition metal hexacyanoferrate (TMHCF) battery electrode with a Fe(CN) 6 additive comprising: a metal current collector; A x M y Fe z (CN) n .mH 2 O particles overlying the current collector; where A cations are selected from a group consisting of alkali and alkaline-earth cations; where M is a transition metal; where x is in a range of 0 to 2; where y is in a range of 0 to 2; where z is in a range of 0.1 to 2; where n is in a range of 1 to 6; where m is in a range of 0 to 7; and, a Fe(CN) 6 additive modifying the A x M y Fe z (CN) n .mH 2 O particles.
  • THCF transition metal hexacyanoferrate
  • a transition metal hexacyanoferrate (TMHCF) battery with a Fe(CN) 6 additive comprising: a cathode comprising: a metal current collector; A x M y Fe z (CN) n .mH 2 O particles overlying the current collector; where A cations are selected from a group consisting of alkali and alkaline-earth cations; where M is a transition metal; where x is in a range of 0 to 2; where y is in a range of 0 to 2; where z is in a range of 0.1 to 2; where n is in a range of 1 to 6; where m is in a range of 0 to 7; an anode selected from a group consisting of an A ⁇ metal, an A ⁇ metal containing composite, and a material that can host A ⁇ atoms, where A ⁇ cations are selected from a group consisting of alkali and alkaline-earth
  • a method for synthesizing a transition metal hexacyanoferrate (TMHCF) battery electrode with a Fe(CN) 6 additive comprising: synthesizing a A x M y Fe z (CN) n .mH 2 O powder; where A cations are selected from a group consisting of alkali and alkaline-earth cations; where M is a transition metal; where x is in a range of 0 to 2; where y is in a range of 0 to 2; where z is in a range of 0.1 to 2; where n is in a range of 1 to 6; where m is in a range of 0 to 7; mixing the A x M y Fe z (CN) n .mH 2 O powder with a conducting carbon and an organic binder in an organic solution, creating a mixture; adding Fe(CN) 6 to the mixture, forming a modified mixture; and, forming the modified mixture with Fe(
  • a method for fabricating a transition metal hexacyanoferrate (TMHCF) battery with a Fe(CN) 6 additive comprising: providing a battery comprising: a cathode with A x M y Fe z (CN) n .mH 2 O particles overlying a current collector; an anode selected from a group consisting of an A ⁇ metal, an A ⁇ metal containing composite, and a material that can host A ⁇ atoms; an electrolyte; adding a Fe(CN) 6 additive to a component selected from a group consisting of the cathode, the anode, and the electrolyte; and, forming a TMHCF battery with Fe(CN) 6 additive.
  • 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).
  • Figs. 2A is a partial cross-sectional view of a transition metal hexacyanoferrate (TMHCF) battery electrode with a Fe(CN) 6 additive.
  • Figs. 2B is a partial cross-sectional view of a A x M y Fe z (CN) n .mH 2 O particle in detail.
  • Fig. 3 is a partial cross-sectional view of a TMHCF battery with a Fe(CN) 6 additive.
  • 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).
  • Figs. 2A is a partial cross-sectional view of a transition metal hexa
  • FIG. 4A is a graph depicting the charge/discharge profiles of Mn-HCF and Na 4 Fe(CN) 6 mixed Mn-HCF electrodes.
  • Fig. 4B is a graph depicting the charge/discharge profiles of Mn-HCF and Na 4 Fe(CN) 6 mixed Mn-HCF electrodes.
  • Fig. 5A depicts the performance of Mn-HCF in a saturated NaClO 4 ethylene carbonate (EC)/diethyl carbonate (DEC) electrolyte with and without Na 4 Fe(CN) 6 .
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • FIG. 5B depicts the performance of Mn-HCF in a saturated NaClO 4 ethylene carbonate (EC)/diethyl carbonate (DEC) electrolyte with and without Na 4 Fe(CN) 6 .
  • Fig. 6 is a flowchart illustrating a method for synthesizing a TMHCF battery electrode with a Fe(CN) 6 additive.
  • Fig. 7 is a flowchart illustrating a method for fabricating a TMHCF battery with a Fe(CN) 6 additive.
  • ferrocyanides or ferricyanides as additives in rechargeable batteries with a transition metal hexacyanoferrate (TMHCF) electrode, which improves the performance of the electrode in a non-aqueous electrolyte.
  • THCF transition metal hexacyanoferrate
  • Ferrocyanides or ferricyanides, A x Fe(CN) 6 (x 3 or 4), dissociate to A + and Fe(CN) 6 3- or Fe(CN) 6 4- ions.
  • TMHCF can be represented as A x M y Fe z (CN) n .mH 2 O, with A being selected from alkali or alkaline metals, and where M can be one or several transition metals.
  • ferrocyanides or ferricyanides improves the capacity of the TMHCF and its capacity retention.
  • a TMHCF battery electrode is provided with a Fe(CN) 6 additive.
  • the electrode is made from A x M y Fe z (CN) n .mH 2 O particles overlying a current collector, where the A cations are either alkali and alkaline-earth cations such as sodium (Na), potassium (K), calcium (Ca), or magnesium (Mg), and where: M is a transition metal; x is in the range of 0 to 2; y is in the range of 0 to 2; z is in the range of 0.1 to 2; n is in the range of 1 to 6; and, m is in the range of 0 to 7.
  • a Fe(CN) 6 additive modifies the A x M y Fe z (CN) n .mH 2 O particles.
  • the Fe(CN) 6 additive may be ferrocyanide ([Fe(CN) 6 ] 4- ) or ferricyanide ([Fe(CN) 6 ] 3- ).
  • the above described electrode may be a cathode.
  • the battery is also made up of an electrolyte and an anode, which may include an A ⁇ metal, an A ⁇ metal containing composite, or a material that can host A ⁇ atoms.
  • the A ⁇ cations are either alkali or alkaline-earth cations, and A is not necessarily the same material as A ⁇ .
  • the electrolyte may be an organic solvent containing A-atom salts, A ⁇ -atom salts, or a combination of the above-mentioned salts.
  • the Fe(CN) 6 may be added to the cathode, the anode, or electrolyte, or in a combination of the above-mentioned components.
  • the method synthesizes a A x M y Fe z (CN) n .mH 2 O powder, and mixes the A x M y Fe z (CN) n .mH 2 O powder with a conducting carbon and an organic binder in an organic solution, creating a mixture.
  • Fe(CN) 6 is added to the mixture, forming a modified mixture. Finally, the modified mixture with Fe(CN) 6 is formed on a metal current collector, creating an electrode.
  • Figs. 2A and 2B are, respectively, a partial cross-sectional view of a transition metal hexacyanoferrate (TMHCF) battery electrode with a Fe(CN) 6 additive, and a A x M y Fe z (CN) n .mH 2 O particle in detail.
  • the electrode 200 comprises a metal current collector 202.
  • a x M y Fe z (CN) n .mH 2 O particles 204 overlie the current collector 202.
  • the A cations are either alkali or alkaline-earth cations, such as sodium (Na), potassium (K), calcium (Ca), or magnesium (Mg), where: M is a transition metal; x is in the range of 0 to 2; y is in the range of 0 to 2; z is in the range of 0.1 to 2; n is in the range of 1 to 6; and, m is in the range of 0 to 7.
  • a Fe(CN) 6 additive 206 modifies the A x M y Fe z (CN) n .mH 2 O particles.
  • the electrode 200 further comprises carbon black conductor particles 208.
  • the Fe(CN) 6 additive 206 is either ferrocyanide ([Fe(CN) 6 ] 4- ) or ferricyanide ([Fe(CN) 6 ] 3- ).
  • Fig. 3 is a partial cross-sectional view of a TMHCF battery with a Fe(CN) 6 additive.
  • the battery 300 comprises a cathode.
  • the battery cathode is the same as the TMHCF electrode described above in the explanation of Figs. 2A and 2B.
  • the electrode 200 (in Fig. 3 a cathode) comprises a metal current collector 202 and A x M y Fe z (CN) n .mH 2 O particles 204 overlying the current collector 202.
  • the A cations are either alkali or alkaline-earth cations, such as Na, K, Ca, or Mg, where: M is a transition metal; x is in the range of 0 to 2; y is in the range of 0 to 2; z is in the range of 0.1 to 2; n is in the range of 1 to 6; and, m is in the range of 0 to 7.
  • the battery 300 further comprises an anode 302 including an A ⁇ metal, an A ⁇ metal containing composite, or a material that can host A ⁇ atoms.
  • a ⁇ cations are either alkali or alkaline-earth cations, such as Na, K, Ca, or Mg. However, A ⁇ need not necessarily be the same element as A.
  • the battery 300 also comprises an electrolyte 304 that may include A-atom salts, A ⁇ -atom salts, or a combination of the above-mentioned salts.
  • the electrolyte 304 fills unoccupied regions around each cathode 200 and anode 302, and a separator 306 is formed between each anode 302 and cathode 200.
  • a Fe(CN) 6 additive modifies the A x M y Fe z (CN) n .mH 2 O particles 204 in the cathode 200.
  • the Fe(CN) 6 may be added to the cathode 200, the anode 302, electrolyte 304, or combinations of the above-mentioned components.
  • the Fe(CN) 6 additive 206 may be either ferrocyanide ([Fe(CN) 6 ] 4- ) or ferricyanide ([Fe(CN) 6 ] 3- ).
  • Fig. 3 depicts one style of battery comprised of a number of cells as an example.
  • the TMHCF battery with Fe(CN) 6 additive is not limited to any particular style of design of battery.
  • TMHCF has the general formula of A x M y Fe z (CN) n .mH 2 O, in which A is alkali-ion or alkaline-ion that can freely move in the structures of TMHCF.
  • a x M y Fe z (CN) n .mH 2 O xA a+ + [M y Fe z (CN) n .mH 2 O] xa- + xae - (1)
  • M y Fe z (CN) n .mH 2 O constitutes the TMHCF framework into/from which A-ions can be easily inserted/extracted.
  • the stability of the framework determines the TMHCF cycling life.
  • TMHCF can also dissolve into the electrolyte. As this happens, the structure of TMHCF electrode starts to collapse from the surface, which shortens the cycling lives of the batteries.
  • ferrocyanides or ferricyanides can be used as additives in rechargeable batteries with TMHCF electrodes to address this problem.
  • a ⁇ can be the same as or different from A in TMHCF.
  • Dissociation of ferrocyanides/ferricyanides maintains a high concentration of Fe(CN) 6 3- /Fe(CN) 6 4- that pushes Equation 2 backward to stabilize the TMHCF structures.
  • Fe(CN) 6 3- or Fe(CN) 6 4- -ions can re-constitute the surface of TMHCF electrodes. As soon as M-ions exit from the surface of the TMHCF electrode, as shown in Equation 2, they react with Fe(CN) 6 3- or Fe(CN) 6 4 -ions to reconstitute the [M y Fe z (CN) n .mH 2 O framework again. Therefore, the performance of TMHCF electrodes is improved.
  • Ferrocyanides or ferricyanides can be added using two different approaches.
  • One approach is to directly mix ferrocyanides or ferricyanides with TMHCF electrode during fabrication, and the other approach is to dissolve ferrocyanides/ferricyanides into the electrolyte.
  • the TMHCF electrodes are made of TMHCF, binder, electronic conductor, and ferrocyanides/ferricyanides.
  • the content of the ferrocyanides/ferricyanides can be from 0 to 50 wt.%.
  • ferrocyanides or ferricyanides can be directly dissolved into electrolyte.
  • the concentration of ferrocyanides/ferricyanides can be from 0 to a saturated concentration.
  • Figs. 4A and 4B are graphs depicting the charge/discharge profiles of Mn-HCF and Na 4 Fe(CN) 6 mixed Mn-HCF electrodes.
  • manganese HCF Na 2 MnFe(CN) 6
  • Sodium ferrocyanide Na 4 Fe(CN) 6
  • 3 wt. % sodium ferrocyanide was mixed into the Mn-HCF electrode. In order to compare these two kinds of electrodes, all capacities were normalized based on the maximum discharge capacity of the Mn-HCF electrode.
  • the addition of 3 wt.% Na 4 Fe(CN) 6 improved the capacity of the Mn-HCF electrode.
  • the capacity of the Na 4 Fe(CN) 6 mixed Mn-HCF electrode was about 20% higher than that of the Mn-HCF electrode.
  • Na 4 Fe(CN) 6 was active for sodium-ion intercalation [NPL12], the incremental capacity was much higher than the contribution of Na 4 Fe(CN) 6 .
  • NPL12 sodium-ion intercalation
  • Mn-HCF electrode There might be two reasons for the improvement of Mn-HCF electrode. One reason might be that the addition of Na 4 Fe(CN) 6 interacted with water inside Mn-HCF, permitting more sodium-ion to enter the MN-HCF interstitial space.
  • Na 4 Fe(CN) 6 provided a relatively high Na-ion concentration for sodium-ion intercalation.
  • Na 4 Fe(CN) 6 also improved the capacity retention of Mn-HCF electrode. In 100 cycles, the capacity retention of Na 4 Fe(CN) 6 -mixed Mn-HCF electrode was at least 5% larger than that of Mn-HCF electrode as shown in Fig. 4B. The mechanism for the capacity retention improvement has been discussed above.
  • Figs. 5A and 5B depict the performance of Mn-HCF in a saturated NaClO 4 ethylene carbonate (EC)/diethyl carbonate (DEC) electrolyte with and without Na 4 Fe(CN) 6 .
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • Na 4 Fe(CN) 6 dissociated to sodium-ions and Fe(CN) 6 4- .
  • Na 4 Fe(CN) 6 was dissolved into the electrolyte.
  • Na-ions and Fe(CN) 6 4- -ions moved to any Mn-HCF particles along the porous structure of Mn-HCF electrode.
  • the additive of Na 4 Fe(CN) 6 improved the Mn-HCF capacity slightly, as shown in Fig. 5A.
  • the Na 4 Fe(CN) 6 additive increased the capacity of the Mn-HCF electrode by 15% in 40 cycles with a charge/discharge current of 0.1C as shown in Fig. 5B.
  • Fig. 6 is a flowchart illustrating a method for synthesizing a TMHCF battery electrode with a Fe(CN) 6 additive.
  • 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 600.
  • Step 602 synthesizes a A x M y Fe z (CN) n .mH 2 O powder.
  • the A cations are either alkali or alkaline-earth cations such as Na, K, Ca, or Mg, and where: M is a transition metal; x is in the range of 0 to 2; y is in the range of 0 to 2; z is in the range of 0.1 to 2; n is in the range of 1 to 6; and, m is in the range of 0 to 7.
  • Step 604 mixes the A x M y Fe z (CN) n .mH 2 O powder with a conducting carbon and an organic binder in an organic solution, creating a mixture.
  • Step 606 adds Fe(CN) 6 to the mixture, forming a modified mixture.
  • the Fe(CN) 6 may be ferrocyanide ([Fe(CN) 6 ] 4- ) or ferricyanide ([Fe(CN) 6 ] 3- ).
  • Step 608 forms the modified mixture with Fe(CN) 6 on a metal current collector, creating an electrode.
  • the modified mixture may be applied as a paste, and then dried.
  • Fig. 7 is a flowchart illustrating a method for fabricating a TMHCF battery with a Fe(CN) 6 additive.
  • the method begins at Step 700.
  • Step 702 provides a battery, as described above in the explanation of Fig. 3.
  • the battery has a cathode with A x M y Fe z (CN) n .mH 2 O particles overlying a current collector, and an anode including an A ⁇ metal, an A ⁇ metal containing composite, or a material that can host A ⁇ atoms.
  • the above-mentioned anode material may be mixed with a conducting carbon and formed on a metal current collector.
  • the battery comprises an electrolyte.
  • Step 704 adds a Fe(CN) 6 additive such as ferrocyanide or ferricyanide.
  • the Fe(CN) 6 can be added to the cathode, as described above in the explanation of Fig. 6, or the anode.
  • Step 704a adds Fe(CN) 6 to the electrode
  • Step 704b performs at least one cycle of battery charge and battery discharge.
  • Step 706 forms a TMHCF battery with Fe(CN) 6 additive.
  • the A cations are either alkali or alkaline-earth cations, such as Na, K, Ca, or Mg, where: M is a transition metal; x is in the range of 0 to 2; y is in the range of 0 to 2; z is in the range of 0.1 to 2; n is in the range of 1 to 6; and, m is in the range of 0 to 7.
  • the A ⁇ cations are either alkali or alkaline-earth cations, such as Na, K, Ca, or Mg.
  • a ⁇ need not necessarily be the same element as A.
  • the electrolyte may include A-atom salts, A ⁇ -atom salts, or a combination of the above-mentioned salts.
  • TMHCF electrode with Fe(CN) 6 additive along with an associated battery, fabrication process, and charge cycling process have been provided. Examples of particular materials and process steps have been presented to illustrate the invention. However, the invention is not limited to merely these examples. Other variations and embodiments of the invention will occur to those skilled in the art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne une électrode de batterie d'hexacyanoferrate de métal de transition (TMHCF) pourvue d'un additif Fe(CN)6. L'électrode est conçue à partir de particules de AxMyFez(CN)n.mH2O recouvrant un collecteur de courant, les cations A étant des cations alcalins ou des cations alcalino-terreux tels que le sodium (Na), le potassium (K), le calcium (Ca), ou le magnesium (Mg), et M étant un métal de transition. Un additif Fe(CN)6 modifie les particules de AxMyFez(CN)n.mH2O. L'additif Fe(CN)6 peut être un ferrocyanure ([Fe(CN)6]4-) ou un ferricyanure ([Fe(CN)6]3-). L'invention concerne également une batterie TMHCF apparentée pourvue de l'additif Fe(CN)6, un procédé de fabrication de TMHCF, et un procédé de fabrication de batterie TMHCF.
PCT/JP2014/002195 2013-04-29 2014-04-17 Électrode de batterie d'hexacyanoferrate modifiée par des ferrocyanures ou des ferricyanures Ceased WO2014178171A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP14792239.7A EP2992563A4 (fr) 2013-04-29 2014-04-17 Électrode de batterie d'hexacyanoferrate modifiée par des ferrocyanures ou des ferricyanures
CN201480024742.6A CN105164833B (zh) 2013-04-29 2014-04-17 利用亚铁氰化物或铁氰化物改性的六氰合铁酸盐电池电极

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US13/872,673 US9246164B2 (en) 2012-03-28 2013-04-29 Protected transition metal hexacyanoferrate battery electrode
US13/872,673 2013-04-29
US13/897,492 US9099719B2 (en) 2012-03-28 2013-05-20 Hexacyanoferrate battery electrode modified with ferrocyanides or ferricyanides
US13/897,492 2013-05-20

Publications (1)

Publication Number Publication Date
WO2014178171A1 true WO2014178171A1 (fr) 2014-11-06

Family

ID=51843316

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/002195 Ceased WO2014178171A1 (fr) 2013-04-29 2014-04-17 Électrode de batterie d'hexacyanoferrate modifiée par des ferrocyanures ou des ferricyanures

Country Status (3)

Country Link
EP (1) EP2992563A4 (fr)
CN (1) CN105164833B (fr)
WO (1) WO2014178171A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10122049B2 (en) 2014-02-06 2018-11-06 Gelion Technologies Pty Ltd Gelated ionic liquid film-coated surfaces and uses thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105869907B (zh) * 2016-05-06 2018-07-24 同济大学 一种碳氮共掺杂NiFe2O4/Ni纳米立方结构复合材料的制备方法
CN109088068B (zh) * 2017-06-13 2020-05-19 宁德时代新能源科技股份有限公司 钠离子电池
KR20200075250A (ko) * 2018-12-18 2020-06-26 현대자동차주식회사 알칼리 토금속이 도핑된 황화물계 고체전해질 및 이의 제조방법
CN117210685A (zh) * 2023-09-01 2023-12-12 南方科技大学 一种利用可循环螯合剂回收退役锂离子电池中有价金属的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5472807A (en) * 1993-11-30 1995-12-05 The United States Of America As Represented By The Secretary Of The Navy Aluminum-ferricyanide battery
JP2011180469A (ja) * 2010-03-03 2011-09-15 National Institute Of Advanced Industrial Science & Technology プルシアンブルー型金属錯体ナノ粒子を具備する電気化学素子、これを用いたエレクトロクロミック素子及び二次電池
JP2011246303A (ja) * 2010-05-26 2011-12-08 National Institute Of Advanced Industrial Science & Technology プルシアンブルー類似体を用いたリチウムイオン２次電池電極材料
JP2012186160A (ja) * 2011-02-18 2012-09-27 Sumitomo Electric Ind Ltd 電池
WO2012177932A2 (fr) * 2011-06-22 2012-12-27 The Board Of Trustees Of The Leland Stanford Junior University Matériaux d'électrode de batterie à longue durée de vie de cycles à haute charge présentant une structure d'ossature ouverte

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3860937B2 (ja) * 1999-08-04 2006-12-20 トヨタ自動車株式会社 ヘキサシアノ鉄錯体およびそれを正極活物質として用いたリチウム二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5472807A (en) * 1993-11-30 1995-12-05 The United States Of America As Represented By The Secretary Of The Navy Aluminum-ferricyanide battery
JP2011180469A (ja) * 2010-03-03 2011-09-15 National Institute Of Advanced Industrial Science & Technology プルシアンブルー型金属錯体ナノ粒子を具備する電気化学素子、これを用いたエレクトロクロミック素子及び二次電池
JP2011246303A (ja) * 2010-05-26 2011-12-08 National Institute Of Advanced Industrial Science & Technology プルシアンブルー類似体を用いたリチウムイオン２次電池電極材料
JP2012186160A (ja) * 2011-02-18 2012-09-27 Sumitomo Electric Ind Ltd 電池
WO2012177932A2 (fr) * 2011-06-22 2012-12-27 The Board Of Trustees Of The Leland Stanford Junior University Matériaux d'électrode de batterie à longue durée de vie de cycles à haute charge présentant une structure d'ossature ouverte

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2992563A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10122049B2 (en) 2014-02-06 2018-11-06 Gelion Technologies Pty Ltd Gelated ionic liquid film-coated surfaces and uses thereof

Also Published As

Publication number Publication date
CN105164833A (zh) 2015-12-16
EP2992563A1 (fr) 2016-03-09
EP2992563A4 (fr) 2016-05-04
CN105164833B (zh) 2017-12-01

Similar Documents

Publication Publication Date Title
US9680152B2 (en) Transition metal hexacyanoferrate battery with carbonaceous anode
US8968925B2 (en) Metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode
JP6334720B2 (ja) シアノメタレート正極電池、及び製造方法
US9246164B2 (en) Protected transition metal hexacyanoferrate battery electrode
CN105190964B (zh) 金属掺杂的过渡金属六氰合铁酸盐(tmhcf)电池电极
KR101354085B1 (ko) 비수계 이차 전지용 활물질, 비수계 이차 전지 및 그의 충방전 방법
EP2951874B1 (fr) Procédé de synthèse d'un matériel de batterie d'hexacyanoferrate de métal de transition
US10483527B2 (en) Cathode material for rechargeable magnesium battery and method for preparing the same
WO2012133527A1 (fr) Batterie rechargeable sodium-ion
WO2014178171A1 (fr) Électrode de batterie d'hexacyanoferrate modifiée par des ferrocyanures ou des ferricyanures
US9742027B2 (en) Anode for sodium-ion and potassium-ion batteries
WO2016002194A1 (fr) Additifs pour électrolyte pour stabilisation d'électrodes en cyanométallate d'un métal de transition
WO2014178170A1 (fr) Électrode protégée de batterie d'hexacyanoferrate de métal de transition
US9099719B2 (en) Hexacyanoferrate battery electrode modified with ferrocyanides or ferricyanides
US9966602B2 (en) Metal cyanometallates
KR20170058673A (ko) 나트륨 2차 전지용 양극 활물질 및 그 제조 방법
US9620815B2 (en) Electrolyte additives for transition metal cyanometallate electrode stabilization
US9419278B2 (en) Rechargeable metal-ion battery with non-aqueous hybrid ion electrolyte
US9443664B2 (en) Supercapacitor with metal cyanometallate anode and carbonaceous cathode
WO2016152055A1 (fr) Batterie à cathode en cyanométallate de métal de transition à anode de galvanoplastie

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201480024742.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14792239

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2014792239

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE