EP2992563A1 - Hexacyanoferrate battery electrode modified with ferrocyanides or ferricyanides - Google Patents
Hexacyanoferrate battery electrode modified with ferrocyanides or ferricyanidesInfo
- Publication number
- EP2992563A1 EP2992563A1 EP14792239.7A EP14792239A EP2992563A1 EP 2992563 A1 EP2992563 A1 EP 2992563A1 EP 14792239 A EP14792239 A EP 14792239A EP 2992563 A1 EP2992563 A1 EP 2992563A1
- Authority
- EP
- European Patent Office
- 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.)
- Withdrawn
Links
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 title description 5
- 239000000654 additive Substances 0.000 claims abstract description 47
- 230000000996 additive effect Effects 0.000 claims abstract description 43
- 239000011734 sodium Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 37
- 150000001768 cations Chemical class 0.000 claims abstract description 33
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 28
- 239000011575 calcium Substances 0.000 claims abstract description 21
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 18
- -1 transition metal hexacyanoferrate Chemical class 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 108
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 229910001415 sodium ion Inorganic materials 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- 230000001351 cycling effect Effects 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- 238000013459 approach Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000264 sodium ferrocyanide Substances 0.000 description 2
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 2
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- FBJUTZMAUXJMMH-UHFFFAOYSA-N azane;5-methyl-2-(4-methyl-5-oxo-4-propan-2-yl-1h-imidazol-2-yl)pyridine-3-carboxylic acid Chemical compound [NH4+].N1C(=O)C(C(C)C)(C)N=C1C1=NC=C(C)C=C1C([O-])=O FBJUTZMAUXJMMH-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- VRWKTAYJTKRVCU-UHFFFAOYSA-N iron(6+);hexacyanide Chemical compound [Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] VRWKTAYJTKRVCU-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- CJYZTOPVWURGAI-UHFFFAOYSA-N lithium;manganese;manganese(3+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[O-2].[Mn].[Mn+3] CJYZTOPVWURGAI-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 229940037179 potassium ion Drugs 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- H01M4/62—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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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.
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Abstract
Description
- 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.
- 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. H2/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 (LiCoO2), or a material having a tunneled structure, such as lithium manganese oxide (LiMn2O4), 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.
- Similar to the lithium-ion batteries, metal-ion batteries use the metal-ion host compounds as their electrode materials in which metal-ions can move easily and reversibly. As for 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 LiCoO2, olivine-structured LiFePO4, spinel-structured LiMn2O4, and so on. Other metal ions, such as Na+, K+, Mg2+, Al3+, Zn2+, 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 AxM1M2(CN)6 (prior art). TMHCF with large interstitial spaces has been investigated as a cathode material for rechargeable lithium-ion batteries [NPL1,2], sodium-ion batteries [NPL3,4], and potassium-ion batteries [NPL5]. With an aqueous electrolyte containing the proper alkali-ions or ammonium-ions, copper and nickel hexacyanoferrates ((Cu,Ni)-HCFs) exhibited a very good cycling life with 83% capacity retained after 40,000 cycles at a charge/discharge rate of 17C [NPL6-8]. However, the materials demonstrated low capacities and energy densities because: (1) just one sodium-ion can be inserted/extracted into/from each Cu-HCF or Ni-HCF molecule, and (2) these TMHCF electrodes must be operated below 1.23 V due to the water electrochemical window. To correct these shortcomings, manganese hexacyanoferrate (Mn-HCF) and iron hexacyanoferrate (Fe-HCF) have been used as cathode materials in non-aqueous electrolyte [NPL9, 10]. Assembled with a sodium-metal anode, the Mn-HCF and Fe-HCF electrodes cycled between 2.0 V and 4.2 V and delivered capacity of about 110 mAh/g.
- Although 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]. In general, TMHCF can be expressed as AxMyFez(CN)n.mH2O, 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. When TMHCF is used in rechargeable batteries, the following reaction occurs in the charge process:
AxMyFez(CN)n.mH2O = xAa+ + [MyFez(CN)n.mH2O]xa- + xae-. (1) - MyFez(CN)n.mH2O constitutes the TMHCF framework into/from which "A" can be easily inserted/extracted. The stability of the framework determines the TMHCF cycling life.
- In the electrolyte, solid state TMHCF has the following dynamic equilibrium with a liquid electrolyte:
AxMyFez(CN)n.mH2O = xAa+ + yMb- + [Fez(CN)n]c- + mH2O. (2) - In terms of the above equation (2), it can be known that TMHCF has a tendency to dissolve into the electrolyte, which changes the surface structures of TMHCF. When alkali-ions or alkaline-ions are extracted from TMHCF, the dissolution of TMHCF can be aggravated and the cycling life shortened.
- V.D. Neff, Some performance characteristics of a Prussian Blue battery, Journal of Electrochemical Society, 132 (1985) 1382-1384. N. Imanishi, T. Morikawa, J. Kondo, Y. Takeda, O. Yamamoto, N. Kinugasa, T. Yamagishi, Lithium intercalation behavior into iron cyanide complex as positive electrode of lithium secondary battery, Journal of Power Sources, 79 (1999) 215-219. Y. Lu, L. Wang, J. Cheng, J.B. Goodenough, Prussian blue: a new framework for sodium batteries, Chemistry Communication, 48(2012)6544-6546. L. Wang, Y. Lu, J. Liu, M. Xu, J. Cheng, D. Zhang, J.B. Goodenough, A superior low-cost cathode for a Na-ion battery, Angew. Chem. Int. Ed., 52(2013)1964-1967. A. Eftekhari, Potassium secondary cell based on Prussian blue cathode, J.Power Sources, 126 (2004) 221-228. C.D. Wessells, R.A. Huggins, Y. Cui, Copper hexacyanoferrate battery electrodes with long cycle life and high power, Nature Communication, 2( 2011) 550. C.D. Wessells, S.V. Peddada, R. A. Huggins, Y. Cui, Nickel hexacyanoferrate nanoparticle electrodes for aqueous sodium and potassium ion batteries. Nano Letters, 11(2011) 5421-5425. C.D. Wessells, S.V. Peddada, M.T. McDowell, R.A. Huggins, Y. Cui, The effect of insertion species on nanostructured open framework hexacyanoferrate battery electrode, J. Electrochem. Soc., 159(2012) A98-A103. T.Matsuda, M. Takachi, Y. Moritomo, A sodium manganese ferrocyanide thin film for Na-ion batteries, Chemical Communications, DOI: 10.1039/C3CC38839E. S.-H. Yu, M. Shokouhimehr, T. Hyeon, Y.-E. Sung, Iron hexacyanoferrate nanoparticles as cathode materials for lithium and sodium rechargeable batteries, ECS Electrochemistry Letters, 2(2013)A39-A41. T. Matsuda, Y. Moritomo, Thin film electrode of Prussian blue analogue for Li-ion battery, Applied Physics Express, 4(2011)047101. J. Qian, M. Zhou, Y. Cao, X. Ai, H. Yang, Nanosized Na4Fe(CN)6/C composite as a low-cost and high-rate cathode material for sodium-ion batteries, Advanced Energy Materials, 2(2012)410-414.
- It would be advantageous if a TMHCF cathode could be treated or modified in such a manner as to support the lattice structure through multiple cycles of charge and discharge.
- According to the one aspect of the present invention, a transition metal hexacyanoferrate (TMHCF) battery electrode with a Fe(CN)6 additive, the electrode comprising: a metal current collector; AxMyFez(CN)n.mH2O 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 AxMyFez(CN)n.mH2O particles.
- According to the another aspect of the present invention, a transition metal hexacyanoferrate (TMHCF) battery with a Fe(CN)6 additive, the battery comprising:
a cathode comprising: a metal current collector; AxMyFez(CN)n.mH2O 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 cations; an electrolyte; and, a Fe(CN)6 additive modifying the AxMyFez(CN)n.mH2O particles in the cathode. - According to the another aspect of the present invention, a method for synthesizing a transition metal hexacyanoferrate (TMHCF) battery electrode with a Fe(CN)6 additive, the method comprising: synthesizing a AxMyFez(CN)n.mH2O 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 AxMyFez(CN)n.mH2O 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(CN)6 on a metal current collector, creating an electrode.
- According to the another aspect of the present invention, a method for fabricating a transition metal hexacyanoferrate (TMHCF) battery with a Fe(CN)6 additive, the method comprising: providing a battery comprising: a cathode with AxMyFez(CN)n.mH2O 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 AxM1M2(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 AxMyFez(CN)n.mH2O particle in detail. Fig. 3 is a partial cross-sectional view of a TMHCF battery with a Fe(CN)6 additive. Fig. 4A is a graph depicting the charge/discharge profiles of Mn-HCF and Na4Fe(CN)6 mixed Mn-HCF electrodes. Fig. 4B is a graph depicting the charge/discharge profiles of Mn-HCF and Na4Fe(CN)6 mixed Mn-HCF electrodes. Fig. 5A depicts the performance of Mn-HCF in a saturated NaClO4 ethylene carbonate (EC)/diethyl carbonate (DEC) electrolyte with and without Na4Fe(CN)6. Fig. 5B depicts the performance of Mn-HCF in a saturated NaClO4 ethylene carbonate (EC)/diethyl carbonate (DEC) electrolyte with and without Na4Fe(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. - Disclosed herein is the use of 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. Ferrocyanides or ferricyanides, AxFe(CN)6 (x = 3 or 4), dissociate to A+ and Fe(CN)6 3- or Fe(CN)6 4- ions. These ions can push Equation 2 backwards, which prevents TMHCF from dissolution in the non-aqueous electrolyte:
AxMyFez(CN)n.mH2O = xAa+ + yMb- + [Fez(CN)n]c- + mH2O. (2) - TMHCF can be represented as AxMyFez(CN)n.mH2O, with A being selected from alkali or alkaline metals, and where M can be one or several transition metals. As an additive, ferrocyanides or ferricyanides improves the capacity of the TMHCF and its capacity retention.
- Accordingly, a TMHCF battery electrode is provided with a Fe(CN)6 additive. The electrode is made from AxMyFez(CN)n.mH2O 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 AxMyFez(CN)n.mH2O particles. The Fe(CN)6 additive may be ferrocyanide ([Fe(CN)6]4-) or ferricyanide ([Fe(CN)6]3-).
- In a TMHCF battery, the above described electrode may be a cathode. In that case, 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.
- Also provided is a method for synthesizing a TMHCF battery electrode with a Fe(CN)6 additive. The method synthesizes a AxMyFez(CN)n.mH2O powder, and mixes the AxMyFez(CN)n.mH2O 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.
- Additional details of the above-described TMHCF electrode, TMHCF battery, TMHCF electrode fabrication process, and a TMHCF battery fabrication process are presented below.
- 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 AxMyFez(CN)n.mH2O particle in detail. The electrode 200 comprises a metal current collector 202. AxMyFez(CN)n.mH2O 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 AxMyFez(CN)n.mH2O particles. In some aspects, 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. In this case, the battery cathode is the same as the TMHCF electrode described above in the explanation of Figs. 2A and 2B. As shown in Figs. 2A and 2B, the electrode 200 (in Fig. 3 a cathode) comprises a metal current collector 202 and AxMyFez(CN)n.mH2O 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.
- Returning to Fig. 3, 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. Again, 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 (see Fig. 2B, 206) modifies the AxMyFez(CN)n.mH2O 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. However, the TMHCF battery with Fe(CN)6 additive is not limited to any particular style of design of battery.
- As described herein, ferrocyanides or ferricyanides are used as additives in rechargeable batteries with a TMHCF electrode to improve their performance. TMHCF has the general formula of AxMyFez(CN)n.mH2O, in which A is alkali-ion or alkaline-ion that can freely move in the structures of TMHCF. When TMHCF is used in rechargeable batteries, the following reaction occurs during the charging process:
AxMyFez(CN)n.mH2O = xAa+ + [MyFez(CN)n.mH2O]xa- + xae- (1) - MyFez(CN)n.mH2O constitutes the TMHCF framework into/from which A-ions can be easily inserted/extracted. The stability of the framework determines the TMHCF cycling life.
- It is inevitable that the solid state compounds dissolve into solutions. TMHCF is unexceptional in this regard. There is a dynamic equilibrium for TMHCF in solution, as follows:
AxMyFez(CN)n.mH2O = xAa+ + yMb- + [Fez(CN)n]c- + mH2O (2) - Therefore, in a battery with TMHCF electrodes, 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.
- However, ferrocyanides or ferricyanides can be used as additives in rechargeable batteries with TMHCF electrodes to address this problem. In the electrolyte, ferrocyanides or ferricyanides, A`xFe(CN)6 (x = 3 or 4), dissociate to A`+ and Fe(CN)6 3-/Fe(CN)6 4-. Here, 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. In addition, 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 [MyFez(CN)n.mH2O 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. As for the first approach, 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.%. As for the second approach, 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 Na4Fe(CN)6 mixed Mn-HCF electrodes. As an example, manganese HCF, Na2MnFe(CN)6, was used as a cathode material in a rechargeable sodium-ion batteries. Sodium ferrocyanide, Na4Fe(CN)6, was added to the batteries as an modifier. Using the first approach mentioned above, 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.
- As shown in Fig. 4A, the addition of 3 wt.% Na4Fe(CN)6 improved the capacity of the Mn-HCF electrode. The capacity of the Na4Fe(CN)6 mixed Mn-HCF electrode was about 20% higher than that of the Mn-HCF electrode. Although Na4Fe(CN)6 was active for sodium-ion intercalation [NPL12], the incremental capacity was much higher than the contribution of Na4Fe(CN)6. There might be two reasons for the improvement of Mn-HCF electrode. One reason might be that the addition of Na4Fe(CN)6 interacted with water inside Mn-HCF, permitting more sodium-ion to enter the MN-HCF interstitial space. The other reason might be that the dissociation of Na4Fe(CN)6 provided a relatively high Na-ion concentration for sodium-ion intercalation. Na4Fe(CN)6 also improved the capacity retention of Mn-HCF electrode. In 100 cycles, the capacity retention of Na4Fe(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 NaClO4 ethylene carbonate (EC)/diethyl carbonate (DEC) electrolyte with and without Na4Fe(CN)6. In the electrolyte, Na4Fe(CN)6 dissociated to sodium-ions and Fe(CN)6 4-. In order to make these ions accessible to all surfaces of Mn-HCF electrode easily, Na4Fe(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 Na4Fe(CN)6 improved the Mn-HCF capacity slightly, as shown in Fig. 5A. However, the Na4Fe(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. 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 600.
- Step 602 synthesizes a AxMyFez(CN)n.mH2O 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 AxMyFez(CN)n.mH2O 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. Typically, Steps 604 and 606 are preformed simultaneously. 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. For example, 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. In summary the battery has a cathode with AxMyFez(CN)n.mH2O 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. Further, 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. In one aspect, Step 704a adds Fe(CN)6 to the electrode, and Step 704b performs at least one cycle of battery charge and battery discharge. Step 706 forms a TMHCF battery with Fe(CN)6 additive.
- As with the battery of Fig. 3, 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.
- Again, the 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 electrolyte may include A-atom salts, A`-atom salts, or a combination of the above-mentioned salts.
- All applications described below are incorporated herein by reference: (1) PROTECTED TRANSITION METAL HEXACYANOFERRATE BATTERY ELECTRODE, invented by Yuhao Lu et al., U.S. Serial No. 13/872,673, filed April 29, 2013, (2) TRANSITION METAL HEXACYANOFERRATE BATTERY CATHODE WITH SINGLE PLATEAU CHARGE/DISCHARGE CURVE, invented by Yuhao Lu et al., U.S. Serial No. 13/752,930, filed January 29, 2013, (3) SUPERCAPACITOR WITH HEXACYANOMETALLATE CATHODE, ACTIVATED CARBON ANODE, AND AQUEOUS ELECTROLYTE, invented by Yuhao Lu et al., U.S. Serial No. 13/603,322, filed September 4, 2012, (4) IMPROVEMENT OF ELECTRON TRANSPORT IN HEXACYANOMETALLATE ELECTRODE FOR ELECTROCHEMICAL APPLICATIONS, invented by Yuhao Lu et al., U.S. Serial No. 13/523,694, filed June 14, 2012, (5) ALKALI AND ALKALINE-EARTH ION BATTERIES WITH HEXACYANOMETALLATE CATHODE AND NON-METAL ANODE, invented by Yuhao Lu et al., U.S. Serial No. 13/449,195, filed April 17, 2012, and (6) ELECTRODE FORMING PROCESS FOR METAL-ION BATTERY WITH HEXACYANOMETALLATE ELECTRODE, invented by Yuhao Lu et al., Serial No. 13/432,993, filed March 28, 2012.
- A 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.
Claims (17)
- A transition metal hexacyanoferrate (TMHCF) battery electrode with a Fe(CN)6 additive, the electrode comprising:
a metal current collector;
AxMyFez(CN)n.mH2O 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 AxMyFez(CN)n.mH2O particles. - The TMHCF battery electrode of claim 1 wherein the Fe(CN)6 additive is selected from a group consisting of ferrocyanide ([Fe(CN)6]4-) and ferricyanide ([Fe(CN)6]3-).
- The TMHCF battery electrode of claim 1 wherein the A cations are selected from a group consisting of sodium (Na), potassium (K), calcium (Ca), and magnesium (Mg).
- A transition metal hexacyanoferrate (TMHCF) battery with a Fe(CN)6 additive, the battery comprising:
a cathode comprising:
a metal current collector;
AxMyFez(CN)n.mH2O 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 cations;
an electrolyte; and,
a Fe(CN)6 additive modifying the AxMyFez(CN)n.mH2O particles in the cathode. - The TMHCF battery of claim 4 wherein the Fe(CN)6 additive is selected from a group consisting of ferrocyanide ([Fe(CN)6]4-) and ferricyanide ([Fe(CN)6]3-).
- The TMHCF battery of claim 4 wherein the electrolyte is an organic solvent containing an ingredient selected from a group consisting of A-atom salts, A`-atom salts, and a combination of the above-mentioned salts.
- The TMHCF battery of claim 4 wherein A is selected from a group consisting of sodium (Na), potassium (K), calcium (Ca), and magnesium (Mg); and,
wherein A` is selected from a group consisting of Na, K, Ca, and Mg. - The TMHCF battery of claim 4 wherein the Fe(CN)6 is added to a battery component selected from a group consisting of the cathode, the anode, and electrolyte, and combinations of the above-mentioned components.
- A method for synthesizing a transition metal hexacyanoferrate (TMHCF) battery electrode with a Fe(CN)6 additive, the method comprising:
synthesizing a AxMyFez(CN)n.mH2O 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 AxMyFez(CN)n.mH2O 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(CN)6 on a metal current collector, creating an electrode. - The method of claim 9 wherein synthesizing the AxMyFez(CN)n.mH2O powder includes A being selected from a group consisting of sodium (Na), potassium (K), calcium (Ca), and magnesium (Mg).
- The method of claim 9 wherein adding the Fe(CN)6 includes adding a material selected from a group consisting of ferrocyanide ([Fe(CN)6]4-) and ferricyanide ([Fe(CN)6]3-).
- A method for fabricating a transition metal hexacyanoferrate (TMHCF) battery with a Fe(CN)6 additive, the method comprising:
providing a battery comprising:
a cathode with AxMyFez(CN)n.mH2O 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. - The method of claim 12 wherein the Fe(CN)6 additive is selected from a group consisting of ferrocyanide ([Fe(CN)6]4-) and ferricyanide ([Fe(CN)6]3-).
- The method of claim 12 wherein providing the battery includes:
A cations being selected from a group consisting of alkali and alkaline-earth cations;
M being a transition metal;
x being in a range of 0 to 2;
y being in a range of 0 to 2;
z being in a range of 0.1 to 2;
n being in a range of 1 to 6;
m being in a range of 0 to 7; and,
A` cations being selected from the group consisting of alkali and alkaline-earth cations. - The method of claim 14 wherein providing the battery includes A being selected from a group consisting of sodium (Na), potassium (K), calcium (Ca), and magnesium (Mg); and,
wherein A` is selected from a group consisting of Na, K, Ca, and Mg. - The method of claim 12 wherein providing the battery includes the electrolyte being an organic solvent containing an ingredient selected from a group consisting of A-atom salts, A`-atom salts, and a combination of the above-mentioned salts.
- The method of claim 12 wherein adding the Fe(CN)6 additive includes:
adding Fe(CN)6 to the electrolyte; and,
performing a charge/discharge cycle.
Applications Claiming Priority (3)
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US13/872,673 US9246164B2 (en) | 2012-03-28 | 2013-04-29 | Protected transition metal hexacyanoferrate battery electrode |
US13/897,492 US9099719B2 (en) | 2012-03-28 | 2013-05-20 | Hexacyanoferrate battery electrode modified with ferrocyanides or ferricyanides |
PCT/JP2014/002195 WO2014178171A1 (en) | 2013-04-29 | 2014-04-17 | Hexacyanoferrate battery electrode modified with ferrocyanides or ferricyanides |
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EP2992563A4 EP2992563A4 (en) | 2016-05-04 |
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