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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
• • 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
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0421—Methods of deposition of the material involving vapour deposition
• • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0438—Processes of manufacture in general by electrochemical processing
  • H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
  • H01M4/623—Binders being polymers fluorinated polymers
• • 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

Definitions

• This invention generally relates to electrochemical cells and, more particularly, to an alkali or alkaline-earth ion battery made from a hexacyanometallate cathode and non- metal anode.
• This invention also relates to electrochemical cells' and, more particularly, to method for forming a carbon- hexacyanometallate battery electrode .
• 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 milli-amp-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 + ) exchange 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) materials is typically a metal oxide with a layered structure , such as lithium cobalt oxide ( L1C0 O2) , or a material having a tunneled structure, such as lithium manganese oxide (LiMn20 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 LiCo02 , olivine-structured LiFePO4, spinel-structured LiMn2O 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 depicts the framework for an electrode material with large interstitial spaces in a metal-ion battery (prior art) . It is inevitable that the large interstitial spaces in these materials readily absorb water molecules and impure ions, as shown. Water molecules also occupy lattices positions in the electrode material. Although these open spaces are very suitable for the intercalation of metal-ions with large sizes, the water molecules and impure ions degrade the electrochemical performance.
• Prussian blue analogues (PBs) with cubic / tetragonal / hexagonal framework have open "zeolytic" lattices that permit Na + / K + -ions to move easily and reversibly in the framework.
• Fig. 2 demonstrates the crystal structure of Prussian blue and its analogues (prior art) .
• Their general molecular formula is AM 1 M2(CN) 6 .zH 2 O , in which tetrahedrally coordinated A site is an alkali or alkaline-earth ion, and M l and M2 are metal ions.
• the Ml and M2 metals are arranged in a three-dimensional checkerboard pattern and shown in a two-dimensional pattern.
• the crystal structure is analogous to that of the ABX3 perovskite.
• Ml and M2 metal ions are in ordered arrangement on the B sites.
• the Ml ions are octahedrally coordinated to the nitrogen ends of the CN- groups, and the M2 ions to their carbon ends.
• the Ml and M2 ions are connected by the C ⁇ N to form the Prussian blue framework with large interstitial spaces.
• the ratio of Ml and M2 may be an arbitrary number.
• the cyanide ligands (C ⁇ N) octahedrally coordinate Ml and M2 to constitute a cubic framework that has a large interstitial space.
• the metal-ions or molecules of 'A' can locate in the interstitial space and balance the local charge.
• the molecular ratio for A:M1:M1:H 2 0 in Prussian blue and its analogues is not precisely 1:1:1:0, the general molecular formula of AM1M2(CN) 6 is used herein for simplicity.
• the typical compounds of AM1M2(CN)6 include Prussian white (K 2 Fe(II)Fe(II)(CN) 6 ), Prussian blue (KFe(II)Fe(III)(CN) 6 ), Berlin green (Fe(III)Fe(III)(CN) 6 ) and their analogues.
• the bond dipole moment of C ⁇ N is around 3.0 Debye, which makes the ordering of the Ml and M2 ions with different spin-states in the framework.
• the material of AM1M2(CN)6 has demonstrated a variety of interesting functions in optics, magnetic, and electrochemistry.
• the electrochemical reaction can take place only if ( 1 ) a redox couple is in the structure, (2) ions can transport in/ out of the structure, and (3) electrons can transport to balance the charge neutrality.
• the electrochemical reaction taking place in Prussian blue can be expressed as follows :
• the redox couple is Fe 2+ / Fe 3+ .
• the Fe 3+ ion obtains an electron and reduces to Fe 2+ , and a potassium-ion moves to the interstitial space of the compound to balance the charge .
• V V eq - V 0 ver
• 'V eq ' is the equilibrium potential of the electrochemical reaction
• 'Vover ' is the overpotential.
• Slower ion or electron transport leads to a high overpotential and a low reaction voltage .
• a large overpotential and small current lead to the poor performance of the electrochemical reaction .
• the AM 1 M2 (CN) 6 material has a large interstitial space in which ions can easily move in and out of the lattice . Ion transport is not a limiting factor affecting the kinetic parameters of the electrochemical reaction .
• AM 1 M2 (CN) 6 has a wide band gap between the valence and conduction bands. This means that the AM 1 M2 (CN) 6 is a very poor electronic conductor.
• the dried Prussian blue, for example, is an insulator, and Prussian white and Berlin green are semiconductors.
• the slow electronic transport along the skeleton of M 1 -N ⁇ C-M2 results in poor electrochemical performance in a system containing AM 1 M2 (CN) 6 .
• the large interstitial sites may host the large sized alkali or alkaline-earth ions (A) .
• Water molecules may also occupy lattice positions in the PB analogues .
• the ion channels connecting the interstitial sites are similar in size to solvated alkali ions such as sodium, potassium, and alkaline-earth ions such as magnesium and calcium, allowing rapid transport of these ions throughout the lattice . Therefore PB is a good choice for an electrode material in sodium / potassium / magnesium/ calcium- ion batteries . Nonetheless, thermogravimetric analysis (TG) suggests that every PB molecule contains four to six water molecules .
• KCuFe(CN) 6 has a theoretical capacity of 85.2 mAh/ g, but its practical capacity is smaller than 60 mAh/ g.
• water may react with the intercalated metal- ions and decrease the coulombic and energy efficiencies of the metal-ion batteries .
• no method has been reported to remove the water and impure ions from the large interstitial spaces and lattice positions of the hexacyanometallate electrode materials for metal-ions batteries.
• most metal-ions batteries with a hexacyanometallate electrode use an aqueous solution as an electrolyte . These batteries have small specific capacities and low voltages .
• the open framework structure of the transition metal hexacyanometallates offers a faster and reversible intercalation process for alkali and alkaline-earth ions (A x ) .
• the metal ions need to be stored in either the anode or cathode electrode before assembly.
• the Li ions are stored in the cathode and the anode is carbon. Therefore , these batteries are assembled in a discharged state. These batteries need to be run through a charge cycle, to move the Li ions to the carbon anode , before they have any power for discharge .
• Li-S Li-air and Na-S batteries
• the metal ions are stored in anode.
• these anodes are made of Li and Na metals.
• These batteries are assembled in the charged state - meaning the battery can discharge immediately after assembly. Since alkali (e . g. , Li, Na, and K), and other alkaline-earth (e.g., Mg and Ca) metals are very reactive with water vapor and oxygen, the manufacturing cost for such a battery would be prohibitively high, as the manufacturing has to be done in controlled environment.
• alkali e . g. , Li, Na, and K
• alkaline-earth e.g., Mg and Ca
• a metal anode for the metal-ion battery.
• a Na-ion battery can be made of a sodium anode and KFe 2 (CN)6 cathode, or a K-ion battery with potassium anode and KFe 2 (CN)6 cathode.
• these batteries must be assembled in controlled environment (H 2 0-free, oxygen-free) if a metal anode is used.
• alkali and alkaline-earth ion batteries could be made with a hexacyanometallate ⁇ 1M2(CN) 6 cathode and a non-metal anode.
• an alkali-ion battery e.g., a sodium-ion battery or potassium-ion battery
• an alkaline-earth-ion battery e.g., a magnesium-ion battery or calcium-ion battery
• the non-metal materials for the negative electrode (anode) include carbonaceous materials, oxides, sulfide, and so on.
• the battery demonstrates high energy, long cycling life and low cost. Also disclosed is a process of forming an electrode that acts as an ion-source for hexacyanometallates, initially without sodium or potassium ions .
• a non-aqueous, polymer, or solid electrolyte can be used in the battery.
• the ratio of M l and M2 can be an arbitrary number.
• the battery demonstrates a high voltage due to the use of a non-aqueous electrolyte .
• a method for forming a hexacyanometallate battery cathode.
• the method provides dried hexacyanometallate particles having a chemical formula A' n M l x M2 y (CN) 6 with a Prussian Blue hexacyanometallate crystal structure, including impurities and H20.
• A' is an alkali or alkaline-earth cation.
• M l is a metal with 2 + or 3+ valance positions.
• M2 is a metal with 2+ or 3+ valance positions, (n) is in the range of 0.5 to 2 , x is in the range of 0.5 to 1 .5, and y is in the range of 0.5 to 1 .5.
• the hexacyanometallate particles are mixed with a binder and electronic conductor powder in a low boiling point solvent. Drying the mixture forms a A'nM l x M2y(CN) 6 paste .
• a metal current collector is coated with the paste, forming a cathode . After drying the paste, the cathode is soaked in an organic first electrolyte including a salt with alkali or alkaline-earth cations, and a first electric field is created in the first electrolyte between the cathode and a first counter electrode .
• the method In response to the first electric field, the method simultaneously removes A' cations , impurities , and water molecules from interstitial spaces and lattice positions in the Prussian Blue hexacyanometallate crystal structure .
• Hexacyanometallate particles having a chemical formula of AVM l x M2 y (CN) 6 , where n ' ⁇ n, are formed overlying the cathode .
• the method then soaks the cathode in an organic second electrolyte including a salt with A cations, where A is an alkali or alkaline-earth cation .
• a cations are added into the interstitial spaces of the A'n'M l xM2 y (CN) 6 crystal structure.
• CN CN 6 crystal structure.
• a cathode is formed with hexacyanometallate particles having the chemical formula A' n 'A m M l x M 2 y (CN) 6 , where m is in a range of 0.5 to 2. Additional details of the above-described method and a battery with a hexacyanometallate cathode and non-metal anode are presented below.
• Described herein is a method to reduce the electron transport path in AM 1 M2 (CN) 6 materials and to improve its performance in electrochemical applications.
• the method produces uniform and small size particles of AM 1 M2 (CN) 6 material, making it a better electrical conductor.
• the method also reduces overpotential and increases the current for the electrochemical reaction of AM 1 M2 (CN) 6 .
• a method for forming a carbon- hexacyanometallate battery electrode .
• the method adds conducting carbon during the synthesis of hexacyanometallate .
• Carbon-hexacyanometallate (AM 1 M2 (CN) 6 ) structures are collected, washed in deionized water, and then dried.
• adding carbon during the synthesis of hexacyanometallate includes : combining conducting carbon with a potassium ferricyanide solution, forming a first solution; stirring the first solution; preparing a Fe2 + solution; combining the Fe 2 + solution with the first solution, forming a second solution; and, stirring the second solution .
• the method may include the following additional steps .
• the carbon-hexacyanometallate structures are mixed with a binder and electronic conductor powder in a low boiling point solvent, forming a carbon-AM 1 M2 (CN) 6 paste .
• a metal current collector is coated with the paste , and the paste is then dried to form an electrode .
• Fig. 1 depicts the framework for an electrode material with large interstitial spaces in a metal-ion battery (prior art) .
• Fig. 2 demonstrates the crystal structure of Prussian blue and its analogues (prior art) .
• Fig. 3 is a partial cross-sectional view of a battery with a hexacyanometallate cathode and non-metal anode .
• Fig. 4 is a partial cross-sectional schematic view of a Na-ion battery in the discharge state, with a Na x M 1 M2(CN) 6 positive electrode and a non-metal negative electrode separated by a Na + -ion permeable membrane .
• Figs. 5A through 5C depict three types of battery configurations.
• Fig. 6 is a flowchart illustrating a method for forming a hexacyanometallate battery cathode.
• Fig. 7 is a flowchart illustrating a method for forming a non-metal battery anode.
• Figs. 8A and 8B are schematic drawings depicting different variations of an intimately contacting carbon- hexacyanometallate structure for battery electrode applications.
• Figs. 9A and 9B are drawings contrasting electron transport in uncoated and conductor-coated AM lM2(CN)e particles.
• Fig. 10 is a schematic drawing depicting a one-step hexacyanometallate coating method during AM 1M2(CN)6 synthesis.
• Fig. 11 is a drawing depicting a conducting film coating on AM1M1(CN) 6 particles.
• Fig. 12 is a flowchart illustrating method for forming a carbon-hexacyanometallate battery electrode in which
• KFe(II)Fe(III)(CN)6 is used as an example.
• Fig. 13 is a flowchart illustrating an alternate method for forming a carbon-hexacyanometallate battery electrode.
• Fig. 14 is a flowchart illustrating another variation of a method for forming a carbon-hexacyanometallate battery electrode .
• Figs. 1 5A and 1 5B are scanning electron microscope (SEM) images of KNiFe(CN) 6 .
• Figs . 16A and 16B depict, respectively, the charge and discharge behavior of the two batteries .
• Fig. 3 is a partial cross-sectional view of a battery with a hexacyanometallate cathode and non-metal anode .
• the battery 1 00 comprises a cathode 102 with hexacyanometallate particles 1 04 overlying a current collector 106.
• the hexacyanometallate particles 104 have the chemical formula A' n 'A m M l x M2 y (CN) 6 , and have a Prussian Blue hexacyanometallate crystal structure (see Fig. 2) .
• the A cations may be either alkali or alkaline-earth cations .
• the A' cations may be either alkali or alkaline-earth cations .
• the A and A' cations may be Na + , K + , Mg 2 + , or Ca 2 + .
• the A and A' cations may be the same or a different material.
• M l is a metal with 2 + or 3 + valance positions .
• M2 is a metal with 2 + or 3+ valance positions.
• the M l and M2 metals may be Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ca, or Mg.
• the Ml metal may be the same metal as the M2 metal, or a different metal than the M2 metal.
• m is in the range of 0.5 to 2
• x is in the range of 0.5 to 1.5
• y is in the range of 0.5 to 1.5
• n' is in the range of 0 to 2.
• the battery 100 further comprises an electrolyte 108 capable of conducting A cations 110.
• An ion-permeable membrane 112 separates a non-metal anode 114 from the cathode 102.
• Some examples of anode materials include carbonaceous materials, oxides, sulfides, nitrides, silicon, composite material including metal nanoparticles with carbonaceous materials, and silicon nanostructures with carbonaceous materials.
• the electrolyte 108 may be a nonaqueous, organic, gel, polymer, solid electrolyte, or aqueous electrolyte.
• the A cations are Na + cations
• the ion permeable membrane 112 is a Na + -ion permeable membrane
• the electrolyte 108 is a Na + soluble non-aqueous electrolyte.
• the general expression for the cathode may be: Na 2 M 1 M2(CN) 6 , NaM 1 M2(CN) 6 , NaKMlM2(CN) 6 , or M 1 M2(CN) 6 .
• Ml, M2 Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ca, Mg, etc.
• the ratio of Ml and M2 can be an arbitrary number. For example: Na 2 Fe2(CN)6, NaFe 2 (CN)6, NaKFe 2 (CN) 6 , and Fe 2 (CN) 6 .
• the A cations are K + cations
• the ion permeable membrane 112 is a K + -ion permeable membrane
• the electrolyte 108 is a K+ soluble nonaqueous electrolyte.
• the general expression for the cathode materials may be: K 2 M1M2(CN) 6 , KM 1 M2(CN) 6 , NaKMlM2(CN) 6 , or M1M2(CN) 6 .
• Ml, M2 Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ca, Mg, etc.
• the ratio of Ml and M2 can be an arbitrary number. For example: K 2 Fe2(CN)6, KFe 2 (CN)6, and NaKFe 2 (CN) 6 .
• the A cations are Mg 2+ cations
• the ion permeable membrane 112 is a Mg 2+ -ion permeable membrane
• the electrolyte 108 is a Mg 2+ soluble nonaqueous electrolyte.
• the general expression for the cathode materials may be: MgMlM2(CN) 6 , Mgo.sM 1 M2(CN) 6 , or M1M2(CN) 6 .
• Ml, M2 Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ca, Mg, etc.
• the ratio of Ml and M2 can be an arbitrary number. For example: MgFe 2 (CN)6, Mgo.sFe 2 (CN)6, or Fe 2 (CN) 6 .
• the ion permeable membrane 112 is a Ca 2+ -ion permeable membrane
• the electrolyte 108 is a Ca 2+ soluble non-aqueous electrolyte.
• the general expression for the Ca-ion battery is the same as the Mg-ion battery, just replacing Mg with Ca in the formulas above .
• the anode 1 14 includes A cations, and the ion-permeable membrane 1 12 is permeable to A cations . More explicitly, the ion-permeable membrane 1 12 is permeable to the A cations used in the anode 1 14.
• an anode is defined as being a non-metal anode if it is a composite material that includes a metal .
• sodium-ion, potassium-ion, magnesium-ion , and calcium-ion batteries are disclosed with positive (cathode) electrodes of A X M 1 M2 (CN) 6 , negative (anode) electrodes of a non-metal material, an ion-permeable membrane separating the cathode and anode, and an electrolyte .
• the material, A X M 1 M2 (CN)6, demonstrates a framework that consists of a M 1 -N-C-M2 skeleton and large interstitial space as shown in Fig. 2.
• A-ions Na, K, Mg and Ca
• the anode is a non-metal material. It can be one of carbonaceous materials, oxides, sulfides or nitrides.
• a nonaqueous electrolyte such as organic electrolyte, gel electrolyte, polymer electrolyte, solid electrolyte, etc., may be used in the battery.
• Fig. 4 is a partial cross-sectional schematic view of a Na-ion battery in the discharge state, with a Na x M 1 M2(CN) 6 positive electrode 102 and a non-metal negative electrode 114 separated by a Na + -ion permeable membrane 112.
• a Na + soluble non-aqueous solution 108, polymer, or solid electrolyte is used in the Na- ion battery.
• the non-metal negative electrode 114 is the carbonaceous material, oxide, sulfide, and so on. In the charge/discharge process, Na + ions "rock" back and forth between the positive electrode 102 and negative electrode 114.
• a K-ion battery would have of K X M 1 M2(CN) 6 positive electrode, a non-metal negative electrode, and a K + - ion permeable membrane separating the cathode and anode electrodes.
• the battery charge reactions at the cathode and anode are shown below.
• the positive electrode For sodium-ion battery, the positive electrode:
• the positive electrode For potassium-ion battery, the positive electrode:
• the positive electrode For magnesium-ion battery, the positive electrode:
• the positive electrode For calcium-ion battery, the positive electrode:
• binder such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.
• the electronic conductor powder may be carbon black, carbon nanotube, carbon nanowire, grapheme, etc., with particle size of 5 nm - 10 pm.
• the water is not shown in the formula.
• the composition of the paste is 60 wt.% - 95 wt.% A' n M 1 M2(CN) 6 , 0 wt.% - 30 wt.% electronic conductor powder, and lwt.% - 15 wt.% binder.
• the paste is coated on a metal foil or mesh (Al, Ti, etc.) that is used as the current collector for the positive electrode. After drying, the electrode undergoes forming process.
• the forming process includes two steps: the first step is to remove the ions (A' n ) and residual water from the A' n M 1 M2(CN) 6 lattice.
• the second step is to fill Na- ions, K-ions, Mg-ions, or Ca-ions into the A' n M 1M2(CN)6 lattice.
• the Na ions and K ions (Mg ions and Ca ions) occupy the A site and these ions are moved in/out of the A'nAmM 1 M2(CN)6 lattice during the discharge/ charge cycles. Additional details of the 2-step forming process are provided in parent application entitled, ELECTRODE FORMING PROCESS FOR METAL-ION BATTERY WITH
• the forming process can be summarized as follows. For simplicity, it is assumed that the ions at the A site are all removed in the first step.
• the A' ions in cathode material A' n M 1M2(CN)6 before the forming process, and the A ions in A m M 1 M2(CN)e after forming process may be a different material.
• K X M 1 M2(CN) 6 is used before the electrode forming process, and the materials change to Na x M 1 M2 (CN)6 or Na x K y M 1M2(CN)6 after forming process for a Na-ion battery application.
• the negative (anode) electrode is fabricated as follows.
• a dried non-metal negative electrode powder e.g., carbonaceous material, oxides, or sulfides
• binder such as PTFE or PVDF, etc.
• an electronic conductor powder carbon black, carbon nanotube, carbon nanowire, grapheme, etc., with particle size of 5 nm - 10 urn
• the composition of the paste is 60 wt. % - 95 wt. % non-metal anode, 0 wt.% - 30 wt.% electronic conductor powder, and l wt. % - 15 wt. % binder.
• the paste is coated on a metal foil or mesh (Cu, Ti, Ni, etc.) that is used as the current collector for the negative electrode .
• the negative electrode has a very low potential that can reduce the organic electrolyte to form an ion-permeable layer on the negative electrode so-called solid electrolyte interphase (SEI) .
• SEI solid electrolyte interphase
• the SEI improves the stability of the negative electrode in the ion battery.
• the reduction reaction exhausts the metal-ions (Na + , K + , Mg 2 + , or Ca 2 + ) from the positive electrode, which decreases the capacity of the positive electrode . So a process of forming the electrode is applied to the negative electrode prior to the electrode slitting and battery assembly. The forming process is performed in a water-free environment.
• the negative electrode (anode) is paired with a counter metal-electrode (e . g. , Na, K, Mg, Ca) in an electrochemical cell that includes an organic electrolyte with metal-ions (Na + , K + , Mg 2 + , Ca 2 + ) .
• a counter metal-electrode e . g. , Na, K, Mg, Ca
• the metal-ions insert into or react with the negative electrode .
• the electrolyte reacts with the negative electrode to form a SEI layer that contains metal ions, carbon, oxygen, and hydrogen on the negative electrode surface .
• an opposite electrical field is applied and the metal-ions are de-inserted from the negative electrode .
• the SEI layer is intact.
• the counter electrode in made with Na, and the electrolyte includes Na ions .
• an-ion permeable inner layer forms on the electrode .
• Figs . 5A through 5C depict three types of battery configurations.
• the battery can be assembled.
• a membrane separates the positive and negative electrode .
• the membrane can be one of polymer, gel, or solid materials .
• the sandwich electrode assembly can be configured according to the container shape of the battery. The electrode assembly is put into a container. If a liquid solution is needed to help the ion transport, it can be injected into the container. After all the electrodes are thoroughly soaked in electrolyte , the container is sealed .
• An all-solid sodium ion-battery or potassium-ion battery uses a different composition for the electrode fabrication.
• the all-solid ion battery consists of the positive electrode and the negative electrode separated by an ion- conduct solid electrolyte .
• ⁇ - ⁇ 1 2 0 3 , NaZr 2 (P0 4 ) 3 , Na 4 Zr 2 (Si0 4 ) 3 and their derivates can be used as the Na+-ion solid electrolyte .
• the 5wt. % - 60 wt.% solid electrolyte powder can be added into the pastes of the positive electrode and the negative electrode to prepare the electrode . After obtaining the electrode , they can be assembled into a battery as described above.
• Fig. 6 is a flowchart illustrating a method for forming a hexacyanometallate battery cathode .
• 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 provides dried hexacyanometallate particles having a chemical formula A' n M l x M2 y (CN) 6 with a Prussian Blue hexacyanometallate crystal structure, including impurities and H2O .
• A' is either an alkali or alkaline-earth cations
• M l is a metal with 2+ or 3+ valance positions .
• M2 is a metal 2 + or 3+ valance positions
• n is in the range of 0.5 to 2
• x is in the range of 0.5 to 1 .5
• y is in the range of 0.5 to 1 .5.
• the A' cations may be Na + , K + , Mg 2 + , or Ca 2 + .
• the M l metal may be Ti, V, Cr, Mn, Fe, Co , Ni, Cu, Zn, Ca, or Mg for example .
• the M2 metal may be Ti, V, Cr, Mn, Fe , Co, Ni, Cu, Zn, Ca, or Mg.
• the M l may be the same metal as the M2 metal or a different metal than the M2 metal.
• the dried hexacyanometallate particles typically have a size in the range of 5 nm to 10 microns.
• Step 604 mixes the hexacyanometallate particles with a binder and electronic conductor powder in a low boiling point solvent.
• low boiling point solvents include amyl acetate, acetone, diethyl carbonate, dimethyl carbonate, and n-methyl-2-pyrrolidone (NMP) .
• the binder may be PTFE or PVDF, for example.
• the electronic conductor powder is carbon black, carbon nanotubes, carbon nanowire , or grapheme , having a particle size in the range of 5 nm to 10 microns .
• Step 606 dries the mixture , forming a A' n M l x M2 y (CN) 6 paste.
• the paste is 60 to 95 weight (wt) % A' n M lxM2y(CN) 6 , 0 to 30 wt % electronic conductor powder, and 1 to 1 5 wt % binder.
• Step 608 coats a metal current collector with the paste, forming a cathode .
• Step 6 10 dries the paste .
• Step 6 12 soaks the cathode in an organic first electrolyte including a salt with either alkali or alkaline-earth cations .
• Step 6 14 accepts a first electric field in the first electrolyte between the cathode and a first counter electrode .
• Step 6 16 simultaneously removes A' cations, impurities, and water molecules from interstitial spaces in the Prussian Blue hexacyanometallate crystal structure .
• Step 618 forms hexacyanometallate particles having a chemical formula of AVM l x M2 y (CN) 6 , where n' ⁇ n, overlying the cathode .
• Step 620 soaks the cathode in an organic second electrolyte including a salt with A cations, where A is either an alkali or alkaline-earth cation .
• A is either an alkali or alkaline-earth cation .
• the A cations are Na + , K + , Mg 2 + , or Ca 2 + .
• the A cations may be the same material as the A' cations or a different material than the A' cations.
• Step 622 accepts a second electric field in the second electrolyte between the cathode and a second counter electrode including A elements.
• Step 624 adds A cations into the interstitial spaces of the AVM l x M2 y (CN) 6 crystal structure .
• Step 626 forms a cathode with hexacyanometallate particles having the chemical formula AVA m M l x M2 y (CN) 6 , where m is in a range of 0.5 to 2.
• Fig. 7 is a flowchart illustrating a method for forming a non-metal battery anode .
• the method begins at Step 700.
• Step 702 provides a dried non-metal electrode powder.
• Step 704 mixes the dried non-metal electrode powder with a binder and an electronic conductor powder in a low boiling point solvent.
• Step 706 forms a paste .
• Step 708 coats a metal current collector with the paste, forming an anode .
• the paste dries .
• Step 7 12 soaks the anode in a first organic electrolyte including a salt with metal ions .
• Step 7 14 accepts a first electric field in the electrolyte between the anode and a metal first counter electrode .
• Step 7 16 forms a metal solid electrolyte interphase (SEI) layer overlying the anode .
• the metal SEI layer additionally includes carbon, oxygen, hydrogen, and combinations of the above- mentioned elements.
• Step 7 18 accepts a second electric field, opposite in polarity to the first electric field between the anode and the first counter electrode .
• Step 720 removes metal ions from the anode while maintaining the SEI layers intact.
• soaking the anode in the first organic electrolyte in Step 7 1 2 includes soaking in a first organic electrolyte with A cations such as Na, K, Mg, or Ca.
• Step 7 14 uses a metal first counter electrode that additional includes the A cations used in Step 7 12.
• Step 7 16 forms the anode from a composite that includes the A cations used in Steps 7 12 and 7 14.
• a battery with a hexacyanometallate cathode and non- metal anode has been provided with an associated cathode fabrication process. 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.
• Figs . 8A and 8B are schematic drawings depicting different variations of an intimately contacting carbon- hexacyanometallate structure for battery electrode applications.
• the structure 300' comprises carbon (C) 302 ' and hexacyanometallate particles 304 '.
• a bond exists between the carbon 302 ' and the hexacyanometallate particles 304 ' that may be either a physical bond, caused by electrostatic attraction, or a chemical bond, caused by chemical reactions.
• x is in the range of 0.5 to 1 .5
• y is in the range of 0.5 to 1 .5.
• the carbon 302 ' may take the form of particles having a size in the range of 1 0 nanometers (nm) to 20 microns, a carbon sheet, graphene, nanoparticles (less than 10 nm) , nanotubes, or wires. As in the conventional meaning of the word, a nanotube has a hollow center axis
• the hexacyanometallate particles 304' is smaller than the carbon 302', with a size in a range of 10 nm to 10 microns.
• Fig. 8A depicts a plurality of hexacyanometallate particles bonded to each carbon form.
• Fig. 8B depicts a plurality of carbon forms bonded to each hexacyanometallate particle.
• the first step is to fabricate the particles for battery electrode.
• the second step is to mix the AM 1 M2(CN)6 particles with conductive carbon particles and organic binders (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.) in a low boiling point solvent to form a paste.
• the mixing can be done by adding together all components and mixing them in a ball mill jar.
• the third step is to coat the paste on a metal foil as the current collector. After the drying process, the electrode can be used in electrochemical cell. However, since the particles are very small, the conductive carbon particles do not totally cover the AMlM2(CN)e particle.
• the carbon can be added and forms intimate contact to AM1M2(CN)6 in three scenarios: during the AM 1 M2 (CN) 6 synthesis, after AM 1 M2 (CN) 6 particle formation and prior to the electrode printing, and after the electrode formation and drying.
• Figs . 9A through 1 1 describe processes for forming C- AM 1 M2 (CN) 6 intimate contact.
• Fig. 10 is a schematic drawing depicting a one-step hexacyanometallate coating method during AM l M2 (CN)e synthesis .
• An electronic conductor for example graphene or other carbonaceous material, is dispersed in a reactant solution .
• the electronic conductor has a large surface area to which a soluble reactant can be uniformly adsorbed.
• the reactants are dropped into a reactor very slowly with a strong stirring.
• AM 1 M2 (CN) 6 with a small particle size uniformly forms on the surface of the electronic conductor.
• the reaction can be simply expressed as:
• a carbon black (surface area: 10 - 100 m 2 / g) is dispersed in a potassium ferricyanide solution (its concentration can be controlled at 0.0005M - 0.5 M) .
• the ratio of potassium ferricyanide to carbon black is determined by its application. In one example, the ratio is 80 : 20.
• a water- soluble surfactant can be added into the solution in order to obtain a uniform carbon suspension .
• the solution is poured into a burette .
• a Fe 2 + solution is prepared.
• the mole ration of Fe 2 + to ferricyanide is 2 : 1 .
• the two solutions are dripped into a beaker very slowly with strong stirring. After the solutions completely drip off, the beaker is still kept stirring for 5 hours.
• the product in the beaker is filtered or centrifuged . After at least three washes in deionized water, the product is dried in a vacuum drier overnight.
• Figs. 1 5A and 1 5B are scanning electron microscope (SEM) images of KNiFe(CN) 6 .
• SEM scanning electron microscope
• Fig. 15A shows KNiFe(CN)6 particles uniformly coated on the surface with carbon powder.
• the carbon black not only improves the electronic conductivity of KNiFe(CN)6, but it also favors the small and uniform KNiFe(C N)6 particle formation.
• the electrical performance of the battery made of C-KNiFe(CN)6 particles was compared to the battery made of KNiFe(CN)6 particles.
• Fig. 1 5B is a more detailed image of a carbon particle .
• Figs. 16A and 16B depict, respectively, the charge and discharge behavior of the two batteries .
• the battery made of C-KNiFe(CN)6 particles (modified) small particle size and better conductivity improves the utilization of the electrode materials and increases specific capacities, as compared to the battery made of (as-synthesized) KNiFe(CN)6 particles.
• the discharge capacity of electrode made of C-KNiFe(CN)6 particles is about 60 mAh/g, but that of pure KNiFe(CN)6 is smaller than 30 mAh/g.
• the battery made of C-KNiFe(CN)6 particles demonstrates a capacity of about 40 mAh/g at the 1C charge rate. With the same conditions, the battery made of pure KNiFe(CN)6 shows a very low capacity.
• Fig. 11 is a drawing depicting a conducting film coating on AM1M1(CN) 6 particles.
• the C-AM1M2(CN) 6 intimate contact can be formed after AM1M2(CN)6 particle synthesis, but prior to the to the electrode printing.
• a layer of electronic conductor, such as carbon 302' can be coated on their surface using physical or chemical methods.
• atomic layer deposition ALD
• PVD physical vapor deposition
• CVD chemical vapor deposition
• hydrothermal synthesis or ball milling method, etc.
• ALD atomic layer deposition
• PVD physical vapor deposition
• CVD chemical vapor deposition
• ball milling method etc.
• two problems are worth noting.
• One is that some electronic conductors have very high reductive activity, for example, carbonaceous materials that can reduce Ml and M2 from the high valence to the low valence.
• the material in the process of using the hydrothermal method to coat the carbon layer on the surface of KFe(II)Fe(III)(CN)6, the material can be reduced to K 2 Fe(II)Fe(II)(CN) 6 .
• the other problem is the selection of the electronic conductor for the coating. After the coating process, the electronic conductor layer is covered on the particles uniformly. For the electrochemical reaction to occur on the AM 1M2(CN)6, the layer of the electronic conductor must be 'A' ion-permeable. In other words, the layer of the electronic conductor cannot retard the 'A' ion transport between the AM 1 M2(CN)6 particle and the electrolyte. In some cases, the conducting film 302' does not have to be continuous so that AM1M2(CN)6 particles have direct contact to the electrolyte and "A" ions are readily intercalating/ deintecalating to the AM1M2(CN)6 particles.
• FIGS. 9A and 9B are drawings contrasting electron transport in uncoated and conductor-coated AM1M2(CN)6 particles.
• the conducting film can be deposited after the electrode formation.
• Obtaining small and uniformly distributed particle is a step to improving the electronic transport in the AM1M2(CN)6.
• an electrode 400' cathode
• the transport path between an electron 402' and ions 404' is shortened.
• the ion (A + ) 404' conduction is through an electrolyte surrounding the AM1M2(CN) 6 particle.
• the A + ions 404' move through the large interstitial sites in a direction towards a more negative potential.
• the electron 402' is moving within the AMlM2(CN)e material.
• the electron 402' movement in the AM1M2(CN)6 particle 404' is basically governed by the electron conductivity behavior of the AM1M2(CN)6 material. It is known that AM1M2(CN)6 has low electron conductivity, which results in a slow electrochemical reaction.
• One example of good electronic conductor is carbon.
• the electronic conductor 406' provides a highway for the fast electrons transport as shown in Fig. 9B.
• 'A'-ions diffuse to the reactive place 408' along the interstitial space, but electrons 402' can move to reactive place along the external electronic conductor 406'. Therefore, the electrochemical reaction has a small overpotential and a large current.
• the A cations may be either alkali or alkaline-earth cations.
• the A cations may be Na + , K + , Mg 2+ , or Ca 2+ .
• Ml is a metal with 2+ or 3+ valance positions.
• M2 is a metal with 2+ or 3+ valance positions.
• the M l and M2 metals may be Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ca, or Mg.
• the M l metal may be the same metal as the M2 metal, or a different metal than the M2 metal.
• Fig. 12 is a flowchart illustrating method for forming a carbon-hexacyanometallate battery electrode in which KFe(II) Fe(III) (CN)6 is used as an example .
• 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 700'.
• Step 702 ' adds conducting carbon during the synthesis of hexacyanometallate .
• the conducting carbon can be the form of a particle having a size in a range of 10 nm to 20 microns, a carbon sheet, graphene , nonoparticles, nanotubes, or wires.
• Step 704 ' collects carbon- hexacyanometallate (AM l M2 (CN)e) structures .
• Step 706' washes the carbon-hexacyanometallate structures in deionized water.
• Step 708 ' dries the carbon- hexacyanometallate structures.
• Step 7 10' mixes the carbon-hexacyanometallate structures with a binder and electronic conductor powder in a low boiling point solvent.
• Step 712' forms a carbon-AM 1 M2(CN) 6 paste.
• Step 714' coats a metal current collector with the paste.
• Step 716' dries the paste to form an electrode.
• adding carbon during the synthesis of hexacyanometallate in Step 702' includes substeps.
• Step 702'a combines conducting carbon with a potassium ferricyanide solution, forming a first solution.
• Step 702'b stirs the first solution.
• Step 702'c prepares a Fe 2+ solution.
• Step 702'd combines the Fe 2+ solution with the first solution, forming a second solution.
• Step 702'e stirs the second solution.
• Step 704' includes collecting carbon- hexacyanometallate (AM 1M2(CN)6) structures from the second solution.
• the combination of Steps 702'a and 702'e form a specific AM 1 M2(CN) 6 material, which may be KFeFe(CN)6 for example. Other methods of enabling Step 702' would be known in the art.
• Step 712' may form a carbon-AMlM2(CN)6 paste with a plurality of hexacyanometallate particles bonded to each carbon form, where the bond is a physical bond or a chemical bond.
• Step 712' may form the carbon-AM 1 M2(CN)6 paste with a plurality of carbon forms bonded (chemical or physical) to each hexacyanometallate particle.
• Step 712' forms the carbon- AM 1 M2 (CN)6 paste with hexacyanometallate particles have a size in the range of 10 nm to 10 microns.
• Fig. 13 is a flowchart illustrating an alternate method for forming a carbon-hexacyanometallate battery electrode .
• the method begins at Step 800'.
• Step 802 ' forms hexacyanometallate particles.
• the hexacyanometallate particles have a size in the range of 10 nm to 10 microns .
• the hexacyanometallate particles may be formed using one of the following processes: template, hydrothermal, co-deposition, or sonochemical synthesis.
• Step 804 coats the hexacyanometallate particles with a conducting carbon .
• the conducting carbon may be in the form of particles having a size in the range of 10 nm to 20 microns, a carbon sheet, graphene , nanoparticles, nanotubes, or wires.
• the coating may be performed using one of the following processes : atomic layer deposition (ALD) , physical vapor deposition (PVD) , chemical vapor deposition (CVD) , hydrothermal synthesis, or ball milling.
• Step 806 ' forms carbon-hexacyanometallate structures .
• Step 808 ' mixes the carbon-hexacyanometallate structures with a binder and electronic conductor powder in a low boiling point solvent.
• Step 8 10' forms a carbon-AM 1 M2 (CN)6 paste.
• Step 8 12 ' coats a metal current collector with the paste .
• Step 8 14 ' dries the paste to form an electrode .
• forming the carbon-AM l M2 (CN) 6 paste in Step 8 10' includes forming a paste with a plurality of carbon atoms bonded to each hexacyanometallate molecule, where the bond is a physical bond or a chemical bond.
• Fig. 14 is a flowchart illustrating another variation of a method for forming a carbon-hexacyanometallate battery electrode.
• the method begins at Step 900 '.
• Step 902 ' forms hexacyanometallate particles.
• the hexacyanometallate particles have a size in the range of 10 nm to 10 microns .
• Step 904 ' mixes the hexacyanometallate particles with a binder and electronic conductor powder in a low boiling point solvent.
• Step 906' forms a carbon- AM 1 M2 (CN) 6 paste .
• Step 908 ' coats a metal current collector with the paste.
• Step 9 10 ' dries the paste to form an electrode .
• Step 9 12 ' coats the electrode with a layer of conducing materials.
• coating the electrode with the layer of conducting materials in Step 9 12 ' includes using a deposition process such as CVD , vapor phase ALD, or liquid phase coating.
• Step 9 12 ' uses a conducting material having a thickness in the range from 0.5 nm to 20 nm, where the material is either carbon or a metal material.
• the C-AM 1 M2 (CN) 6 in the conducting material coating the electrode includes carbon that either fully covers or partially covers the AM 1 M2(CN)e particle surfaces.
• This invention can be also constructed as below.
• a battery with a hexacyanometallate cathode and non-metal anode comprising:
• hexacyanometallate particles having a chemical formula A' n 'A m M l x M2 y (CN)6, and having a Prussian Blue hexacyanometallate crystal structure,
• a cations are selected from a group consisting of alkali and alkaline-earth cations
• A' cations are selected from a group consisting of alkali and alkaline-earth cations
• M l is a metal selected from a group consisting of 2+ and 3+ valance positions
• M2 is a metal selected from a group consisting of 2+ and 3+ valance positions
• m is in a range of 0.5 to 2 ;
• x is in a range of 0.5 to 1 .5;
• y is in a range of 0.5 to 1 .5 ;
• n' is in a range of 0 to 2 ;
• an ion-permeable membrane separating the anode from the cathode .
• ion permeable membrane is a Na + -ion permeable membrane
• electrolyte is a Na + soluble non-aqueous electrolyte .
• ion permeable membrane is a K + -ion permeable membrane
• electrolyte is a K + soluble non-aqueous electrolyte .
• electrolyte is a K + soluble non-aqueous electrolyte .
• ion permeable membrane is a Mg 2+ -ion permeable membrane
• electrolyte is a Mg 2+ soluble non-aqueous electrolyte.
• ion permeable membrane is a Ca 2+ -ion permeable membrane
• electrolyte is a Ca 2+ soluble non-aqueous electrolyte.
• a cations are selected from a group consisting of the same material as the A' cations and a different material than the A' cations.
• anode includes A cations
• A' is selected from a group consisting of alkali and alkaline-earth cations
• M l is a metal selected from a group consisting of 2 + and 3+ valance positions
• M2 is a metal selected from a group consisting of 2 + and 3+ valance positions
• n is in a range of 0.5 to 2 ;
• x is in a range of 0.5 to 1 .5 ;
• hexacyanometallate particles having a chemical formula of A'n'M l x M2 y (CN) 6 , where n' ⁇ n, overlying the cathode .
• A'n'M l x M2 y (C N) 6 subsequent to forming A'n'M l x M2 y (C N) 6 , soaking the cathode in an organic second electrolyte including a salt with A cations, where A is selected from a group consisting of alkali and alkaline-earth cations;
• M2 metal is selected from a group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ca, and Mg.
• the method of (14) wherein providing the dried hexacyanometallate particles includes providing particles having a size in a range of 5 nanometers (nm) to 10 microns.
• mixing the hexacyanometallate particles with the binder and electronic conductor powder includes mixing with an electronic conductor powder selected from a group consisting of carbon black, carbon nanotubes, carbon nanowire, and grapheme, having a particle size in a range of 5 nm to 10 microns .
• the method of ( 14) wherein forming the A'nM l x M2y(CN)6 paste includes forming a paste with 60 to 95 weight (wt) % A' n M l x M2 y (CN)6, 0 to 30 wt % electronic conductor powder, and 1 to 15 wt % binder.
• a method for forming a non-metal battery anode comprising:
• SEI solid electrolyte interphase
• the method of (26) wherein forming the metal SEI layer overlying the anode includes forming an SEI with additional elements selected from a group consisting of carbon, oxygen, hydrogen, and combinations of the above- mentioned elements.
• the method of (26) wherein soaking the anode in the first organic electrolyte includes soaking in a first organic electrolyte with A cations selected from a group consisting of Na, Ka, Mg, and Ca;
• accepting the first electric field includes accepting the first electric field between the anode and a metal first counter electrode additional with the selected A cations ;
• forming the metal SEI layer includes additionally forming the anode from a composite with the selected A cations.
• a method for forming a carbon-hexacyanometallate battery electrode comprising:
• AM 1 M2 (CN) 6 ) structures includes collecting carbon- hexacyanometallate (AM 1 M2 (CN) 6 ) structures from the second solution.
• adding conducting carbon includes the conducting carbon being in a form selected from a group consisting of a particle having a size in a range of 10 nanometers (nm) to 20 microns, a carbon sheet, graphene, nonoparticles, nanotubes, and wires.
• the method of (34) wherein forming the carbon- AM 1 M2 (CN) 6 paste includes forming a paste with a plurality of hexacyanometallate particles bonded to each carbon form, where the bond is selected from a group consisting of a physical bond and a chemical bond.
• the method of (33) wherein forming the carbon- AM 1 M2 (CN) 6 paste includes forming a paste with a plurality of carbon forms bonded to each hexacyanometallate particle, where the bond is selected from a group consisting of a physical bond and a chemical bond.
• the method of (33) wherein forming the carbon- AM 1 M2 (CN) 6 paste includes forming a paste with hexacyanometallate particles have a size in a range of 10 nm to 10 microns .
• hexacyanometallate AM 1 M2 (CN) 6
• CN hexacyanometallate
• a method for forming a carbon-hexacyanometallate battery electrode comprising:
• the method of (43) wherein coating the hexacyanometallate particles with the conducting carbon includes using conducting carbon in a form selected from a group consisting of a particle having a size in a range of 10 nanometers (nm) to 20 microns, a carbon sheet, graphene, nanoparticles , nanotubes, and wires.
• the method of (44) wherein forming the carbon- AM 1 M2 (CN)6 paste includes forming a paste with a plurality of carbon atoms bonded to each hexacyanometallate molecule, where the bond is selected from a group consisting of a physical bond and a chemical bond.
• hexacyanometallate particles The method of (43) wherein forming hexacyanometallate particles includes forming the hexacyanometallate particles using a process selected from a group consisting of template, hydrothermal, co-deposition, and sonochemical synthesis .
• the method of (43) wherein coating the hexacyanometallate particles with the conducting carbon includes using a process selected from a group consisting of atomic layer deposition (ALD) , physical vapor deposition (PVD) , chemical vapor deposition (CVD) , hydrothermal synthesis, and ball milling.
• ALD atomic layer deposition
• PVD physical vapor deposition
• CVD chemical vapor deposition
• the method of (43) wherein forming hexacyanometallate particles includes forming hexacyanometallate particles having a size in a range of 10 nm to 10 microns .
• a method for forming a carbon-hexacyanometallate battery electrode comprising:
• hexacyanometallate particles forming hexacyanometallate particles; mixing the hexacyanometallate particles with a binder and a conducting carbon powder in a low boiling point solvent;
• the method of (50) wherein coating the electrode with the layer of conducting materials includes using a deposition process selected from a group consisting of chemical vapor deposition (CVD) , vapor phase atomic layer deposition (ALD) , and liquid phase coating.
• CVD chemical vapor deposition
• ALD vapor phase atomic layer deposition
• the method of (50) wherein coating the electrode with the layer of conducting materials includes using a conducting material having a thickness in a range from 0.5 nanometers (nm) to 20 nm, where the material is selected from a group consisting of carbon (C) and a metal material.
• the method of (50) wherein coating the electrode with the layer of conducting materials includes coating with carbon in a manner selected from a group consisting of fully covering and partially covering the AM 1 M2 (CN)6 particle surfaces.
• the method of (50) wherein forming the hexacyanometallate particle includes forming hexacyanometallate particles having a size in a range of 10 nm to 10 microns.

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