Abstract: A method is provided for synthesizing sodium iron(II)-hexacyanoferrate(II). A Fe(CN)6 material is mixed with the first solution and either an antioxidant or a reducing agent. The Fe(CN)6 material may be either ferrocyanide ([Fe(CN)6]4?) or ferricyanide ([Fe(CN)6]3?). As a result, sodium iron(II)-hexacyanoferrate(II) (Na1+XFe[Fe(CN)6]Z.MH2O is formed, where X is less than or equal to 1, and where M is in a range between 0 and 7. In one aspect, the first solution including includes A ions, such as alkali metal ions, alkaline earth metal ions, or combinations thereof, resulting in the formation of Na1+XAYFe[Fe(CN)6]Z.MH2O, where Y is less than or equal to 1. Also provided are a Na1+XFe[Fe(CN)6]Z.MH2O battery and Na1+XFe[Fe(CN)6]Z.MH2O battery electrode.

Abstract: Methods are presented for synthesizing metal cyanometallate (MCM). A first method provides a first solution of AXM2Y(CN)Z, to which a second solution including M1 is dropwise added. As a result, a precipitate is formed of ANM1PM2Q(CN)R.FH2O, where N is in the range of 1 to 4. A second method for synthesizing MCM provides a first solution of M2C(CN)B, which is dropwise added to a second solution including M1. As a result, a precipitate is formed of M1[M2S(CN)G]1/T. DH2O, where S/T is greater than or equal to 0.8. Low vacancy MCM materials are also presented.

Abstract: A battery is provided with a hexacyanometallate cathode. The battery cathode is made from hexacyanometallate particles overlying a current collector. The hexacyanometallate particles have the chemical formula AXM1MM2N(CN)Z.d[H2O]ZEO.e[H2O]BND, where A is a metal from Groups 1A, 2A, or 3A of the Periodic Table, where M1 and M2 are each a metal with 2+ or 3+ valance positions, where “ZEO” and “BND” indicate zeolitic and bound water, respectively, where d is 0, and e is greater than 0 and less than 8. The anode material may primarily be a material such as hard carbon, soft carbon, oxides, sulfides, nitrides, silicon, metals, or combinations thereof. The electrolyte is non-aqueous. A method is also provided for fabricating hexacyanometallate with no zeolitic water content in response to dehydration annealing at a temperature of greater than 120 degrees C. and less than 200 degrees C.

Abstract: A transition metal hexacyanoferrate (TMH) cathode battery is provided. The battery has a AxMn[Fe(CN)6]y.zH2O cathode, where the A cations are either alkali or alkaline-earth cations, such as sodium or potassium, where x is in the range of 1 to 2, where y is in the range of 0.5 to 1, and where z is in the range of 0 to 3.5. The AxMn[Fe(CN)6]y.zH2O has a rhombohedral crystal structure with Mn2+/3+ and Fe2+/3+ having the same reduction/oxidation potential. The battery also has an electrolyte, and anode made of an A metal, an A composite, or a material that can host A atoms. The battery has a single plateau charging curve, where a single plateau charging curve is defined as a constant charging voltage slope between 15% and 85% battery charge capacity. Fabrication methods are also provided.

Abstract: A method is provided for fabricating a cyanometallate cathode battery. The method provides a cathode of AXM1YM2Z(CN)N.MH2O, where “A” is selected from a first group of metals, and where M1 and M2 are transition metals. The method provides an anode and a metal ion-permeable membrane separating the anode from the cathode. A third electrode is also provided including “B” metal ions selected from the first group of metals. Typically, the first group of metals includes alkali and alkaline metals. The method intercalates “B” metal ions from the third electrode to the anode, the cathode, or both the anode and cathode to form a completely fabricated battery. In one aspect, a solid electrolyte interface (SEI) layer including the “B” metal ions overlies a surface of the anode, the cathode, or both the anode and cathode. A cyanometallate cathode battery is also provided.

Abstract: A sodium or potassium battery is provided, prior to an initial charge and discharge cycle, with a halogen salt additive. As is conventional, the battery is made up of the following components: an anode, a cathode, and an electrolyte. In addition, the battery includes a halogen salt (MX), where M is a metal and X is a halogen element. The halogen salt is added to the anode, the cathode, the electrolyte, or combinations thereof. The concentration MX with respect to the component(s) to which it is added is in the range of 0.01% to 10% in weight. The element X can be selected from the group of halogen elements listed in the Periodic Table. M is a material such as lithium, sodium, potassium, cesium, magnesium, calcium, barium, titanium, manganese, iron, cobalt, nickel, copper, zinc, ammonium, or combinations thereof. Advantageously, the electrolyte may be either aqueous or non-aqueous.

Abstract: A method is provided for synthesizing sodium iron(II)-hexacyanoferrate(II). A Fe(CN)6 material is mixed with the first solution and either an anti-oxidant or a reducing agent. The Fe(CN)6 material may be either ferrocyanide ([Fe(CN)6]4?) or ferricyanide ([Fe(CN)6]3?). As a result, sodium iron(II)-hexacyanoferrate(II) (Na1+XFe[Fe(CN)6]Z.MH2O is formed, where X is less than or equal to 1, and where M is in a range between 0 and 7. In one aspect, the first solution including includes A ions, such as alkali metal ions, alkaline earth metal ions, or combinations thereof, resulting in the formation of Na1+XAYFe[Fe(CN)6]Z.MH2O, where Y is less than or equal to 1. Also provided are a Na1+XFe[Fe(CN)6]Z.MH2O battery and Na1+XFe[Fe(CN)6]Z.MH2O battery electrode.

Abstract: An alkali/oxidant battery is provided with an associated method of creating battery capacity. The battery is made from an anode including a reduced first alkali metal such as lithium (Li), sodium (Na), and potassium (K), when the battery is charged. The battery's catholyte includes an element, in the battery charged state, such as nickel oxyhydroxide (NiOOH), manganese(IV) (oxide Mn( 4+)O2), or iron(III) oxyhydroxide Fe(3+)(OH)3), with the alkali metal hydroxide. An alkali metal ion permeable separator is interposed between the anolyte and the catholyte. For example, if the catholyte includes nickel(II) hydroxide (Ni(OH)2) in a battery discharged state, then it includes NiOOH in a battery charged state. To continue the example, the anolyte may include dissolved lithium ions (Li+) in a discharged state, with solid phase reduced Li formed on the anode in the battery charged state.

Abstract: A method is provided for charging a supercapacitor. The method initially provides a supercapacitor with a metal cyanometallate (MCM) particle anode, an electrolyte including a salt (DB) made up of cations (D+) anions (B?), and a cathode including carbonaceous materials (?). The method connects an external charging device between the anode and cathode, and the charging device supplies electrons to the anode and accepting electrons from the cathode. In response to the charging device, cations are inserted into the anode while anions are absorbed on the surface of the cathode. A supercapacitor device is also presented.

Abstract: A method is provided for fabricating an antimony anode. The method disperses antimony (Sb) particles in a layered carbon network using a process such as mechanical mixing, ball milling, stirring, or ultrasound sonication, forming a Sb/carbon composite. The Sb/carbon composite is mixed with a binder, forming a mixture, and the mixture is deposited on a current collector. Advantageously, the binder may be an aqueous (water soluble) binder. In one aspect, prior to dispersing the Sb particles in the layered carbon network, the Sb particles are coated with carbon. For example, the Sb particles may be dispersed in a solution including a polymer, where the solution may be an aqueous or organic. Alternatively, the Sb particles may be dispersed in a solution including a monomer. The monomer solution is polymerized to form polymer sheathed Sb core-shell structures, and then carbonized. Associated Sb anodes and Sb anode batteries are also provided.

Abstract: A method is provided for forming a rechargeable metal-ion battery with a non-aqueous hybrid ion electrolyte. The method provides a transition metal hexacyanometallate (TMHCM) cathode (AXM1YM2Z(CN)N.MH2O), where “A” is from a first group of metals, and M1 and M2 are transition metals. The electrolyte includes a first type of cation from the first group of metals, different than “A”. The method connects the cathode and anode to external circuitry to perform initial charge/discharge operations. As a result, a hybrid ion electrolyte is formed including the first type of cation and “A” cations. Subsequently, cations are inserted into the anode during charging, which alternatively may be only “A” cations, only the first type of cation, or both the “A” cations and the first type of cation. Only “A” cations, only the first type, or both “A” and the first type of cation are inserted into the TMHCM during discharge.

Abstract: A mechanism is presented for shielding a cathode in a metal cyanometallate battery. A battery is provided with an anode, a cathode, an electrolyte, and an ion-permeable membrane separating the anode from the cathode. The cathode is made up of a plurality of metal cyanometallate layers overlying the current collector. At least one of the metal cyanometallate layers is an active layer formed from an active material AXM1YM2Z(CN)N·MH2O, where “A” is an alkali metal, alkaline earth metal, or combination thereof. At least one of the metal cyanometallate layers is a shield layer comprising less than 50 percent by weight (wt %) active material. In response to applying an external voltage potential between the cathode and the anode, the method charges the battery. Upon discharge, the shield layer blocks metal particles from contacting active layers. Simultaneously, the shield layer transports metal ions from the electrolyte to the active layers.

Abstract: A transition metal hexacyanoferrate (TMH) cathode battery is provided. The battery has a AxMn[Fe(CN)6]y.zH2O cathode, where the A cations are either alkali or alkaline-earth cations, such as sodium or potassium, where x is in the range of 1 to 2, where y is in the range of 0.5 to 1, and where z is in the range of 0 to 3.5. The AxMn[Fe(CN)6]y.zH2O has a rhombohedral crystal structure with Mn2+/3+ and Fe2+/3+ having the same reduction/oxidation potential. The battery also has an electrolyte, and anode made of an A metal, an A composite, or a material that can host A atoms. The battery has a single plateau charging curve, where a single plateau charging curve is defined as a constant charging voltage slope between 15% and 85% battery charge capacity. Fabrication methods are also provided.

Abstract: A method is provided for forming a metal-ion battery electrode with large interstitial spacing. A working electrode with hexacyanometallate particles overlies a current collector. The hexacyanometallate particles have a chemical formula AmM1xM2y(CN)6.zH2O, and have a Prussian Blue hexacyanometallate crystal structure, where A is either alkali or alkaline-earth cations. M1 and M2 are metals with 2+ or 3+ valance positions. The working electrode is soaked in an organic first electrolyte including a salt including alkali or alkaline earth cations. A first electric field is created in the first electrolyte between the working electrode and a first counter electrode, causing A cations and water molecules to be simultaneously removed from interstitial spaces in the Prussian Blue hexacyanometallate crystal structure, forming hexacyanometallate particles having the chemical formula of Am?M1xM2y(CN)6.z?H2O, where m?<m and z?<z, overlying the working electrode.

Abstract: A protected transition metal hexacyanoferrate (TMHCF) battery cathode is presented, made from AxMyFez(CN)n·mH2O particles, where the A cations are either alkali or alkaline-earth cations, and M is a transition metal. In one aspect the cathode pas tion layer may be materials such as oxides, simple salts, carbonaceous materials, or polymers that form a film overlying the AxMyFez(CN)n·mH2O particles. In another aspect, the cathode passivation layer is a material such as oxygen, nitrogen, sulfur, fluorine, chlorine, or iodine that interacts with the AxMyFez(CN)n·mH2O particles, to cure defects in the AxMyFez(CN)n·mH2O crystal lattice structure. Also presented are TMHCF battery synthesis methods.

Abstract: An alkali-ion battery is provided with a transition metal cyanometallate (TMCM) sheet cathode and a non-alkaline metal anode. The fabrication method mixes TMCM powders, conductive additives, and a polytetrafluoroethylene binder with a solution containing water, forming a wet paste. The wet paste is formed into a free-standing sheet of cathode active material, which is laminated to a cathode current collector, forming a cathode electrode. The free-standing sheet of cathode active material has a thickness typically in the range of 100 microns to 2 millimeters. The cathode electrode is assembled with a non-alkaline metal anode electrode and an ion-permeable membrane interposed between the cathode electrode and anode electrode, forming an assembly. The assembly is dried at a temperature of greater than 100 degrees C. The dried assembly is then inserted into a container (case) and electrolyte is added. Thick anodes made from free-standing sheets of active material can be similarly formed.

Abstract: A method is provided for forming a metal-ion battery electrode with large interstitial spacing. A working electrode with hexacyanometallate particles overlies a current collector. The hexacyanometallate particles have a chemical formula AmM1xM2y(CN)6.zH2O, and have a Prussian Blue hexacyanometallate crystal structure, where A is either alkali or alkaline-earth cations. M1 and M2 are metals with 2+ or 3+ valance positions. The working electrode is soaked in an organic first electrolyte including a salt including alkali or alkaline earth cations. A first electric field is created in the first electrolyte between the working electrode and a first counter electrode, causing A cations and water molecules to be simultaneously removed from interstitial spaces in the Prussian Blue hexacyanometallate crystal structure, forming hexacyanometallate particles having the chemical formula of Am?M1xM2y(CN)6.z?H2O, where m?<m and z?<z, overlying the working electrode.

Abstract: A first method for fabricating an anode for use in sodium-ion and potassium-ion batteries includes mixing a conductive carbon material having a low surface area, a hard carbon material, and a binder material. A carbon-composite material is thus formed and coated on a conductive substrate. A second method for fabricating an anode for use in sodium-ion and potassium-ion batteries mixes a metal-containing material, a hard carbon material, and binder material. A carbon-composite material is thus formed and coated on a conductive substrate. A third method for fabricating an anode for use in sodium-ion and potassium-ion batteries provides a hard carbon material having a pyrolyzed polymer coating that is mixed with a binder material to form a carbon-composite material, which is coated on a conductive substrate. Descriptions of the anodes and batteries formed by the above-described methods are also provided.

Abstract: A protected transition metal hexacyanoferrate (TMHCF) battery cathode is presented, made from AxMyFez(CN)n.mH2O particles, where the A cations are either alkali or alkaline-earth cations, and M is a transition metal. In one aspect the cathode passivation layer may be materials such as oxides, simple salts, carbonaceous materials, or polymers that form a film overlying the AxMyFez(CN)n.mH2O particles. In another aspect, the cathode passivation layer is a material such as oxygen, nitrogen, sulfur, fluorine, chlorine, or iodine that interacts with the AxMyFez(CN)n.mH2O particles, to cure defects in the AxMyFez(CN)n.mH2O crystal lattice structure. Also presented are TMHCF battery synthesis methods.

Abstract: A sodium or potassium battery is provided, prior to an initial charge and discharge cycle, with a halogen salt additive. As is conventional, the battery is made up of the following components: an anode, a cathode, and an electrolyte. In addition, the battery includes a halogen salt (MX), where M is a metal and X is a halogen element. The halogen salt is added to the anode, the cathode, the electrolyte, or combinations thereof. The concentration MX with respect to the component(s) to which it is added is in the range of 0.01% to 10% in weight. The element X can be selected from the group of halogen elements listed in the Periodic Table. M is a material such as lithium, sodium, potassium, cesium, magnesium, calcium, barium, titanium, manganese, iron, cobalt, nickel, copper, zinc, ammonium, or combinations thereof. Advantageously, the electrolyte may be either aqueous or non-aqueous.