Abstract: A method is provided for forming a metal battery electrode with a pyrolyzed coating. The method provides a metallorganic compound of metal (Me) and materials such as carbon (C), sulfur (S), nitrogen (N), oxygen (O), and combinations of the above-listed materials, expressed as MeXCYNZSXXOYY, where Me is a metal such as tin (Sn), antimony (Sb), or lead (Pb), or a metal alloy. The method heats the metallorganic compound, and as a result of the heating, decomposes materials in the metallorganic compound. In one aspect, decomposing the materials in the metallorganic compound includes forming a chemical reaction between the Me particles and the materials. An electrode is formed of Me particles coated by the materials. In another aspect, the Me particles coated with a material such as a carbide, a nitride, a sulfide, or combinations of the above-listed materials.

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 sodium-containing particle electrolyte structure. The method provides sodium-containing particles (e.g., NASICON), dispersed in a liquid phase polymer, to form a polymer film with sodium-containing particles distributed in the polymer film. The liquid phase polymer is a result of dissolving the polymer in a solvent or melting the polymer in an extrusion process. In one aspect, the method forms a plurality of polymer film layers, where each polymer film layer includes sodium-containing particles. For example, the plurality of polymer film layers may form a stack having a top layer and a bottom layer, where with percentage of sodium-containing particles in the polymer film layers increasing from the bottom layer to the top layer. In another aspect, the sodium-containing particles are coated with a dopant. A sodium-containing particle electrolyte structure and a battery made using the sodium-containing particle electrolyte structure are also presented.

Abstract: A reactive separator is provided for a metal-ion battery. The reactive separator is made up of a reactive layer that is chemically reactive to alkali or alkaline earth metals, and has a first side and a second side. A first non-reactive layer, chemically non-reactive with alkali or alkaline earth metals, is adjacent to the reactive layer first side. A second non-reactive layer, also chemically non-reactive with alkali or alkaline earth metals, is adjacent to the reactive layer second side. More explicitly, the first and second non-reactive layers are defined as having less than 5 percent by weight (wt %) of materials able to participate in electrochemical reactions with alkali or alkaline earth metals. The reactive layer may be formed as a porous membrane embedded with reactive components, where the porous membrane is carbon or a porous polymer. Alternatively, the reactive layer is formed as a polymer gel embedded with reactive components.

Abstract: A method is provided for forming a metal battery electrode with a pyrolyzed coating. The method provides a metallorganic compound of metal (Me) and materials such as carbon (C), sulfur (S), nitrogen (N), oxygen (O), and combinations of the above-listed materials, expressed as MeXCYNZSXXOYY, where Me is a metal such as tin (Sn), antimony (Sb), or lead (Pb), or a metal alloy. The method heats the metallorganic compound, and as a result of the heating, decomposes materials in the metallorganic compound. In one aspect, decomposing the materials in the metallorganic compound includes forming a chemical reaction between the Me particles and the materials. An electrode is formed of Me particles coated by the materials. In another aspect, the Me particles coated with a material such as a carbide, a nitride, a sulfide, or combinations of the above-listed materials.

Abstract: A method is provided for the self-repair of a transition metal cyanometallate (TMCM) battery electrode. The battery is made from a TMCM cathode, an anode, and an electrolyte including solution formed from a solvent and an alkali or alkaline earth salt. The electrolyte includes an additive represented as G-R-g: where G and g are independently include materials with nitrogen (N) sulfur (S), oxygen (O), or combinations of the above-recited elements; and where R is an alkene or alkane group. In response to charging and discharging the battery in a plurality of cycles, the method creates vacancies in a surface of the TMCM cathode. Then, the method fills the vacancies in the surface of the TMCM cathode with the electrolyte additive. An electrolyte and TMCM battery using the above-mentioned additives are also provided.

Abstract: An air cathode battery is provided that uses a zinc slurry anode with carbon additives. The battery is made from an air cathode and a zinc slurry anode. The zinc slurry anode includes zinc particles, an alkaline electrolyte, with a complexing agent and carbon additives in the alkaline electrolyte. A water permeable ion-exchange membrane and electrolyte chamber separate the zinc slurry from the air cathode. The carbon additives may, for example, be graphite, carbon fiber, carbon black, or carbon nanoparticles. The proportion of carbon additives to zinc is in the range of 2.5 to 10% by weight. The proportion of alkaline electrolyte in the zinc slurry is in the range of 50 to 80% by volume.

Abstract: A battery structure is provided for making alkali ion and alkaline-earth ion batteries. The battery has a hexacyanometallate cathode, a non-metal anode, and non-aqueous electrolyte. A method is provided for forming the hexacyanometallate battery cathode and non-metal battery anode prior to the battery assembly. The cathode includes hexacyanometallate particles overlying a current collector. The hexacyanometallate particles have the chemical formula A?n?AmM1xM2y(CN)6, and have a Prussian Blue hexacyanometallate crystal structure.

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: A method is provided for fabricating a battery using an anode preloaded with consumable metals. The method forms an ion-permeable membrane immersed in an electrolyte. A preloaded anode is immersed in the electrolyte, comprising MeaX, where X is a material such as carbon, metal capable of being alloyed with Me, intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials. Me is a metal such as alkali metals, alkaline earth metals, and combinations of the above-listed metals. A cathode is also immersed in the electrolyte and separated from the preloaded anode by the ion-permeable membrane. The cathode comprises M1YM2Z(CN)N.MH2O. After a plurality of initial charge and discharge operations are preformed, an anode is formed comprising MebX overlying the current collector in a battery discharge state, where 0?b<a.

Abstract: A battery with a corrosion-resistant ion-exchange membrane system is presented. The battery has an acidic catholyte, an anode metal that is chemically reactive towards water, and an ion-exchange membrane system. Some examples of anode metals include alkali metals, alkaline earth metals, and aluminum (Al). The ion-exchange membrane system includes a solid, cation-permeable, water-impermeable first membrane adjacent to the anode, prone to decomposition upon chemical reaction with an acid, an anion-permeable second membrane adjacent to the cathode, and a buffer compartment including a solution, interposed between the first membrane and the second membrane. In response to discharging the battery, the solution in the buffer compartment accepts cations from the anode and anions from the cathode, forming a cation-anion salt solution in the buffer compartment. The second membrane prevents the transportation of protons from the catholyte to the buffer compartment, and so prevents the corrosion of the first membrane.

Abstract: A system and method are presented for the large scale synthesis of metal cyanometallates (MCMs). First and second precursor solutions are added to a main reactor, where the first precursor includes M1 metal cations. The second precursor solution includes AX?M2(CN)Z?, where M1 and M2 are from a first group of metals and A is from a second group of metals including alkali or alkaline earth metals. In response to stirring the first and second precursors, MCM particles are formed with the formula AXM1NM2M(CN)Z.d[H2O]ZEO.e[H2O]BND, in solution. In response to aging in the secondary reactor, the size of the MCM particles is increases. The aged MCM particles in solution are then transferred to a separation tank, where the aged MCM particles are filtered from the solution and collected. The solution reclaimed from the separation tank back is added back into the main reactor.

Abstract: A battery structure is provided for making alkali ion and alkaline-earth ion batteries. The battery has a hexacyanometallate cathode, a non-metal anode, and non-aqueous electrolyte. A method is provided for forming the hexacyanometallate battery cathode and non-metal battery anode prior to the battery assembly. The cathode includes hexacyanometallate particles overlying a current collector. The hexacyanometallate particles have the chemical formula A?n?AmM1xM2y(CN)6, and have a Prussian Blue hexacyanometallate crystal structure.

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 method is provided for synthesizing iron hexacyanoferrate (FeHCF). The method forms a first solution of a ferrocyanide source [A4Fe(CN)6.PH2O] material dissolved in a first solvent, where “A” is an alkali metal ion. A second solution is formed of a Fe(II) source dissolved in a second solvent. A reducing agent is added and, optionally, an alkali metal salt. The first and second solutions may be purged with an inert gas. The second solution is combined with the first solution to form a third solution in a low oxygen environment. The third solution is agitated in a low oxygen environment, and AX+1Fe2(CN)6.ZH2O is formed, where X is in the range of 0 to 1. The method isolates the AX+1Fe2(CN)6.ZH2O from the third solution, and dries the AX+1Fe2(CN)6.ZH2O under vacuum at a temperature greater than 60 degrees C.

Abstract: A battery is provided with an associated method for transporting metal-ions in the battery using a low temperature molten salt (LTMS). The battery comprises an anode, a cathode formed from a LTMS having a liquid phase at a temperature of less than 150° C., a current collector submerged in the LTMS, and a metal-ion permeable separator interposed between the LTMS and the anode. The method transports metal-ions from the separator to the current collector in response to the LTMS acting simultaneously as a cathode and an electrolyte. More explicitly, metal-ions are transported from the separator to the current collector by creating a liquid flow of LTMS interacting with the current collector and separator.

Abstract: A method is presented for fabricating an anode preloaded with consumable metals. The method provides a material (X), which may be one of the following materials: carbon, metals able to be electrochemically alloyed with a metal (Me), intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials. The method loads the metal (Me) into the material (X). Typically, Me is an alkali metal, alkaline earth metal, or a combination of the two. As a result, the method forms a preloaded anode comprising Me/X for use in a battery comprising a M1YM2Z(CN)N.MH2O cathode, where M1 and M2 are transition metals. The method loads the metal (Me) into the material (X) using physical (mechanical) mixing, a chemical reaction, or an electrochemical reaction. Also provided is preloaded anode, preloaded with consumable metals.

Abstract: A method is provided for cycling power in a transition metal cyanometallate (TMCM) cathode battery. The method provides a battery with a TMCM cathode, an anode, and an electrolyte, where TMCM corresponds to the chemical formula of AXM1NM2M(CN)Y-d(H2O), where “A” is an alkali or alkaline earth metal, and where M1 and M2 are transition metals. The method charges the battery using a first charging current, or greater. In response to the charging current, a plating of “A” metal is formed overlying a plating surface of the anode. In response to discharging the battery, the “A” metal plating is removed from the anode plating surface. In one aspect, in an initial charging of the battery, a permanent solid electrolyte interphase (SEI) layer is formed overlying the anode plating surface. In subsequent charging and discharging cycles, the permanent SEI layer is maintained overlying the anode plating surface.

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: A system and method are presented for the large scale synthesis of metal cyanometallates (MCMs). First and second precursor solutions are added to a main reactor, where the first precursor includes M1 metal cations. The second precursor solution includes AX?M2(CN)Z?, where M1 and M2 are from a first group of metals and A is from a second group of metals including alkali or alkaline earth metals. In response to stirring the first and second precursors, MCM particles are formed with the formula AXM1NM2M(CN)Z.d[H2O]ZEO.e[H2O]BND, in solution. In response to aging in the secondary reactor, the size of the MCM particles is increases. The aged MCM particles in solution are then transferred to a separation tank, where the aged MCM particles are filtered from the solution and collected. The solution reclaimed from the separation tank back is added back into the main reactor.