Sharp Laboratories of America, Inc

University of Texas System

Long Wang

Yuhao Lu

Jong-Jan Lee

Sean Vail

David R Evans

Motoaki Nishijima

Hidayat Kisdarjono

Jie Song

Methods are presented for synthesizing metal cyanometallate (MCM). A first method provides a first solution of AM2(CN), to which a second solution including M1 is dropwise added. As a result, a precipitate is formed of AM1M2(CN).HO, where N is in the range of 1 to 4. A second method for synthesizing MCM provides a first solution of M2(CN), which is dropwise added to a second solution including M1. As a result, a precipitate is formed of M1[M2(CN)].HO, where S/T is greater than or equal to 0.8. Low vacancy MCM materials are also presented.

Metal cyanometallates

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 MeCNSO, 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.

Battery electrode with metal particles and pyrolyzed coating

A method is provided for synthesizing metal cyanometallate (MCM). The method provides a solution of AM1(CN); where 'A' is selected from a first group of metals and M1 is selected from a second group of metals. The method adds a material including M2 to the solution to form a liquid phase material that may be either a suspension or a solution. M2 is selected from the second group of metals. The method adds acid to the liquid phase material. The addition of acid to the liquid phase material decomposes the M2 material into M2-ions. Simultaneous with the addition of the acid, a precipitate of AM1M2(CN)HO is formed, whereis in a range of 1 to 2. A variation of the above-described synthesis method is also provided.

Metal cyanometallate synthesis method

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.

Anode for sodium-ion and potassium-ion batteries

A method is provided for fabricating a transition metal hexacyanometallate (TMHCM) electrode with a water-soluble binder. The method initially forms an electrode mix slurry comprising TMHCF and a water-soluble binder. The electrode mix slurry is applied to a current collector, and then dehydrated to form an electrode. The electrode mix slurry may additionally comprise a carbon additive such as carbon black, carbon fiber, carbon nanotubes, graphite, or graphene. The electrode is typically formed with TMHCM greater than 50%, by weight, as compared to a combined weight of the TMHCM, carbon additive, and binder. Also provided are a TMHCM electrode made with a water-soluble binder and a battery having a TMHCM cathode that is made with a water-soluble binder.

Transition metal hexacyanometallate electrode with water-soluble binder

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.

NASICON-polymer electrolyte structure

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.

Reactive separator for a metal-ion battery

Fabrication method for metal battery electrode with pyrolyzed coating

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.

Electrolyte additives for transition metal cyanometallate electrode stabilization

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.

Air cathode battery using zinc slurry anode with carbon additive

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 MeX, 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 M1M2(CN)HO. After a plurality of initial charge and discharge operations are preformed, an anode is formed comprising MeX overlying the current collector in a battery discharge state, where 0&#x2266;b&#x3c;a.

Battery with an anode preload with consumable metals

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 M1M2(CN)HO 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.

Battery anode with preloaded metals

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 AM1M2(CN)-d(HO), 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 &#x201c;A&#x201d; 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.

Transition metal cyanometallate cathode battery with metal plating anode

Methods are presented for synthesizing metal cyanometallate (MCM). A first method provides a first solution of AM2(CN), to which a second solution including M1 is dropwise added. As a result, a precipitate is formed of AM1M2(CN).FHO, where N is in the range of 1 to 4. A second method for synthesizing MCM provides a first solution of M2(CN), which is dropwise added to a second solution including M1. As a result, a precipitate is formed of M1[M2(CN)]. DHO, where S/T is greater than or equal to 0.8. Low vacancy MCM materials are also presented.

Method for the synthesis of metal cyanometallates

A method is provided for fabricating a cyanometallate cathode battery. The method provides a cathode of AM1M2(CN)HO, 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 &#x201c;B&#x201d; 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 &#x201c;B&#x201d; metal ions overlies a surface of the anode, the cathode, or both the anode and cathode. A cyanometallate cathode battery is also provided.

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Vancouver, WA, United States of America

Long Wang