Sharp Laboratories of America, Inc

Sharp Kabushiki Kaisha Corporation

University of Texas System

Oregon State University

Yuhao Lu

Jong-Jan Lee

Long Wang

Sean Vail

David R Evans

Hidayat Kisdarjono

Motoaki Nishijima

Jie Song

Xin Zhao

Seizoh Kakimoto

Wei Pan

Gregory M Stecker

Xiulei Ji

Wei Luo

Clement Bommier

David Evans

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 MnO), or iron(III) oxyhydroxide Fe(OH)), 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)) 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.

Alkali/oxidant battery

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 AM1M2(CN).zHO, 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 AM1M2(CN).z'HO, where m&#x2032;&#x3c;m and z&#x2032;&#x3c;z, overlying the working electrode.

Metal-ion battery with hexacyanometallate electrode

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 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'AM1M2(CN), and have a Prussian Blue hexacyanometallate crystal structure.

Non-metal anode alkali and alkaline-earth ion batteries with hexacyanometallate cathode

A battery and an associated method are provided for generating power using an air cathode battery with a slurry anode. The method provides a battery with an air cathode separated from an anode current collector by an electrically insulating separator and an extrusion gap. The anode current collector extruder has a first plate with a plurality of slurry outlet perforations, and a sleeve having a first partition immediately adjacent to the extruder first plate, with a plurality of slurry inlet perforations. Active slurry is provided under pressure to an extruder inlet, and the extruder first plate slurry outlet perforations are selectively aligned with sleeve first partition slurry inlet perforations. Active slurry deposits are formed in the extrusion gap to mechanically charge the battery. In the discharge position, the sleeve moves so that the perforations no longer align, and slurry in the extruder is isolated from slurry in the extrusion gap.

Large-scale metal-air battery with slurry anode

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 graphene-doped, carbohydrate-derived hard carbon (G-HC) composite material for alkali metal-ion batteries. The method provides graphene oxide (GO) dispersed in an aqueous solution. A carbohydrate is dissolved into the aqueous solution and subsequently the water is removed to create a precipitate. In one aspect, the carbohydrate is sucrose. The precipitate is dehydrated and exposed to a thermal treatment of less than 1200 degrees C. to carbonize the carbohydrate. The result is the formation of a graphene-doped, carbohydrate-derived hard carbon (G-HC) composite. Typically, the G-HC composite is made up of graphene in the range of 0.1 and 20% by weight (wt %), and HC in the range of 80 to 99.9 wt %. The G-HC composite has a specific surface area of less than 10 square meters per gram (m/g). A G-HC composite suitable for use in alkali metal-ion batteries electrodes is also provided.

Hard carbon composite for alkali metal-ion batteries

An electrochemical battery is provided with an aluminum anode current collector and an antimony (Sb)-based electrochemically active material overlying the aluminum current collector. The Sb-based electrochemically active material may be pure antimony, Sb with other metal elements, or Sb with non-metal elements. For example, the Sb-based electrochemically active material may be one of the following: Sb binary or ternary alloys of sodium, silicon, tin, germanium, bismuth, selenium, tellurium, thallium, aluminum, gold, cadmium, mercury, cesium, gallium, titanium, lead, carbon, and combinations thereof. The aluminum current collector may additionally include a material such as magnesium, iron, nickel, titanium, and combinations thereof. In one aspect, the anode further composed of a coating interposed between the aluminum current collector and the Sb-based electrochemically active material. This coating may be a non-corrodible metal or a carbonaceous material. The cathode is may be composed of a number of different active materials including sodium-based Prussian Blue analogs.

Antimony-based anode on aluminum current collector

A transition metal hexacyanoferrate (TMH) cathode battery is provided. The battery has a AMn[Fe(CN)].zHO 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 AMn[Fe(CN)].zHO has a rhombohedral crystal structure with Mnand Fehaving 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.

Transition metal hexacyanoferrate battery with carbonaceous anode

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

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.

Alkali-ion battery with enhanced transition metal cyanometallate electrode structure

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.

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Vancouver, WA, United States of America

Yuhao Lu