Sharp Laboratories of America, Inc

Oregon State University

Sean Vail

Yuhao Lu

Jong-Jan Lee

Long Wang

David R Evans

Wei Pan

Alexey Y Koposov

Xin Zhao

Motoaki Nishijima

Gary Foley

Hidayat Kisdarjono

Gregory M Stecker

Xiulei Ji

Jie Song

Wei Luo

Clement Bommier

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 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 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 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

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 AM2(CN), 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 AM1M2(CN).d[HO].e[HO], 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.

System and method for large scale synthesis of metal cyanometallates

A method is provided for synthesizing iron hexacyanoferrate (FeHCF). The method forms a first solution of a ferrocyanide source [AFe(CN)HO] 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 AFe(CN)HO is formed, where X is in the range of 0 to 1. The method isolates the AFe(CN)HO from the third solution, and dries the AFe(CN)HO under vacuum at a temperature greater than 60 degrees C.

Method for the synthesis of iron hexacyanoferrate

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&#xb0; 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.

Battery with low temperature molten salt (LTMS) cathode

A method is provided for synthesizing sodium iron(II)-hexacyanoferrate(II). A Fe(CN)material is mixed with the first solution and either an anti-oxidant or a reducing agent. The Fe(CN)material may be either ferrocyanide ([Fe(CN)]) or ferricyanide ([Fe(CN)]). As a result, sodium iron(II)-hexacyanoferrate(II) (NaFe[Fe(CN)].HO is formed, where X is less than or equal to 1, and whereis 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 NaAFe[Fe(CN)].HO, where Y is less than or equal to 1. Also provided are a NaFe[Fe(CN)].HO battery and NaFe[Fe(CN)].HO battery electrode.

Sodium iron(II)-hexacyanoferrate(II) battery 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).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 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.

Sodium and potassium ion batteries with halogen salts

A method is provided for synthesizing sodium iron(II)-hexacyanoferrate(II). A Fe(CN)material is mixed with the first solution and either an anti-oxidant or a reducing agent. The Fe(CN)material may be either ferrocyanide ([Fe(CN)]) or ferricyanide ([Fe(CN)]). As a result, sodium iron(II)-hexacyanoferrate(II) (NaFe[Fe(CN)].HO is formed, where X is less than or equal to 1, and whereis 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 NaAFe[Fe(CN)].HO, where Y is less than or equal to 1. Also provided are a NaFe[Fe(CN)]HO battery and NaFe[Fe(CN)].HO battery electrode.

Sodium iron(II)-hexacyanoferrate(II) battery electrode and synthesis method

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.

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Vancouver, WA, United States of America

Sean Vail