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: A method is provided for synthesizing a metal (M) meso-tetraphenylporphyrin polymer. The method begins with the provision of a free-base (H2)-meso-tetra-4-(trialkylsilyl)ethynylphenylporphyrin (H2-tetra-C?C-TriAS-TPP) including a trialkylsilyl (TriAS) moiety attached to an ethynyl termini. In response to a reaction with a metal (M)-containing material, the H2-tetra-C?C-TriAS-TPP is converted to a metal (M)-tetra-4-(trialkylsilyl)ethynylphenylporphyrin (M-tetra-C?C-TriAS-TPP). Then, the M-tetra-C?C-TriAS-TPP is converted to a M-tetra-4-ethynylphenylporphyrin (M-tetra-C?C-TPP) monomer by removing the trialkylsilyl (TriAS) moiety from the ethynyl termini. Finally, a plurality of M-tetra-C?C-TPP monomers are coupled together to supply a metal (M)-meso-tetraphenylporphyrin polymer (M-poly-meso-TPP), whereby meso-phenyl groups of adjacent M-tetra-C?C-TPP monomers in the M-poly-meso-TPP are connected through a butadiyne linking moiety. In one aspect, the metal is zinc.

Abstract: A method is provided for forming an alkali metal-doped solution-processed metal chalcogenide. A first solution is formed that includes a first material group of metal salts, metal complexes, or combinations thereof, dissolved in a solvent. The first material group may include one or more of the following elements: copper (Cu), indium (In), and gallium (Ga). An alkali metal-containing material is added to the first solution, and the first solution is deposited on a conductive substrate. The alkali metal-containing material may be sodium (Na). An alkali metal-doped first intermediate film results, comprising metal precursors from corresponding members of the first material group. Then, thermally annealing is performed in an environment of selenium (Se), Se and hydrogen (H2), hydrogen selenide (H2Se), sulfur (S), S and H2, hydrogen sulfide (H2S), or combinations thereof. The metal precursors in the alkali metal-doped first intermediate film are transformed, and an alkali metal-doped chalcogenide layer is formed.

Abstract: A method is provided for synthesizing a metal (M) meso-tetraphenylporphyrin polymer. The method begins with the provision of a free-base (H2)-meso-tetra-4-(trialkylsilyl)ethynylphenylporphyrin (H2-tetra-C?C-TriAS-TPP) including a trialkylsilyl (TriAS) moiety attached to an ethynyl termini. In response to a reaction with a metal (M)-containing material, the H2-tetra-C?C-TriAS-TPP is converted to a metal (M)-tetra-4-(trialkylsilyl)ethynylphenylporphyrin (M-tetra-C?C-TriAS-TPP). Then, the M-tetra-C?C-TriAS-TPP is converted to a M-tetra-4-ethynylphenylporphyrin (M-tetra-C?C-TPP) monomer by removing the trialkylsilyl (TriAS) moiety from the ethynyl termini. Finally, a plurality of M-tetra-C?C-TPP monomers are coupled together to supply a metal (M)-meso-tetraphenylporphyrin polymer (M-poly-meso-TPP), whereby meso-phenyl groups of adjacent M-tetra-C?C-TPP monomers in the M-poly-meso-TPP are connected through a butadiyne linking moiety. In one aspect, the metal is zinc.

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 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.

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 co-sensitized dye-sensitized solar cell (DSC) is provided, made from a transparent substrate and a transparent conductive oxide (TCO) film overlying the transparent substrate. An n-type semiconductor layer overlies the TCO, and is co-sensitized with a first dye (D1) and a second dye (D2). A redox electrolyte is in contact with the co-sensitized n-type semiconductor layer, and a counter electrode overlies the redox electrolyte. The first dye (D1) has a first optical absorbance local maxima at a first wavelength (A1) and a second optical absorbance local maxima at a second wavelength (A2), longer than the first wavelength. The second dye (D2) has a third optical absorbance local maxima at a third wavelength (A3) between the first wavelength (A1) and the second wavelength (A2). In one aspect, the first dye (D1) includes a porphyrin material, for example, a metalloporphyrin obtained by complexation with a transition metal such as zinc (i.e. zinc porphyrin (ZnP)).

Abstract: A dye-sensitized solar cell (DSC) is provided with energy-donor enhancement. A transparent conductive oxide (TCO) film is formed overlying a transparent substrate, and an n-type semiconductor layer is formed overlying the TCO. The n-type semiconductor layer is exposed to a dissolved dye (D1) having optical absorbance local maximums at a first wavelength (A1) and second wavelength (A2), longer than the first wavelength. The n-type semiconductor layer is functionalized with the dye (D1), forming a sensitized n-type semiconductor layer. A redox electrolyte is added that includes a dissolved energy-donor material (ED1) in contact with the sensitized n-type semiconductor layer. The energy-donor material (ED1) is capable of non-radiative energy transfer to the dye (D1), which is capable of charge transfer to the n-type semiconductor.

Abstract: A method is provided for forming an alkali metal-doped solution-processed metal chalcogenide. A first solution is formed that includes a first material group of metal salts, metal complexes, or combinations thereof, dissolved in a solvent. The first material group may include one or more of the following elements: copper (Cu), indium (In), and gallium (Ga). An alkali metal-containing material is added to the first solution, and the first solution is deposited on a conductive substrate. The alkali metal-containing material may be sodium (Na). An alkali metal-doped first intermediate film results, comprising metal precursors from corresponding members of the first material group. Then, thermally annealing is performed in an environment of selenium (Se), Se and hydrogen (H2), hydrogen selenide (H2Se), sulfur (S), S and H2, hydrogen sulfide (H2S), or combinations thereof. The metal precursors in the alkali metal-doped first intermediate film are transformed, and an alkali metal-doped chalcogenide layer is formed.

Abstract: A method is provided for forming a Group VA-doped solution-processed metal chalcogenide. The method forms a first solution including a first material group, dissolved in solvent. A Group VA-containing material is added to the first solution. The Group VA-containing material may include arsenic (As), antimony (Sb), bismuth (Bi), or combinations thereof. The first solution is deposited on a conductive substrate, and a Group VA-doped first intermediate film is formed comprising metal precursors from corresponding members of the first material group. Thermal annealing is performed in an environment of selenium (Se), Se and hydrogen (H2), hydrogen selenide (H2Se), sulfur (S), S and H2, hydrogen sulfide (H2S), or combinations thereof. As a result, the metal precursors in the Group VA-doped first intermediate film are transformed, forming a Group VA-doped metal chalcogenide layer. In one aspect, an antimony-doped Cu—In—Ga—Se chalcogenide (CIGS) is formed.