Low vacancy Fe-substituted Mn-based prussian blue analogue

A method of producing a TMCCC Formula II material, comprising the steps of:

• (a) Admixing a solvent additive, a sodium salt and water to produce a first reaction mixture;
• (b) Admixing an iron (III) source, a manganese (II) source and a first solvent to produce a second reaction mixture;
• (c) Admixing a sodium hexacyanoferrate (II) source, a potassium hexacyanoferrate (III) source and a second solvent to produce a third reaction mixture;
• (d) Contacting said second reaction mixture and said third reaction mixture to said first reaction mixture to produce a TMCCC;
• (e) Admixing a buffer and said TMCCC to produce a fourth reaction mixture;
• and
• (f) Contacting said fourth reaction mixture with a sulfur-containing reducing agent to produce a Prussian white TMCCC including the Formula II material;
• and
• wherein said Formula II includes:
• Nab1Kb2Rbb3Csb4Frb5Tia1Va2Cra3Mna4Fea5COa6Nia7Cua8Zna9Caa10Mga11[R(CN)6]cvacr(H2O)n(SO4)j wherein R(CN)6 includes a coordination complex selected from the group consisting of hexacyanoferrate, hexacyanocobaltate, hexacyanochromate, and hexacyanomanganate;
• wherein vac identifies an R(CN)6 vacancy;
• wherein for at least one element of a set of alkali metal parameters {b1, b2}, {b1, b2}>0;
• wherein for each element of the set {b1, b2, b3, b4, b5} excluding non-zero elements of said set of alkali metal parameters, 0≤{b1, b2, b3, b4, b5};
• wherein for each element of the set {b1, b2, b3, b4, b5} {b1, b2, b3, b4, b5}≤2;
• wherein b1+b2+b3+b4+b5≤2;
• wherein for each element of the set {a1, a2, a3, a4, a5, a6, a7, a8, a9, a10, a11}, 0≤{a1, a2, a3, a4, a6, a7, a8, a9, a10, a11}≤1, a5>0;
• wherein at least two of {a1, a2, a3, a4, a5, a6, a7, a8, a9, a10, a11} are >0;
• wherein 0<c≤1;
• wherein 0≤r≤0.25;
• wherein j>0;
• wherein c+r=1;
• and wherein n≥0.