Low vacancy Fe-substituted Mn-based prussian blue analogue

Patent metadata

Field	Value
Publication number	US-12304825-B2
Application number	US-202418604260-A
Country	US
Kind code	B2
Filing date	Mar 13, 2024
Priority date	Mar 13, 2023
Publication date	May 20, 2025
Grant date	May 20, 2025

Abstract

A system and method implementing and manufacturing transition metal cyanide coordination compounds (TMCCC) comprising Na, Fe, Mn, C, H, N, S, and O, wherein the TMCCC have 0-14% hexacyanometallate vacancies such as for application in electrochemical cells, including sodium ion secondary batteries; further including both sodium and potassium with and without sulfate.

First claim

What is claimed as new and desired to be protected by Letters Patent of the United States is:

1. An electrochemical device, comprising:
an electrically-conductive structure including a TMCCC represented by Formula II:
Na b1 K b2 Rb b3 Cs b4 Fr b5 Ti a1 V a2 Cr a3 Mn a4 Fe a5 CO a6 Ni a7 Cu a8 Zn a9 Ca a10 Mg a11 [R(CN) 6 ] c vac r n(H 2 O)j(SO 4 ) (Formula II);
wherein R(CN) 6 is a coordination complex selected from the group consisting of hexacyanoferrate, hexacyanocobaltate, hexacyanochromate, and hexacyanomanganate;
wherein vac identifies an R(CN) 6 vacancy;
wherein ay, y=1 to 11, represent transition metal parameters;
wherein bx, x=1 to 5 represent alkali metal parameters;
wherein for each element of a first set of alkali metal parameters {b1, b2}, {b1, b2}>0;
wherein for each element of a second set of alkali metal parameters {b3, b4, b5}, 0≤{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, a6, a7, a8, a9, a10, a11}≤1;
wherein for each element of the set {a4, a5}>0;
wherein 0<c≤1;
wherein 0≤r≤0.25;
wherein 0≤j;
wherein c+r=1;
wherein 0≤n; and
wherein b1>b2.

2. The electrochemical device of claim 1 wherein said TMCCC includes a monoclinic structure, a rhombohedral structure, a cubic crystal structure, or mixtures thereof.

3. The electrochemical device of claim 2 wherein j=0.

4. The electrochemical device of claim 1 wherein j=0.

5. The electrochemical device of claim 1 wherein 0<b2≤0.44.

6. The electrochemical device of claim 5 wherein 2≤b1/b2≤60.

7. The electrochemical device of claim 1 wherein 2≤b1/b2≤60.

8. An electrochemical device, comprising:
an electrically-conductive structure including a TMCCC represented by Formula II:
Na b1 K b2 Rb b3 Cs b4 Fr b5 Ti a1 V a2 Cr a3 Mn a4 Fe a5 CO a6 Ni a7 Cu a8 Zn a9 Ca a10 Mg a11 [R(CN) 6 ] c vac r n(H 2 O)j(SO 4 ) (Formula II);
wherein R(CN) 6 is a coordination complex selected from the group consisting of hexacyanoferrate, hexacyanocobaltate, hexacyanochromate, and hexacyanomanganate;
wherein vac identifies an R(CN) 6 vacancy;
wherein ay, y=1 to 11, represent transition metal parameters;
wherein bx, x=1 to 5 represent alkali metal parameters;
wherein for each element of a first set of alkali metal parameters {b1, b2}, {b1, b2}>0;
wherein for each element of a second set of alkali metal parameters {b3, b4 b5}, 0≤{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, a6, a7, a8, a9, a10, a11}≤1;
wherein for each element of the set {a4, a5}>0;
wherein 0<c≤1;
wherein 0≤r≤0.25;
wherein 0≤j;
wherein c+r=1;
wherein 0≤n;
wherein j>0.

9. An electrochemical device, comprising:
an electrically-conductive structure including a TMCCC represented by Formula II:
Na b1 K b2 Rb b3 Cs b4 Fr b5 Ti a1 V a2 Cr a3 Mn a4 Fe a5 CO a6 Ni a7 Cu a8 Zn a9 Ca a10 Mg a11 [R(CN) 6 ] c vac r n(H 2 O)j(SO 4 ) (Formula II);
wherein R(CN) 6 is a coordination complex selected from the group consisting of hexacyanoferrate, hexacyanocobaltate, hexacyanochromate, and hexacyanomanganate;
wherein vac identifies an R(CN) 6 vacancy;
wherein ay, y=1 to 11, represent transition metal parameters;
wherein bx, x=1 to 5 represent alkali metal parameters;
wherein for each element of a first set of alkali metal parameters {b1, b2}, {b1, b2}>0;
wherein for each element of a second set of alkali metal parameters {b3, b4, b5}, 0≤{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, a6, a7, a8, a9, a10, a11}≤1;
wherein for each element of the set {a4, a5}>0;
wherein 0<c≤1;
wherein 0≤r≤0.25;
wherein 0≤j;
wherein c+r=1;
wherein 0≤n;
wherein said TMCCC includes a monoclinic structure, a rhombohedral structure, a cubic crystal structure, or mixtures thereof; and
wherein j>0.

Assignees

• Natron Energy Inc

Inventors

• Mamuye Ashenafi Damtew
• Friebel Daniel
• Shrivastava Aniruddh

Classifications

• H01B1/10 Primary

  sulfides · CPC title

• C01P2002/76

  by a space-group or by other symmetry indications · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• C01P2004/03

  obtained by SEM · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title