Metal-Doped Transition Metal Hexacyanoferrate (TMHCF) Battery Electrode

• US 20130266861A1
• Filed: 06/01/2013
• Published: 10/10/2013
• Est. Priority Date: 03/28/2012
• Status: Active Grant

• Current Assignee: Sharp Kabushiki Kaisha (Hon Hai Precision Industry Co., Ltd.)
• Original Assignee: Sharp Laboratories of America Incorporated (Hon Hai Precision Industry Co., Ltd.)
• Inventors: Lu, Yuhao, Lee, Jong-Jan, Evans, David
• Granted Patent: US 8,968,925 B2
• Time in Patent Office: Days
• US Class Current: 429/211
• CPC Class Codes: H01M 10/054 Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/1397 of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/58 of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A method is provided for synthesizing a metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode. The method prepares a first solution of A_xFe(CN)₆ and Fe(CN)₆, where A cations may be alkali or alkaline-earth cations. The method adds the first solution to a second solution containing M-ions and M′-ions. M is a transition metal, and M′ is a metal dopant. Subsequent to stirring, the mixture is precipitated to form A_xM_cM′_dFe_z(CN)_n.mH₂O particles. The A_xM_cM′_dFe_z(CN)_n.mH₂O particles have a framework and interstitial spaces in the framework, where M and M′ occupy positions in the framework. Alternatively, the method prepares A_aA′_bM_yFe_z(CN)_n.mH₂O particles. A and A′ occupy interstitial spaces in the A_aA′_bM_yFe_z(CN)_n.mH₂O particle framework. A metal-doped TMHCF electrode is also provided.

Claims

1. A metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode, the electrode comprising:

a metal current collector;

A_xM_yFe_z(CN)_n.mH₂O particles overlying the current collector;

where A cations are selected from a group consisting of alkali and alkaline-earth cations;

where M is a transition metal;

where x is less than or equal to 2;

where y is less than or equal to 2;

where z is in a range of 0.1 to 2;

where n is in a range of 1 to 6;

where m is in a range of 0 to 7; and

,

a metal dopant modifying the A_xM_yFe_z(CN)_n.mH₂O particles.

2. The TMHCF battery electrode of claim 1 wherein the A cations are selected from a group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), calcium (Ca), and magnesium (Mg).

3. The TMHCF battery electrode of claim 1 wherein transition metal M is selected from a group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), niobium (Nb), ruthenium (Ru), tin (Sn), indium (In), and cadmium (Cd).

4. The TMHCF battery electrode of claim 1 wherein the metal-dopant modified A_xM_yFe_z(CN)_n.mH₂O particles form A_aA′

_bM_yFe_z(CN)_n.mH₂O particles having a framework and interstitial spaces in the framework;

where A′

is a metal dopant;

where A and A′

occupy interstitial spaces;

where b is less than or equal to 1; and

,

where “

a”

is less than or equal to 2.

5. The TMHCF battery electrode of claim 4 wherein the A′

metal dopant is a material other than A, selected from a group consisting of ammonium-ions (NH₄⁺), Li, Na, K, Rb, Cs, Ca, and Mg.

6. The TMHCF battery electrode of claim 1 wherein the metal-dopant modified A_xM_yFe_z(CN)_n.mH₂O particles form A_xM_cM′

_dFe_z(CN)_n.mH₂O particles having a framework and interstitial spaces in the framework;

where M′

is a metal dopant;

where M and M′

occupy positions in the framework;

where d is less than or equal to 1; and

,

where c is less than or equal to 2.

7. The TMHCF battery electrode of claim 6 wherein the M′

metal dopant is a material other than M, selected from a group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Ru, Sn, In, and Cd.

8. The TMHCF battery electrode of claim 1 wherein the metal dopant modified A_xM_yFe_z(CN)_n.mH₂O particles are selected from a group consisting of A_aA′

_bM_yFe_z(CN)_n.M′

H₂O and A_cM_yM′

_dFe_z(CN)_n.M′

H₂O, where A′ and

M′

are metal dopants.

9. The TMHCF battery electrode of claim 1 wherein the metal dopant modified A_xM_yFe_z(CN)_n.mH₂O particles have a greater electrical conductivity and longer cycling life than A_xM_yFe_z(CN)_n.mH₂O particles.

10. A method for synthesizing a metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode, the method comprising:

preparing a first solution of A_xFe(CN)₆ and Fe(CN)₆;

where A cations are selected from a group consisting of alkali and alkaline-earth cations;

where x is less than or equal to 2;

adding the first solution to a second solution containing M-ions and M′

-ions, forming a mixture;

where M is a transition metal;

where M′

is a metal dopant;

subsequent to stirring, precipitating the mixture;

forming A_xM_cM′

_dFe_z(CN)_n.mH₂O particles;

where n is in a range of 1 to 6;

where m is in a range of 0 to 7;

where d is less than or equal to 1;

where c is less than or equal to 2; and

,

where z is in a range of 0.1 to 2.

11. The method of claim 10 wherein forming A_xM_cM′

_dFe_z(CN)_n.mH₂O particles includes forming A_xM_cM′

_dFe_z(CN)_n.mH₂O particles having a framework and interstitial spaces in the framework, where M and M′

occupy positions in the framework.

12. The method of claim 10 wherein adding the first solution to the second solution containing M-ions and M′

-ions includes the M′

metal dopant being a material other than M, selected from a group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), niobium (Nb), ruthenium (Ru), tin (Sn), indium (In), and cadmium (Cd).

13. The method of claim 10 wherein preparing the first solution of A_xFe(CN)₆ and Fe(CN)₆ includes the A cations being selected from a group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), calcium (Ca), and magnesium (Mg).

14. The method of claim 10 wherein adding the first solution to the second solution containing M-ions and M′

-ions includes the M-ions being selected from a group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Ru, Sn, In, and Cd.

15. The method of claim 10 wherein preparing the first solution of A_xFe(CN)₆ and Fe(CN)₆ includes the Fe(CN)₅ being a material selected from a group consisting of ferrocyanide ([Fe(CN)₆]⁴⁻

) and ferricyanide ([Fe(CN)₆]³⁻

).

16. The method of claim 10 wherein preparing the first solution of A_xFe(CN)₆ and Fe(CN)₆ includes the A_xFe(CN)₆ having a molar concentration in a range of 0.001 moles (M) to 2 M;

and,

wherein adding the first solution to the second solution containing M-ions and M′

-ions includes the M-ions having a molar concentration in a range of 0.001 M to 10 M.

17. A method for synthesizing a metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode, the method comprising:

preparing a first solution of A_xFe(CN)₆ and Fe(CN)₆,

where A cations are selected from a group consisting of alkali and alkaline-earth cations;

where x is less than or equal to 2;

adding the first solution to a second solution containing M-ions, where M is a transition metal;

adding A′

-ions to a solution selected from a group consisting of the first solution, the second solution, and both the first and second solutions, forming a mixture, where A′

is a metal dopant;

subsequent to stirring, precipitating the mixture;

forming A_aA′

_bM_yFe_z(CN)_n.mH₂O particles;

where n is in a range of 1 to 6;

where y is less than or equal to 2;

where z is in a range of 0.1 to 2;

where m is in a range of 0 to 7;

where b is less than or equal to 1; and

,

where “

a”

is less than or equal to 2.

18. The method of claim 17 wherein forming A_aA′

_bM_yFe_z(CN)_n.mH₂O particles includes forming A_aA′

_bM_yFe_z(CN)_n.mH₂O particles having a framework and interstitial spaces in the framework, where A and A′

occupy interstitial spaces.

19. The method of claim 17 wherein preparing the first solution of A_xFe(CN)₆ and Fe(CN)₆ includes the A cations being selected from a group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), calcium (Ca), and magnesium (Mg).

20. The method of claim 17 wherein adding A′

-ions to the solution includes the A′

metal dopant being a material other than A, selected from a group consisting of ammonium-ions (NH₄⁺), Li, Na, K, Rb, Cs, Ca, and Mg.

21. The method of claim 17 wherein adding the first solution to the second solution containing M-ions includes the M-ions being selected from a group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), niobium (Nb), ruthenium (Ru), tin (Sn), indium (In), and cadmium (Cd).

22. The method of claim 17 wherein preparing the first solution of A_xFe(CN)₆ and Fe(CN)₆ includes the Fe(CN)₅ being a material selected from a group consisting of ferrocyanide ([Fe(CN)₆]⁴⁻

) and ferricyanide ([Fe(CN)₆]³⁻

).

23. The method of claim 17 wherein preparing the first solution of A_xFe(CN)₆ and Fe(CN)₆ includes the A_xFe(CN)₆ having a molar concentration in a range of 0.001 moles (M) to 2 M;

and,

wherein adding the first solution to the second solution containing M-ions includes the M-ions having a molar concentration in a range of 0.001 M to 10 M.