IP Library Granted Patent US 9,745,202
Granted Patent B2
US 9,745,202 · App. 14/731,607 · Granted Aug 29, 2017

Metal cyanometallate synthesis method

Inventors: Jie Song (Vancouver, WA); Yuhao Lu (Vancouver, WA); Long Wang (Vancouver, WA)
Assignees: Board of Regents, U of Texas System; Sharp Laboratories of America, Inc
C01C3/12H01M4/58H01M10/054Y10T29/49108
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Quick Facts
Patent No.
US 9,745,202
App. No.
14/731,607
Granted
Aug 29, 2017
Kind
B2
Abstract

A method is provided for synthesizing metal cyanometallate (MCM). The method provides a solution of A X M1 Y (CN) Z ; where “A” is selected from a first group of metals and M1 is selected from a second group of metals. The method adds a material including M2 to the solution to form a liquid phase material that may be either a suspension or a solution. M2 is selected from the second group of metals. The method adds acid to the liquid phase material. The addition of acid to the liquid phase material decomposes the M2 material into M2-ions. Simultaneous with the addition of the acid, a precipitate of A N M1 P M2 Q (CN) R .F H 2 O is formed, where N is in a range of 1 to 2. A variation of the above-described synthesis method is also provided.

Claims (46)

1. A method for synthesizing metal cyanometallate (MCM), the method comprising:

providing a solution of A X M1 Y (CN) Z ;

where “A” is selected from a first group of metals consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al), magnesium (Mg), and combinations thereof;

where M1 is selected from a second group of metals 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), cadmium (Cd), Ca, Mg, strontium (Sr), and barium (Ba);

where X is in a range of 0 to 10;

where Y is in a range of 1 to 10;

where Z is in a range of 1 to 10;

adding a material including M2 to the solution to form a liquid phase material selected from a group consisting of a suspension and a solution;

where M2 is selected from the second group of metals;

adding an acid to the liquid phase material;

simultaneously with the addition of the acid, forming a precipitate of A N M1 P M2 Q (CN) R .F H 2 O;

where N is in a range of 1 to 2;

where P is less than or equal to 2;

where F is in a range of 0 to 20;

where Q is less than or equal to 2; and,

where R is less than or equal to 6.

2. The method of claim 1 wherein adding the acid to the liquid phase material includes the acid decomposing the material including M2 into M2-ions.

3. The method of claim 1 wherein adding the acid to the liquid phase material includes adding an acid selected from a group consisting of hydrochloric acid (HCl), sulfuric acid (H 2 SO 4 ), sulfurous acid (H 2 SO 3 ), acetic acid (CH 3 COOH), formic acid (CHOOH), oxalic acid (C 2 H 2 O 4 ), and ascorbic acid.

4. The method of claim 1 wherein adding the acid to the liquid phase material includes additionally adding a reducing agent to the liquid phase material.

5. The method of claim 4 wherein adding the reducing agent to the liquid phase material includes adding a reducing agent selected from a group consisting of sodium borohydride, sodium hyposulfite, sodium sulfite, and polyvinylpyrrolidon.

6. The method of claim 1 wherein adding the acid to the liquid phase material includes adding the acid to the liquid phase material in an inert atmosphere.

7. The method of claim 1 further comprising:

drying the precipitate in a vacuum environment at a temperature in a range between 0 and 200 degrees Centigrade (C.).

8. The method of claim 1 wherein adding the material including M2 to the solution includes adding a material selected from a group consisting of pure M2 and compounds selected from a group consisting of oxides, sulfides, sulfites, carbonates, cyanides, and fluorides.

9. A method for synthesizing metal cyanometallate (MCM), the method comprising:

providing a solution of A X M1 Y (CN) Z ;

where “A” is selected from a first group of metals consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al), magnesium (Mg), and combinations thereof;

where M1 is selected from a second group of metals 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), cadmium (Cd), Ca, Mg, strontium (Sr), and barium (Ba);

where X is in a range of 0 to 10;

where Y is in a range of 1 to 10;

where Z is in a range of 1 to 10;

adding an acid to the solution;

simultaneously with the addition of the acid, forming a precipitate of A N M1 D (CN) E .G H 2 O;

where N is in a range of 1 to 2;

where G is in a range of 0 to 20;

where D is less than or equal to 2; and,

where E is less than or equal to 6.

10. The method of claim 9 wherein adding the acid to the solution includes:

the acid decomposing the A X M1 Y (CN) Z ; and,

releasing M1-ions into the solution.

11. The method of claim 9 wherein adding the acid to the solution includes adding an acid selected from a group consisting of hydrochloric acid (HCl), sulfuric acid (H 2 SO 4 ), sulfurous acid (H 2 SO 3 ), acetic acid (CH 3 COOH), formic acid (CHOOH), oxalic acid (C 2 H 2 O 4 ), and ascorbic acid.

12. The method of claim 9 wherein adding the acid to the solution includes additionally adding a reducing agent to the solution.

13. The method of claim 12 wherein adding the reducing agent to the solution includes adding a reducing agent selected from a group consisting of sodium borohydride, sodium hyposulfite, sodium sulfite, and polyvinylpyrrolidon.

14. The method of claim 9 wherein adding the acid to the solution includes adding the acid to the solution in an inert atmosphere.

15. The method of claim 9 further comprising:

drying the precipitate in a vacuum environment at a temperature in a range between 0 and 200 degrees Centigrade (C.).

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 13, 2021
From: SHARP LABORATORIES OF AMERICA, INC.
To: SHARP KABUSHIKI KAISHA
Reel/Frame 054906/0896 →
CONFIRMATORY LICENSE Recorded Sep 29, 2017
From: SHARP LABORATORIES OF AMERICA, INC.
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 043741/0259 →
CORRECTIVE ASSIGNMENT TO CORRECT THE RECEIVING PARTY PREVIOUSLY RECORDED AT REEL: 043004 FRAME: 0652. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jul 17, 2017
From: SONG, JIE; LU, YUHAO; WANG, LONG
To: BOARD OF REGENTS, UNIV. OF TEXAS; SHARP LABORATORIES OF AMERICA, INC.
Reel/Frame 043339/0971 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 14, 2017
From: SONG, JIE; LU, YUHAO; WANG, LONG
To: SHARP LABORATORIES OF AMERICA, INC.
Reel/Frame 043004/0652 →
Continuity (20)
Continuation In Part 14271498 · May 7, 2014
Continuation In Part 14230882 · Mar 31, 2014
Continuation In Part 14198755 · Mar 6, 2014
Continuation In Part 14198702 · Mar 6, 2014
Continuation In Part 14198663 · Mar 6, 2014
Continuation In Part 14193782 · Feb 28, 2014
Continuation In Part 14193501 · Feb 28, 2014
Continuation In Part 14174171 · Feb 6, 2014
Continuation In Part 14067038 · Oct 30, 2013
Continuation In Part 14059599 · Oct 22, 2013
Continuation In Part 13907892 · Jun 1, 2013
Continuation In Part 13897492 · May 20, 2013
Continuation In Part 13872673 · Apr 29, 2013
Continuation In Part 13752930 · Jan 29, 2013
Continuation In Part 13603322 · Sep 4, 2012
Continuation In Part 13523694 · Jun 14, 2012
Continuation In Part 13499195 · Apr 17, 2012
Continuation In Part 13432993 · Mar 28, 2012
Provisional Application 62008869 · Jun 6, 2014
Related Publication 20150266746A1 · Sep 24, 2015