Metal cyanometallate synthesis method

Patent metadata

Field	Value
Publication number	US-9745202-B2
Application number	US-201514731607-A
Country	US
Kind code	B2
Filing date	Jun 5, 2015
Priority date	Mar 28, 2012
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

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.

First claim

We claim:

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.).

Assignees

• Univ Texas
• Sharp Laboratories America Inc
• Board Of Regents U Of Texas System
• Sharp Laboratories America Inc

Inventors

• Song Jie
• Lu Yuhao
• Wang Long

Classifications

• C01C3/12 Primary

  Simple or complex iron cyanides · CPC title

• Y10T29/49108

  Electric battery cell making · CPC title

• H01M4/58

  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 title

• H01M10/054

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title