US4512905A
Expired / Lapsed
US
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Method of making sodium zirconium silico-phosphates
Assignee: Texas A&M University System
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Filing: 1982-12-23
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Granted: 1985-04-23
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Expires: 2002-12-23
Abstract
Abstract Homogeneous sodium zirconium silico-phosphates having the formula Na1+x+4yZr2-y(SiO4)x(PO4)3-x where x is from 1 to 2.8 and y is between 0 and about 0.5, are prepared by heating a zirconium phosphate with an aqueous, alkaline sodium silicate solution and calcining the resulting solid orthorhombic crystalline product. The calcined product is useful as a solid electrolyte for transporting sodium ions in a sodium-sulfur storage battery.
Inventors
- 👤 Abraham Clearfield
- 👤 Paul Jerus
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 21:19
CPC Classifications
G; G01; G01N; G01N27/00; G01N27/26; G01N27/403; G01N27/406; G01N27/407; G01N27/4073; C; C01; C01B; C01B33/00; C01B33/20; G02; G02F; G02F1/00; G02F1/01; G02F1/15; G02F1/1514; G02F1/1523; G02F1/1525; H; H01; H01M; H01M10/00; H01M10/36; H01M10/39; H01M10/3909; H01M6/00; H01M6/14; H01M6/18; H01M6/185; Y; Y02; Y02E; Y02E60/00; Y02E60/10
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
98 words
A method of preparing a crystalline compound which provides fast sodium ion transport which comprises heating a hydrated orthorhombic crystalline solid having the formula on a water-free basis Na.sub.1+x+4y Zr.sub.2-y (SiO.sub.4).sub.x (PO.sub.4).sub.3-x where x is between about 1.0 and about 2.8 and y is between 0 and 0.5, at a temperature between about 1,000° C. and about 1,250° C. until the orthorhombic crystalline solid is converted to a homogeneous, fast sodium ion conducting, monoclinic or rhombohedral crystalline sodium zirconium silico-phosphate of the formula indicated above, or a mixture of the two free from any separate, detectable zirconia phase.
Claim 2
Independent Claim
98 words
A method of preparing a crystalline compound which provides fast sodium ion transport which comprises heating a hydrated orthorhombic crystalline solid having the formula on a water-free basis Na.sub.1+x+4y Zr.sub.2-y (SiO.sub.4).sub.x (PO.sub.4).sub.3-x where x is between about 1.0 and about 2.8 and y is between 0 and 0.5, at a temperature between about 1,000° C. and about 1,250° C. until the orthorhombic crystalline solid is converted to a homogeneous, fast sodium ion conducting, monoclinic or rhombohedral crystalline sodium zirconium silico-phosphate of the formula indicated above, or a mixture of the two free from any separate, detectable zirconia phase.
Claim 3
Dependent Claim
28 words
A method of preparing a crystalline compound which provides fast sodium ion transport in accordance with claim 1 in which x is between about 1.8 and about 2.3.
Claim 4
Dependent Claim
36 words
A method of preparing a crystalline compound which provides fast sodium ion transport in accordance with claim 1 which comprises heating the orthorhombic crystalline solid at a temperature between about 1,100° C. and about 1,225° C.
Claim 5
Independent Claim
245 words
A method of preparing a crystalline compound which provides fast sodium ion transport and having the formula: Na.sub.1+x+4y Zr.sub.2-y (SiO.sub.4).sub.x (PO.sub.4).sub.3-x where x is between about 1.0 and about 2.8 and y is between 0 and 0.5, which comprises the steps: heating an aqueous dispersion comprising soda and silica in solution in a mol ratio of soda to silica of between about 0.9:1 and about 4:1 and a powdered zirconium phosphate having the formula Zr(MPO 4 ) 2 .zH 2 O where M is hydrogen, sodium or a mixture of hydrogen and sodium, and z is an integer from 0 to 10, in an amount to provide a mol ratio of silica to zirconium phosphate of between about 1.2:1 and about 1.8:1, the proportions of the soda, silica and phosphate in the reaction mixture being in excess of the proportions of these materials in the final product, said heating being conducted at a temperature between about 250° C. and about 350° C., until reaction occurs and a precipitate is formed, separating precipitated material from supernatant liquid, and washing and drying such separated precipitate to recover a hydrated orthorhombic crystalline solid, and calcining the hydrated orthorhombic crystalline solid at a temperature between about 1000° C. and about 1250° C. until conversion to a homogeneous, fast sodium ion conducting, monoclinic or rhombohedral crystalline, sodium zirconium silico-phosphate of the formula indicated above, or a mixture of the two, free from any separate, detectable zirconia phase, is substantially complete.
Claim 6
Independent Claim
245 words
A method of preparing a crystalline compound which provides fast sodium ion transport and having the formula: Na.sub.1+x+4y Zr.sub.2-y (SiO.sub.4).sub.x (PO.sub.4).sub.3-x where x is between about 1.0 and about 2.8 and y is between 0 and 0.5, which comprises the steps: heating an aqueous dispersion comprising soda and silica in solution in a mol ratio of soda to silica of between about 0.9:1 and about 4:1 and a powdered zirconium phosphate having the formula Zr(MPO 4 ) 2 .zH 2 O where M is hydrogen, sodium or a mixture of hydrogen and sodium, and z is an integer from 0 to 10, in an amount to provide a mol ratio of silica to zirconium phosphate of between about 1.2:1 and about 1.8:1, the proportions of the soda, silica and phosphate in the reaction mixture being in excess of the proportions of these materials in the final product, said heating being conducted at a temperature between about 250° C. and about 350° C., until reaction occurs and a precipitate is formed, separating precipitated material from supernatant liquid, and washing and drying such separated precipitate to recover a hydrated orthorhombic crystalline solid, and calcining the hydrated orthorhombic crystalline solid at a temperature between about 1000° C. and about 1250° C. until conversion to a homogeneous, fast sodium ion conducting, monoclinic or rhombohedral crystalline, sodium zirconium silico-phosphate of the formula indicated above, or a mixture of the two, free from any separate, detectable zirconia phase, is substantially complete.
Claim 7
Dependent Claim
34 words
A method of preparing a crystalline compound which provides fast sodium ion transport in accordance with claim 4 in which the mol ratio of soda to silica is between about 1:1 and about 3:1.
Claim 8
Dependent Claim
36 words
A method of preparing a crystalline compound which provides fast sodium ion transport in accordance with claim 4 in which the aqueous dispersion is heated at a temperature between about 275° C. and about 325° C.
Claim 9
Dependent Claim
36 words
A method of preparing a crystalline compound which provides fast sodium ion transport in accordance with claim 4 in which the solid product is calcined at a temperature between about 1,100° C. and about 1,225° C.
Claim 10
Dependent Claim
23 words
A method of preparing a crystalline compound which provides fast sodium ion transport in accordance with claim 4 in which M is hydrogen.
Claim 11
Dependent Claim
22 words
A method of preparing a crystalline compound in accordance with claim 4 in which x is between about 1.8 and about 2.3.
References Cited (Backward Citations)
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