Titanyl sulfate hydrate powder, method for producing titanyl sulfate hydrate powder, method for producing aqueous titanyl sulfate solution, method of producing electrolyte solution, and method for producing redox flow battery

Patent metadata

Field	Value
Publication number	US-11753309-B2
Application number	US-201917270357-A
Country	US
Kind code	B2
Filing date	Aug 29, 2019
Priority date	Aug 30, 2018
Publication date	Sep 12, 2023
Grant date	Sep 12, 2023

Abstract

There is provided a titanyl sulfate hydrate powder comprising 25 to 40% by mass of titanium element in terms of TiO 2 , 40 to 60% by mass of sulfur element in terms of H 2 SO 4 , and niobium element in such an amount that a molar ratio of niobium element to titanium element (Nb/Ti) is 0.00005 to 0.012, with a molar ratio of the sulfur element content to the titanium element content (S/Ti) being 1.1 to 1.5, and comprising crystalline titanyl sulfate dihydrate (TiOSO 4 ·2H 2 O). Thus, the present invention can provide a titanyl sulfate hydrate powder with a high dissolution rate in water and a production method therefor, as well as a method for producing an aqueous titanyl sulfate solution, a method for producing an electrolyte and a method for producing a redox flow battery, using the titanyl sulfate hydrate powder.

First claim

The invention claimed is:

1. A titanyl sulfate hydrate powder comprising 25 to 40% by mass of titanium element in terms of TiO 2 , 40 to 60% by mass of sulfur element in terms of H 2 SO 4 , and niobium element in such an amount that a molar ratio of niobium element to titanium element (Nb/Ti) is 0.00005 to 0.012, with a molar ratio of the sulfur element content to the titanium element content (S/Ti) being 1.1 to 1.5, and comprising crystalline titanyl sulfate dihydrate (TiOSO 4 ·2H 2 O).

2. The powder according to claim 1 , wherein a time taken to dissolve the powder in water at 25° C. to a concentration of 550 g/L is 10 hours or less.

3. The powder according to claim 1 , wherein in X-ray diffraction measurement, a height of a peak at a diffraction angle (2θ) of 27.0+/−0.5° is 0.024 to 0.1 times of a height of a peak at 10.7+/−0.5°.

4. The powder according to claim 1 , wherein for particles contained in the powder, an average short-axis length is 2 to 5 μm and an average aspect ratio is 2 to 30.

5. The powder according to claim 1 for producing an electrolyte for a battery.

6. A method for producing the powder according to claim 1 , comprising adding, to an aqueous solution containing 50 to 300 g/L of titanium element in terms of TiO 2 , 650 to 1200 g/L of sulfur element in terms of H 2 SO 4 , and niobium element in such an amount that a molar ratio of niobium element to titanium element (Nb/Ti) is 0.0005 to 0.02, seed crystals of titanyl sulfate dihydrate (TiOSO 4 ·2H 2 O) containing titanium element in the mole number of 0.003 to 0.05 times to the mole number of titanium element in the aqueous solution, and heating the mixture at 50 to 120° C. to deposit crystals of titanyl sulfate hydrate.

7. A method for producing an aqueous solution of titanyl sulfate, comprising dissolving the powder according to claim 1 in water to prepare an aqueous solution containing 80 to 300 g/L of titanium element in terms of TiO 2 , sulfur element in such an amount that a molar ratio of sulfur element to titanium element (S/Ti) is 1.1 to 1.5, and niobium element in such an amount that a molar ratio of niobium element to titanium element (Nb/Ti) is 0.00005 to 0.012.

8. A method for producing an electrolyte for a battery, comprising dissolving the powder according to claim 1 in water to prepare an aqueous solution containing 1.0 to 3.7 mol/L of titanium ions.

9. The method for producing an electrolyte according to claim 8 , wherein in addition to the powder, a metal salt or an acid is further dissolved.

10. The method for producing an electrolyte according to claim 9 , wherein in addition to the powder, another metal salt selected from the group consisting of Mn, Fe, Ce, Cr, V and Sn is dissolved to prepare an aqueous solution containing 1.0 to 3.7 mol/L of titanium ions and 0.3 to 5 mol/L of the other metal ions.

11. The method for producing an electrolyte according to claim 9 , wherein in addition to the powder, sulfuric acid is dissolved to prepare an aqueous solution containing 1.0 to 3.7 mol/L of titanium ions and 3 to 9 mol/L of sulfate ions.

12. A method for producing a redox flow battery, comprising supplying the electrolyte prepared by the method according to claim 8 as a positive electrode electrolyte or a negative electrode electrolyte, to a battery cell comprising a positive electrode, a negative electrode and a membrane interposed between the electrodes.

13. The method for producing a redox flow battery according to claim 12 , wherein the positive electrode electrolyte is an aqueous solution containing 1.0 to 3.7 mol/L of titanium ions and containing 0.3 to 5 mol/L of other metal ions selected from the group consisting of Mn, Fe, Ce, Cr, V and Sn, and the negative electrode electrolyte is an aqueous solution containing 1.0 to 3.7 mol/L of titanium ions and 3 to 9 mol/L of sulfate ions.

14. The method for producing a redox flow battery according to claim 12 , wherein both of the positive electrode electrolyte and the negative electrode electrolyte are an aqueous solution containing 1.0 to 3.7 mol/L of titanium ions and 0.3 to 5 mol/L of other metal ions selected from the group consisting of Mn, Fe, Ce, Cr, V and Sn.

Assignees

• Tayca Corp
• Sumitomo Electric Industries

Inventors

• Fukuda Jun
• Tsurumura Tatsuya
• Kaku Hirokazu
• Tatsumi Ryouta

Classifications

• C01G23/008 Primary

  Titanium- and titanyl sulfate (C01G23/001 takes precedence) · CPC title

• Y02E60/50

  Fuel cells · CPC title

• C01P2002/52

  containing elements as dopants · CPC title

• C01P2002/72

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

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title