Nanocrystal oxide/glass composite mesoporous powder or thin film, process for producing the same, and utilizing the powder or thin film, various devices, secondary battery and lithium storing device

• US 7,771,871 B2
• Filed: 11/16/2004
• Issued: 08/10/2010
• Est. Priority Date: 11/17/2003
• Status: Expired due to Fees

• Current Assignee: National Institute of Advanced Industrial Science and Technology (Government of Japan)
• Original Assignee: National Institute of Advanced Industrial Science and Technology (Government of Japan)
• Inventors: Homma, Itaru, Zhou, Haoshen
• Primary Examiner(s): Ryan; Patrick
• Assistant Examiner(s): ANTHONY, JULIAN
• Application Number:
  US10/595,856
• Publication Number:
  US 20070027015A1
• Time in Patent Office: 2,093 Days
• Field of Search: 429/218.1, 429/220, 429/221, 429/223, 429/224, 429/231.5, 429/231.95, 423/304, 423/592.1, 204/284, 977/781
• US Class Current: 429/218.1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C03C 1/008 for the production of films or coatings
• CPC Class Codes: C03C 14/006 the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
• CPC Class Codes: C03C 2214/16 Microcrystallites, e.g. of optically or electrically active material
• CPC Class Codes: C03C 2214/32 comprising a sol-gel process
• CPC Class Codes: C04B 2235/365 Borosilicate glass
• CPC Class Codes: C04B 35/46 based on titanium oxides or titanates containing also zirconium or hafnium oxides, zirconates or hafnates C04B35/49
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y10S 977/781 Possessing nonosized surface openings that extend partially into or completely through the host material

Abstract

The present invention aims to realize (1) manufacture of a mesoporous composite powder or thin film composed of nanocrystalline metal oxide—glass having a three-dimensional structure with a large specific surface area, (2) construction of a porous structure framework with nanocrystalline metal oxide crystal and a slight amount of glass phase (SiO₂ or P₂O₅, B₂O₃), (3) control of crystal growth of metal oxide with a slight amount of glass phase (SiO₂ or P₂O₅, B₂O₃), (4) simplification of the manufacturing process, and (5) use thereof in manufacture of a lithium intercalation electric device, photocatalytic device, solar battery and energy storage device. Provided are a nanocrystal oxide—glass mesoporous composite powder or thin film having a three-dimensional structure with regularly arranged mesopores, and a secondary battery comprising the same.

Claims

1. A nanocrystal oxide—

glass mesoporous composite powder or film having a three-dimensional structure with regularly arranged mesopores and in which a glass phase contains P₂O₅.

5. A manufacturing method of nanocrystal oxide—

glass mesoporous composite powder according to claim 1, comprising the steps of;

using a block macromolecule or interface activating agent as a template, and adding hydrochloric acid (HCl) to an aqueous solution of metal alkoxide, metal chloride, or PO(OC₂H₅)₃ or a solution obtained by dissolving these in alcohol such as ethanol;

manufacturing powder having a glass phase metal oxide—

inorganic oxide composite mesostructure with a sol-gel process;

maturing and gelling this between room temperature and 90°

C.;

removing the block macromolecule or interface activating agent by performing heat treatment thereto in the atmosphere at 350 to 400°

C. and manufacturing a glass phase metal oxide—

glass phase mesoporous composite film; and

additionally performing heat treatment thereto at 400 to 700°

C. so as to change the phase of the glass phase metal oxide into crystallite.

6. A method according to claim 5, wherein an inorganic oxide of a stable glass phase is P₂O₅.

7. A method according to claim 5, wherein a dissimilar metal oxide selected from a group consisting of MnO₂, NiO, Fe₂O₃, CuO, Li₂O, WO₃ and SnO₂ is added in a slight amount at a synthesizing stage, and the mesoporous powder is formed from a nanocrystal oxide, a glass phase of inorganic oxide, and said dissimilar metal oxide having a multicomponent glass phase.

8. A method according to claim 5, wherein metal alkoxide or metal chloride is Ti(OC₃H₇)₄, Zr(OC₄H₉)₄, NbCl₅, LiCl, NiCl₂, FeCl₃, CuCl₂, MnCl₂, SnCl₄ or WCl₅.

9. A method according to claim 5, wherein said powder is used in the manufacture of a lithium battery, lithium intercalation electric device, photocatalytic device, solar battery, or energy storage device.

10. A manufacturing method of nanocrystal oxide—

glass mesoporous composite film according to claim 1, comprising the steps of;

using a block macromolecule or interface activating agent as a template, adding hydrochloric acid (HCl) to metal alkoxide, metal chloride, or an aqueous solution of PO(OC₂H₅)₃ or a solution obtained by dissolving these in alcohol such as ethanol, and obtaining a sol solution by performing hydrolysis while adjusting the pH;

forming a film having a glass phase metal oxide-inorganic oxide-block macromolecule or interface activating agent composite mesostructure on a substrate by delivering the sol solution in drops onto a substrate, rapidly rotating the substrate, and evaporating and gelling the solvent;

maturing and gelling this between room temperature and 90°

C.;

removing the block macromolecule or interface activating agent by performing heat treatment thereto in the atmosphere at 350 to 400°

C. and manufacturing a glass phase metal oxide—

glass phase mesoporous composite film; and

additionally performing heat treatment thereto at 400 to 700°

C. so as to change the phase of the glass phase metal oxide into crystallite.

11. A method according to claim 10, wherein an inorganic oxide of a stable glass phase is P₂O₅.

12. A method according to claim 10, wherein a dissimilar metal oxide selected from a group consisting of MnO₂, NiO, Fe₂O₃, CuO, Li₂O, WO₃ and SnO₂ is added in a slight amount at a synthesizing stage, and the mesoporous film is formed from a nanocrystal oxide, a glass phase of inorganic oxide, and said dissimilar metal oxide having a multicomponent glass phase.

13. A method according to claim 10, wherein metal alkoxide or metal chloride is Ti(OC₃H₇)₄, Zr(OC₄H₉)₄, NbCl₅, LiCl, NiCl₂, FeCl₃, CuCl₂, MnCl₂, SnCl₄ or WCl₅.

14. A method according to claim 10, wherein said film is used in the manufacture of a lithium battery, lithium intercalation electric device, photocatalytic device, solar battery, or energy storage device.

15. A secondary battery having said nanocrystal oxide—

glass mesoporous composite film according to claim 1, said film forming a nanocrystal oxide—

glass mesoporous composite electrode of said secondary battery.

16. The secondary battery according to claim 15, wherein the average diameter of said mesopores is 2 nm to 10 nm.

17. A secondary battery according to claim 15, wherein a framework of the nanocrystal oxide—

glass mesoporous composite electrode has a hexagonal or cubic structure and contains uniform crystallite oxides of several nano-orders.

18. A secondary battery according to claim 17, wherein a thickness of a wall of the framework is 2 nm to 9 nm.

19. A secondary battery according to claim 15, wherein the nanocrystal oxide is one or more types of metal oxides selected from the group consisting of TiO₂, NiO, MnO₂, FeO, Fe₂O₃, Fe₃O₄, CoO, CoO₂, CrO₂, CO₃O₄, WO₃, SnO and SnO₂.

20. A secondary battery according to claim 15, wherein the glass phase includes one or more inorganic oxides selected from the group consisting of SiO₂ and B₂O₃.

21. A secondary battery according to claim 15, wherein the glass phase is a multicomponent glass phase containing one or more metal oxides selected from the group consisting of MnO₂, NiO, Fe₂O₃, CuO, Li₂O, WO₃ and SnO₂ at a molar ratio of 2% to 60% in relation to the glass phase.

22. A secondary battery according to claim 15, wherein both an ionic conductive path and electronic conductive path are provided in a framework of the nanocrystal oxide—

glass mesoporous composite electrode by adding ion conductive or electron conductive dissimilar metal oxides in a network-shaped glass phase at a molar ratio of 2% to 60% in relation to the glass phase.

23. A secondary battery according to claim 15, wherein the nanocrystal oxide—

glass mesoporous composite is used as the electrode of the secondary battery, and its energy density of charging or discharging is able to maintain a rate of more than 60% of 0.1 A/g even when increasing the charging or discharging rate to ten times 0.1 A/g (1.0 A/g ), and even one hundred times 0.1 A/g (10 A/g ).

24. A secondary battery according to claim 15, wherein the nanocrystal oxide—

glass mesoporous composite is used as the electrode of the secondary battery so as to increase the surface area, and the charging/discharging capacity has a large capacity of 1.0 to 5.0 times the maximum theoretical capacity in relation to active oxides selected from the group consisting of TiO₂, NiO, MnO₂, FeO, Fe₂O₃, Fe₃O₄, CoO, CoO₂, CrO₂, Co₃O₄, WO₃, SnO and SnO₂.

25. A secondary battery according to claim 15, wherein the nanocrystal oxide—

glass mesoporous composite is used as the electrode of the secondary battery, and a high reversible ratio of 95% or higher is realized even when increasing the charging or discharging rate to ten times 0.1 A/g (1.0 A/g ), and even one hundred times 0.1 A/g (10 A/g).

26. A secondary battery according to claim 15, wherein the nanocrystal oxide—

glass mesoporous composite is used as the electrode of lithium, and a high reversible capacity of 60% to 70% or higher of the initial capacity is realized after a charging/discharging cycle of several hundred cycles even when increasing the charging or discharging rate to ten times 0.1 A/g (1.0 A/g ), and even one hundred times 0.1 A/g (10 A/g).

27. A secondary battery according to claim 15, wherein a nanocrystal oxide—

a glass phase of inorganic oxide—

dissimilar metal oxide to which a slight amount of dissimilar metal oxide was added has a high reversible capacity at a rate of 40% to 70% or higher of 0.1 A/g even when the charging/discharging rate is increased to a rate of one hundred times, five hundred times or one thousand times 0.1 A/g.

28. A secondary battery according to claim 15, wherein the battery has a high reversible ratio, r >

95%.

29. A nanocrystal oxide—

glass mesoporous composite powder or film according to claim 1, wherein a porous structure framework contains uniform nanocrystal oxides.

30. A nanocrystal oxide—

glass mesoporous composite powder or film according to claim 1, wherein the powder or film has a large specific surface area in a range of 50 to 400 m²/g.

2. A nanocrystal oxide—

glass mesoporous composite powder or film having a hexagonal or cubic three-dimensional structure and in which a glass phase contains P₂O₅.

3. A nanocrystal oxide—

glass mesoporous composite powder or film according to claim 2, wherein a porous structure framework contains uniform nanocrystal oxides.

4. A nanocrystal oxide—

glass mesoporous composite powder or film according to claim 2, wherein the powder or film has a large specific surface area in a range of 50 to 400 m²/g.