Active material, method of preparing the active material electrode including the active material, and secondary battery including the electrode

Patent metadata

Field	Value
Publication number	US-9887419-B2
Application number	US-201414467284-A
Country	US
Kind code	B2
Filing date	Aug 25, 2014
Priority date	Aug 26, 2013
Publication date	Feb 6, 2018
Grant date	Feb 6, 2018

Abstract

An electrode active material including a vanadium oxide represented by Formula 1,

VO x   Formula 1
wherein vanadium in the vanadium oxide has a mixed oxidation state of a plurality of oxidation numbers, and the oxidation numbers include an oxidation number of +3, and wherein, in Formula 1 above, 1.5<x<2.5.

First claim

What is claimed is:

1. An electrode active material comprising a vanadium oxide initially represented by Formula 1,
VO x   Formula 1

wherein vanadium in the vanadium oxide has a mixed oxidation state of a plurality of oxidation numbers,
wherein the plurality of oxidation numbers comprise an oxidation number of +3,
wherein, in Formula 1, 1.5<x<2.5, and
wherein the vanadium having an oxidation number of +3 is contained in an amount in a range of about 10 atomic percent to about 30 atomic percent, based on a total amount of vanadium having a mixed oxidation state of oxidation numbers of +3, +4, and +5.

2. The electrode active material of claim 1 , wherein the vanadium comprises a mixed oxidation state of 3 oxidation numbers.

3. The electrode active material of claim 1 , wherein the plurality of oxidation numbers comprises an oxidation number of +4 and an oxidation number of +5.

4. The electrode active material of claim 3 , wherein the vanadium having an oxidation number of +4 is contained in an amount in a range of about 40 atomic percent to about 60 atomic percent, based on a total amount of vanadium having a mixed oxidation state of oxidation numbers of +3, +4, and +5, and the vanadium having an oxidation number of +5 has an amount in a range of about 25 atomic percent to about 50 atomic percent, based on a total amount of vanadium having a mixed oxidation state of oxidation numbers of +3, +4, and +5.

5. The electrode active material of claim 1 , wherein the vanadium oxide comprises a nanostructure.

6. The electrode active material of claim 5 , wherein the vanadium oxide nanostructure is a vanadium oxide nanosheet, a vanadium oxide nanotube, or a combination thereof.

7. The active material of claim 6 , wherein the vanadium oxide nanosheet is comprises a layer or a plurality of stacked layers.

8. The electrode active material of claim 6 , wherein the vanadium oxide comprises a vanadium oxide nanosheet which comprises about 1 to about 10 layers and has an interlayer distance in a range of about 2.5 nanometers to about 3.5 nanometers.

9. The electrode active material of claim 6 , wherein the vanadium oxide comprises a vanadium oxide nanosheet which has a shape of a circle, an ellipse, a triangle, a quadrangle, a pentagon, a hexagon, or combination thereof.

10. The electrode active material of claim 6 , wherein the vanadium oxide comprises a vanadium oxide nanotube which is a multiwall nanotube.

11. The electrode active material of claim 6 , wherein, the vanadium oxide comprises a vanadium oxide nanotube which has a length in a range of about 1 micrometer to about 2 micrometers, an inner diameter in a range of about 15 nanometers to about 50 nanometers, and an outer diameter in a range of about 50 nanometers to about 100 nanometers.

12. The electrode active material of claim 1 , wherein in Formula 1, wherein x satisfies the condition of 1.9≦x<2.2.

13. The electrode active material of claim 1 , wherein in Formula 1, x is in a range of about 1.995 to about 2.13.

14. The electrode active material of claim 1 , wherein, when analyzed by X-ray diffraction analysis, a (001) peak and a (002) peak occur at a Bragg angle of 10° two-theta or less, an intensity ratio of the (002) peak to the (001) peak is 0.6 or less, and a full width at half maximum of the (001) peak is 0.5 or less.

15. An electrode comprising the electrode active material of claim 1 .

16. A secondary battery comprising the electrode of claim 15 .

17. The secondary battery of claim 16 , wherein in the electrode active material of the electrode of the secondary battery comprising the vanadium oxide represented by Formula 1, the vanadium having an oxidation number of +3 is contained in an amount in a range of about 10 atomic percent to about 25 atomic percent, based on a total amount of vanadium having a mixed oxidation state of oxidation numbers of +3, +4, and +5, and
wherein the content of the vanadium having an oxidation number of +3, +4, and +5 is determined after charging and discharging the secondary battery.

18. The secondary battery of claim 16 , wherein in the electrode active material of the electrode of the secondary battery comprising the vanadium oxide represented by Formula 1, the vanadium having an oxidation number of +4 is contained in an amount in a range of about 40 atomic percent to about 60 atomic percent, based on a total amount of vanadium having a mixed oxidation state of oxidation numbers of +3, +4, and +5,
wherein the vanadium having an oxidation number of +5 is contained in an amount in a range of about 30 atomic percent to about 50 atomic percent, based on the total amount of vanadium having a mixed oxidation state of oxidation numbers of +3, +4, and +5, and
wherein the content of the vanadium having an oxidation number of +3, +4, and +5 is determined after charging and discharging the secondary battery.

19. A magnesium secondary battery comprising the electrode of claim 15 .

20. A sodium secondary battery comprising the electrode of claim 15 .

21. A lithium secondary battery comprising the electrode of claim 15 .

22. A method of preparing an electrode active material comprising a vanadium oxide represented by Formula 1,
VO x ,  Formula 1

wherein the vanadium in the vanadium oxide has a mixed oxidation state of a plurality of oxidation numbers, wherein the oxidation numbers comprise an oxidation number of +3, wherein, in Formula 1, 1.5<x<2.5, and wherein the vanadium having an oxidation number of +3 is contained in an amount in a range of about 10 atomic percent to about 30 atomic percent, based on a total amount of vanadium having a mixed oxidation state of oxidation numbers of +3, +4, and +5 the method comprising:
contacting a reducing agent, a solvent, and a starting material comprising vanadium oxide to obtain a mixture; and
applying an electromagnetic wave to the mixture to reduce the starting material, to prepare the vanadium oxide represented by Formula 1.

23. The method of claim 22 , wherein the reducing agent comprises an amine.

24. The method of claim 23 , wherein the reducing agent comprises octadecylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, heptadecylamine, hexadecylamine, or combination thereof.

25. The method of claim 22 , wherein the electromagnetic wave is a microwave.

26. The method of claim 25 , wherein the microwave is applied to the mixture with an output in a range of about 200 watts to about 1,500 watts and a frequency in a range of about 1 gigahertz to about 2.45 gigahertz.

27. The method of claim 22 , wherein the reducing of the starting material is performed by a microwave-hydrothermal reaction.

28. The method of claim 22 , wherein an amount of the reducing agent is in a range of about 0.1 mole to about 1 mole, based on 1 mole of the vanadium oxide.

29. The method of claim 22 , wherein the starting material containing vanadium is divanadium pentoxide, vanadium oxydiacetate, or combination thereof.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Kim Ryounghee
• Lee Seoksoo
• Han Dongwook
• Benayad Anass
• Kim Jusik
• Chang Wonseok

Classifications

• H01M4/483 Primary

  for non-aqueous cells (H01M4/485 takes precedence) · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M10/054

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

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title