Active material having surface treatment layer for battery and method of preparing the same
An active material for a battery has a surface treatment layer that includes a conductive agent and at least one coating-element-containing compound selected from the group consisting of a coating-element-containing hydroxide, a coating-element-containing oxyhydroxide, a coating-element-containing oxycarbonate, a coating-element-containing hydroxycarbonate, and a mixture thereof.
1. An active material for a battery, comprising:
a material that undergoes reversible electrochemical oxidation-reduction reactions and having a surface; and
a surface treatment layer on the surface and comprising:
a conductive agent, and
at least one coating-element-containing compound selected from the group consisting of a coating-element-containing hydroxide, a coating-element-containing oxyhydroxide, a coating-element-containing oxycarbonate, a coating-element-containing hydroxycarbonate, and a mixture thereof,
wherein said material is selected from the group consisting of a compound that reversibly forms a lithium-containing compound by a reaction with lithium ions, a material that reversibly intercalates/deintercalates lithium ions and a lithiated intercalation compound, and
wherein the lithiated intercalation compound is selected from the group consisting of a lithium-containing metal oxide, a lithium-containing chalcogenide compound, and a carbon-based material.
2. The active material of claim 1 , wherein the coating element is soluble in an organic solvent or water.
3. The active material of claim 2 , wherein the coating element is at least one selected from the group consisting of an alkali metal, an alkaline earth metal, a group 13 element of the Periodic Table, a group 14 element of the Periodic Table, a group 15 element of the Periodic Table, and a transition metal.
4. The active material of claim 3 , wherein the coating element is at least one selected from the group consisting of Mg, Al, Co, K, Na, Ca, Si, Ti, B, As, Zr, Sn, V, Ge, Ga, and a combination thereof.
5. The active material of claim 1 , wherein the coating-element-containing compound has either an amorphous or a crystalline phase.
6. The active material of claim 1 , wherein a thickness of said surface-treatment layer is 1 to 300 nm.
7. The active material of claim 6 , wherein a thickness of said surface-treatment layer is 1 to 100 nm.
8. The active material of claim 1 , wherein an amount of the coating element is 2×10 −5 to 2% by weight of the active material.
9. The active material of claim 8 , wherein the amount of the coating element is 0.001 to 2% by weight of the active material.
10. The active material of claim 1 , wherein the conductive agent is at least one material selected from the group consisting of a carbon-based conductive agent, a graphite-based conductive agent, a metal-based conductive agent, and a metallic-compound-based conductive agent.
11. The active material of claim 1 , wherein an amount of the conductive agent is 0.5 to 10% by weight of the active material.
12. The active material of claim 11 , wherein the amount of the conductive agent is 1 to 5% by weight of the active material.
13. The active material of claim 1 , wherein the coating element comprises Al, and
the surface treatment layer on the surface comprises the conductive agent and an Al-containing compound selected from the group consisting of an Al-containing hydroxide, an Al-containing oxyhydroxide, an Al-containing oxycarbonate, an Al-containing hydroxycarbonate, and a mixture thereof.
14. The active material of claim 13 , wherein the surface treatment layer is coated on the surface by a method comprising:
adding the conductive agent and the coating-element source to a solvent selected from the group consisting of water, organic solvent, and a mixture thereof to prepare a coating liquid;
adding the material to the coating liquid to coat the material; and
drying the coated material to form the surface-treatment layer comprising the conductive agent and the at least one coating-element-containing compound selected from the group consisting of the coating-element-containing hydroxide, the coating-element-containing oxyhydroxide, the coating-element-containing oxycarbonate, the coating-element-containing hydroxycarbonate, and the mixture thereof.
15. The active material of claim 1 , wherein an average particle size of said material is 1 to 50 μm.
16. The active material of claim 15 , wherein the average particle size is 5 to 20 μm.
17. The active material of claim 1 , wherein the active material is prepared by:
adding the conductive agent and the coating-element source to a solvent selected from the group consisting of water, organic solvent, and a mixture thereof to prepare a coating liquid;
adding the material to the coating liquid to coat the surface of the material; and
drying the coated material to form the surface-treatment layer comprising the conductive agent and the at least one coating-element-containing compound selected from the group consisting of the coating-element-containing hydroxide, the coating-element-containing oxyhydroxide, the coating-element-containing oxycarbonate, the coating-element-containing hydroxycarbonate, and the mixture thereof.
18. The active material of claim 17 , wherein the material to be coated is selected from the group consisting of a metal, a lithium-containing alloy, a compound that reversibly forms a lithium-containing compound by a reaction with lithium ions, a material that reversibly intercalates/deintercalates the lithium ions and a lithiated intercalation compound.
19. The active material of claim 18 , wherein the material is the lithiated intercalation compound that is selected from the group consisting of a lithium-containing metal oxide, a lithium-containing chalcogenide compound, and a carbon-based material.
20. The active material of claim 18 , wherein the material is the lithiated intercalation compound that is at least one selected from the group consisting of a lithium compound with the following formulas (1) to (13):
Li x Mn 1−y M y A 2
(1)
Li x Mn 1−y M y O 2−z X z
(2)
Li x Mn 2 O 4−z X z
(3)
Li x Mn 2−y M y A 4
(4)
Li x Co 1−y M y A 2
(5)
Li x Co 1−y M y O 2−z X z
(6)
Li x Ni 1−y M y A 2
(7)
Li x Ni 1−y M y O 2−z X z
(8)
Li x Ni 1−y Co y O 2−z X z
(9)
Li x Ni 1−y−z Co y M z A α
(10)
Li x Ni 1−y−z Co y M z O 2−α X α
(11)
Li x Ni 1−y−z Mn y M z A α
(12)
Li x Ni 1−y−z Mn y M z O 2−α X α
(13)
wherein
0.95≦x≦1.1; 0≦y≦0.5; 0≦z≦0.5; 0≦α≦2;
M is at least one element selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, and rare earth elements;
A is at least one element selected from the group consisting of O, F, S, and P; and
X is at least one element selected from the group consisting of F, S, and P.
21. The active material of claim 17 , wherein the coating element is soluble in an organic solvent or water.
22. The active material of claim 21 , wherein the coating element is at least one selected from the group consisting of an alkali metal, an alkaline earth metal, a group 13 element of the Periodic Table, a group 14 element of the Periodic Table, a group 15 element of the Periodic Table, and a transition metal.
23. The active material of claim 22 , wherein the coating element is at least one selected from the group consisting of Mg, Al, Co, K, Na, Ca, Si, Ti, B, As, Zr, Sn, V, Ge, Ga, and a combination thereof.
24. The active material of claim 17 , wherein an amount of the coating-element source is 0.1 to 50% by weight of the coating liquid.
25. The active material of claim 24 , wherein the amount of the coating-element source is 5 to 30% by weight of the coating liquid.
26. The active material of claim 17 , wherein said adding the coating liquid to coat the material and said drying the coated material comprises mixing a mixture of the material with the coating liquid while heating the mixture of the material and the coating liquid by increasing a temperature of the mixture.
27. The active material of claim 24 , wherein said mixing of the mixture further comprises mixing under one of a vacuum condition and a condition of injecting purging gas, while increasing the temperature.
28. The active material of claim 17 , further comprising sieving the dried coated material through a sieve.
29. The active material of claim 17 , wherein the adding the material to the coating liquid comprises:
mixing the material and the coating liquid to coat the material while removing the added solvent so as to produce the surface-treatment layer on the material, the produced surface-treatment layer comprising the conductive agent and the at least one coating-element-containing compound selected from the group consisting of the coating-element-containing hydroxide, the coating-element-containing oxyhydroxide, the coating-element-containing oxycarbonate, the coating-element-containing hydroxycarbonate, and the mixture thereof.
30. The active material of claim 29 , wherein said adding the conductive agent and the coating-element source to the solvent further comprises forming the coating liquid as one of a solution and a suspension.
31. The active material of claim 30 , wherein the conductive agent and the coating-element source are added to the solvent using a reflux method.
32. The active material of claim 29 , wherein the coating-element source comprises an Al-containing source.
33. The active material of claim 29 , wherein the coating-element source comprises a B-containing source.
34. The active material of claim 29 , wherein said mixing the material and the coating liquid to coat the material while removing the added solvent comprises:
adding the material and the coating liquid to a mixing vessel,
mixing the material and the coating liquid in the mixing vessel to coat the material with the coating liquid,
transferring the coated material to a tray, and
drying the coated material while in the tray to remove the solvent to produce the surface-treatment layer.
35. The active material of claim 29 , wherein said mixing the material and the coating liquid to coat the material while removing the added solvent comprises:
adding the material and the coating liquid to a mixing vessel, and
mixing the material and the coating liquid in the mixing vessel to coat the material while removing the solvent.
36. The active material of claim 35 , wherein said mixing the material and the coating liquid to coat the material further comprises raising a temperature of the mixing vessel while mixing the material and the coating liquid to coat the material and to evaporate the solvent.
37. The active material of claim 36 , wherein said mixing the material and the coating liquid to coat the active material further comprises introducing a purging gas to the mixing vessel to evaporate the solvent and to remove impure gasses from the mixing vessel.
38. The active material of claim 37 , wherein the purging gas comprises CO 2 , N 2 , Ar, or any inert gas.
39. The active material of claim 36 , wherein the raising the temperature comprises raising the temperature to at or between 50 and 100° C.
40. The active material of claim 39 , wherein the raising the temperature comprises circulating warm liquid around an exterior wall of the mixing vessel.
41. The active material of claim 34 , wherein the drying the coated material comprises drying at a temperature at or between room temperature and 200° C. for at or between 1 and 24 hours.
42. An active material for a battery, comprising:
a material that undergoes reversible electrochemical oxidation-reduction reactions and having a surface; and
a surface treatment layer on the surface and comprising:
a conductive agent, and
at least one coating-element-containing compound selected from the group consisting of a coating-element-containing hydroxide, a coating-element-containing oxyhydroxide, a coating-element-containing oxycarbonate, a coating-element-containing hydroxycarbonate, and a mixture thereof,
wherein said material is selected from the group consisting of a compound that reversibly forms a lithium-containing compound by a reaction with lithium ions, a material that reversibly intercalates/deintercalates lithium ions and a lithiated intercalation compound, wherein the lithiated intercalation compound being at least one selected from the group consisting of a lithium compound with the following formulas (1) to (13):
Li x Mn 1−y M y A 2
(1)
Li x Mn 1−y M y O 2−z X z
(2)
Li x Mn 2 O 4−z X z
(3)
Li x Mn 2−y M y A 4
(4)
Li x Co 1−y M y A 2
(5)
Li x Co 1−y M y O 2−z X z
(6)
Li x Ni 1−y M y A 2
(7)
Li x Ni 1−y M y O 2−z X z
(8)
Li x Ni 1−y Co y O 2−z X z
(9)
Li x Ni 1−y−z Co y M z A α
(10)
Li x Ni 1−y−z Co y M z O 2−α X α
(11)
Li x Ni 1−y−z Mn y M z A α
(12)
Li x Ni 1−y−z Mn y M z O 2−α X α
(13)
wherein
0.95≦x≦1.1; 0≦y≦0.5; 0≦z≦0.5; 0≦α≦2;
M is at least one element selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, and rare earth elements;
A is at least one element selected from the group consisting of O, F, S, and P; and
X is at least one element selected from the group consisting of F, S, and P.
43. An active material for a battery, comprising:
a material that undergoes reversible electrochemical oxidation-reduction reactions and having a surface; and
a surface treatment layer on the surface and comprising:
a conductive agent, and
at least one coating-element-containing compound selected from the group consisting of a coating-element-containing hydroxide, a coating-element-containing oxyhydroxide, a coating-element-containing oxycarbonate, a coating-element-containing hydroxycarbonate, and a mixture thereof,
wherein said material is selected from the group consisting of a compound that reversibly forms a lithium-containing compound by a reaction with lithium ions, a material that reversibly intercalates/deintercalates lithium ions and a lithiated intercalation compound and wherein the coating element comprises B, and the surface treatment layer on the surface comprises the conductive agent and a B-containing compound selected from the group consisting of a B-containing hydroxide, a B-containing oxyhydroxide, a B-containing oxycarbonate, a B-containing hydroxycarbonate, and a mixture thereof.
44. An electrode for use in a battery, comprising:
a current collector; and
an active material on said current collector, said active material being coated with a layer comprising:
a conductive agent, and
at least one compound selected from the group consisting of a coating-element-containing hydroxide, a coating-element-containing oxyhydroxide, a coating-element-containing oxycarbonate, a coating-element-containing hydroxycarbonate, and a mixture thereof,
wherein said active material is selected from the group consisting of a compound that reversibly forms a lithium-containing compound by a reaction with lithium ions, a material that reversibly intercalates/deintercalates lithium ions and a lithiated intercalation compound and wherein the lithiated intercalation compound is selected from the group consisting of a lithium-containing metal oxide, a lithium-containing chalcogenide compound, and a carbon-based material.
45. A battery comprising:
a first electrode comprising a current collector and a coated active material, the coated active material comprising a layer including a conductive agent and at least one compound selected from the group consisting of a coating-element-containing hydroxide, a coating-element-containing oxyhydroxide, a coating-element-containing oxycarbonate, a coating-element-containing hydroxycarbonate, and a mixture thereof;
an electrolyte; and
a counter electrode spaced apart from said first electrode to perform reversible oxidation-reduction reactions with said first electrode through said electrolyte,
wherein said active material is selected from the group consisting of a compound that reversibly forms a lithium-containing compound by a reaction with lithium ions, a material that reversibly intercalates/deintercalates lithium ions and a lithiated intercalation compound, and
wherein the lithiated intercalation compound is selected from the group consisting of a lithium-containing metal oxide, a lithium-containing chalcogenide compound, and a carbon-based material.