Positive electrode mix for secondary batteries including irreversible additive
View Patent ↗Disclosed is a positive electrode mix for secondary batteries including an irreversible additive. More particularly, provided is a positive electrode mix for secondary batteries including an irreversible additive that decreases irreversible efficiency of a positive electrode active material and a positive electrode.
1. A positive electrode mix for secondary batteries comprising an irreversible additive that decreases irreversible efficiency of a positive electrode active material and a positive electrode,
wherein the irreversible additive is a lithium molybdenum sulfide represented by Formula 1 below:
Li 2+x Mo 6-y M y S 8-z (1),
wherein −0.1≤x≤0.5, 0≤y≤0.5, −0.1≤z≤0.5, and M is a metal or transition metal cation having an oxidation number of +2 to +4, and
the irreversible additive has an operation voltage of 1.0 V to 2.5 V with respect to Li, and
wherein the positive electrode mix further comprises a positive electrode active material comprising a lithium transition metal oxide represented by Formula 2 or 3 below:
Li x M y Mn 2-y O 4-z A z (2),
wherein in Formula 2:
M is at least one element selected from the group consisting of Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Ti and Bi;
A is at least one monovalent or divalent anion; and
0.9≤x≤1.2, 0<y<2, and 0≤z<0.2,
(1− x )LiM′O 2-y A y - x Li 2 MnO 3-y′ A y′ (3),
wherein in Formula 3:
M′ is Mn a M b ;
M is at least one selected from the group consisting of Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn and Period II transition metals;
A is at least one selected from the group consisting of anions such as PO 4 , BO 3 , CO 3 , F and NO 3 ; and
0<x<1, 0<y≤0.02, 0<y′≤0.02, 0.5≤a≤1.0, 0≤b≤0.5, and a+b=1.
2. The positive electrode mix according to claim 1 , wherein the irreversible additive exhibits conductivity.
3. The positive electrode mix according to claim 2 , wherein an electric resistance value of the irreversible additive is 5 μΩm to 100 μΩm.
4. The positive electrode mix according to claim 1 , wherein the lithium molybdenum sulfide is Li 2.3 MO 6 S 7.7 .
5. The positive electrode mix according to claim 1 , wherein the irreversible additive is comprised in an amount of 0.1 wt % to 5 wt % with respect to a total weight of the positive electrode mix.
6. The positive electrode mix according to claim 1 , wherein the positive electrode mix further comprises a binder and a conductive material.
7. The positive electrode mix according to claim 1 , wherein the irreversible additive is uniformly mixed with the positive electrode active material and coated on a positive electrode collector.
8. The positive electrode mix according to claim 1 , wherein the irreversible additive is coated while forming a layer with the positive electrode active material on a positive electrode collector.
9. The positive electrode mix according to claim 8 , wherein a thickness of the irreversible additive layer is 0.1% or more and less than 20% with respect to a total thickness of a positive electrode mix layer.
10. The positive electrode mix according to claim 8 , wherein the irreversible additive layer further comprises a conductive material.
11. The positive electrode mix according to claim 10 , wherein the conductive material is comprised in an amount of less than 20 wt % with respect to a total weight of the irreversible additive.
12. A positive electrode manufactured by coating the positive electrode mix according to claim 1 on an electrode collector.
13. A secondary battery comprising an electrode assembly, which comprises the positive electrode according to claim 12 , a negative electrode, and a separator disposed between the positive electrode and the negative electrode, impregnated with an electrolyte solution.
14. The secondary battery according to claim 13 , wherein the negative electrode comprises a silicon (Si)-based material as a negative electrode active material.
15. The secondary battery according to claim 14 , wherein the negative electrode active material further comprises a carbon-based material, and the carbon-based material is comprised in an amount of 70 wt % to 99.9 wt % with respect to the total weight of the negative electrode active material.
16. The secondary battery according to claim 15 , wherein the carbon-based material is at least one selected from the group consisting of artificial crystalline graphite, natural crystalline graphite, amorphous hard carbon, low-crystalline soft carbon, carbon black, acetylene black, Ketjen black, Super-P, graphene and fibrous carbon.
17. The secondary battery according to claim 16 , wherein the carbon-based material is artificial crystalline graphite and/or natural crystalline graphite.
18. The secondary battery according to claim 13 , wherein the secondary battery is a lithium ion battery, a lithium ion polymer battery or a lithium polymer battery.
19. A battery module comprising the secondary battery according to claim 13 as a unit cell.
20. A battery pack comprising the battery module according to claim 19 .
21. A device comprising the battery pack according to claim 20 as a power source.
22. The device according to claim 21 , wherein the device is an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or a system for storing power.