Positive-electrode plate and manufacturing method thereof, lithium-ion secondary battery, battery module, battery pack, and apparatus
This application provides a positive-electrode plate, including a current collector, and a first active substance layer and a second active substance layer that are sequentially disposed on a surface of the current collector. The first active substance layer includes a first positive-electrode active material, and the first positive-electrode active material includes at least one of a compound represented by Formula (I) Li 1+x1 Mn a1 M 1-a1 O 2-y1 A y1 or a compound represented by Formula (II) Li 1+x2 Mn a2 N 2-a2 O 4-y2 B y2 . The second active substance layer includes a second positive-electrode active material having a pH value of from 10˜12. In this application, the active substance layer that includes high-pH positive-electrode active material is disposed outside the active substance layer that includes a lithium manganese-based positive-electrode active material, so as to make a layered electrode plate.
1. A positive-electrode plate, comprising a current collector, and a first active substance layer and a second active substance layer that are sequentially disposed on a surface of the current collector, wherein
the first active substance layer comprises a first positive-electrode active material, and the first positive-electrode active material comprises at least one of a compound represented by Formula (I) or a compound represented by Formula (II):
Li 1+x1 Mn a1 M 1-a1 O 2-y1 A y1 Formula (I)
where −0.1≤x1≤0.2, 0.5≤a1≤1, 0≤y1<0.2, M comprises one or more of Ni, Fe, Cr, Co, Ti, Zn, V, Al, Zr, and Ce, and A comprises one or more of S, N, F, Cl, Br, and I;
Li 1+x2 Mn a2 L 2-a2 O 4-y2 B y2 Formula (II)
in the Formula (II), −0.1≤x2≤0.2, 1.5≤a2≤2, 0≤y2<0.5, L comprises one or more of Ni, Fe, Cr, Co, Ti, Zn, V, Al, Zr, and Ce, and B comprises one or more of S, N, F, Cl, Br, and I; and
the second active substance layer comprises a second positive-electrode active material having a pH value of from 10 to 12; and the pH value is measured as follows: at 25° C., adding 5 g of a purchased or self-made second positive-electrode active material into 500 ml of deionized water, stirring at a speed of 30 r/min for 2 hours by using a magnetic stirrer, placing into an ultrasonic cleaner to perform ultrasonic treatment for 2 hours, setting aside a homogeneously dispersed solution for 1 hour, and then measuring the pH value of the solution by using a pH tester; and
a specific surface area BET2 of the second positive-electrode active material is not lower than a specific surface area BET1 of the first positive-electrode active material, and 1.2≤BET2/BET1≤2.
2. The positive-electrode plate according to claim 1 , wherein the second positive-electrode active material is selected from one or more of lithium iron phosphate, lithium manganese iron phosphate, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide.
3. The positive-electrode plate according to claim 2 , wherein the second positive-electrode active material comprises other transition metal elements, non-transition metal elements, or non-metal elements than constituent elements of the second positive-electrode active material, wherein the transition metal elements are one or more of Ni, Fe, Co, Zr, Cr, Ti, Zn, and V, the non-transition metal elements are one or more of Al and Ce, and the non-metal elements are one or more of S, N, F, Cl, Br, and I; and/or
wherein the second positive-electrode active material comprises a coating layer disposed on a surface of the second positive-electrode active material, and the coating layer has a material selected from one or more of boron oxide, zirconium oxide, titanium oxide, aluminum oxide, magnesium oxide, or zinc oxide.
4. The positive-electrode plate according to claim 3 , wherein the second positive-electrode active material comprises a compound represented by Formula (III):
Li 1+x3 Ni a3 Co b3 M′ 1-a3-b3 O 2-y3 A′ y3 Formula (III)
in the Formula (III), −0.1≤x3≤0.2, 0.5≤a3<1, 0<b3<0.5, 0.7≤a3+b3<1, 0≤y3<0.2, M′ comprises one or more of Mn, Fe, Cr, Ti, Zn, V, Al, Zr, and Ce, and A′ comprises one or more of S, N, F, Cl, Br, and I.
5. The positive-electrode plate according to claim 2 , wherein the second positive-electrode active material comprises a coating layer disposed on a surface of the second positive-electrode active material, and the coating layer has a material selected from one or more of boron oxide, zirconium oxide, titanium oxide, aluminum oxide, magnesium oxide, or zinc oxide.
6. The positive-electrode plate according to claim 2 , wherein the second positive-electrode active material comprises other transition metal elements, non-transition metal elements, or non-metal elements than constituent elements of the second positive-electrode active material, wherein the transition metal elements are one or more of Ni, Fe, Co, Zr, Cr, Ti, Zn, and V, the non-transition metal elements are one or more of Al and Ce, and the non-metal elements are one or more of S, N, F, Cl, Br, and I; and
wherein the second positive-electrode active material comprises a coating layer disposed on a surface of the second positive-electrode active material, and the coating layer has a material selected from one or more of boron oxide, zirconium oxide, titanium oxide, aluminum oxide, magnesium oxide, or zinc oxide.
7. The positive-electrode plate according to claim 2 , wherein the second positive-electrode active material comprises a compound represented by Formula (III):
Li 1+x3 Ni a3 Co b3 M′ 1-a3-b3 O 2-y3 A′ y3 Formula (III)
in the Formula (III), −0.1≤x3≤0.2, 0.5≤a3≤1, 0<b3<0.5, 0.7≤a3+b3<1, 0≤y3<0.2, M′ comprises one or more of Mn, Fe, Cr, Ti, Zn, V, Al, Zr, and Ce, and A′ comprises one or more of S, N, F, Cl, Br, and I.
8. The positive-electrode plate according to claim 1 , wherein the second positive-electrode active material comprises a compound represented by Formula (III):
Li 1+x3 Ni a3 Co b3 M′ 1-a3-b3 O 2-y3 A′ y3 Formula (III)
in the Formula (III), −0.1≤x3≤0.2, 0.5≤a3<1, 0<b3<0.5, 0.7≤a3+b3<1, 0≤y3<0.2, M′ comprises one or more of Mn, Fe, Cr, Ti, Zn, V, Al, Zr, and Ce, and A′ comprises one or more of S, N, F, Cl, Br, and I.
9. The positive-electrode plate according to claim 1 , wherein a ratio of mass m1 of the first positive-electrode active material per unit area in the first active substance layer to mass m2 of the second positive-electrode active material per unit area in the second active substance layer satisfies: 1<ml/m2≤19.
10. The positive-electrode plate according to claim 1 , wherein the second positive-electrode active material is a lithium-transition metal composite oxide or a lithium-transition metal composite phosphate having a pH value of from 10 to 12.
11. The positive-electrode plate according to claim 1 , wherein the second positive-electrode active material is a lithium-transition metal composite oxide or a lithium-transition metal composite phosphate having a pH value of from 10 to 12.
12. A lithium-ion secondary battery, comprising a casing, a positive-electrode plate, a negative-electrode plate, a separator, and an electrolyte, wherein the positive-electrode plate is the positive-electrode plate according to claim 1 .
13. The lithium-ion secondary battery according to claim 12 , wherein
the negative-electrode plate has an active material selected from one or more of soft carbon, hard carbon, artificial graphite, natural graphite, silicon, silicon oxide compound, silicon carbon composite, or lithium titanate;
the electrolyte comprises an organic solvent and a lithium salt, wherein the organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, or ethyl methyl carbonate, and the lithium salt is selected from one or more of LiPF 6 , LiBF 4 , LiBOB, LiAsF 6 , Li(CF 3 SO 2 ) 2 N, LiCF 3 SO 3 , or LiClO 4 ; and
the separator is selected from one or more of polyethylene, polypropylene, a non-woven fabric, or polyvinylidene fluoride.
14. A battery module, comprising the lithium-ion secondary battery according to claim 1 .
15. A battery pack, comprising the battery module according to claim 14 .
16. An apparatus, comprising the lithium-ion secondary battery according to claim 12 , wherein the lithium-ion secondary battery is used as a power supply of the apparatus.
17. The apparatus according to claim 16 , wherein the apparatus comprises a mobile device, an electric vehicle, an electric train, a satellite, a ship, and an energy storage system.
18. The apparatus according to claim 16 , wherein the apparatus comprises a mobile device, an electric vehicle, an electric train, a satellite, a ship, and an energy storage system.
19. A manufacturing method of the positive-electrode plate according to claim 1 , wherein the method comprises the following steps of:
(1) adding a first positive-electrode active material, a conductive agent, and a binder into an organic solvent, stirring for 60 to 180 minutes with a stirring linear speed controlled within a range of 4 m/min to 12 m/min, and homogeneously mixing to obtain a slurry marked as slurry A;
(2) adding a second positive-electrode active material having a pH value of from 10 to 12, a conductive agent, and a binder into an organic solvent system, and stirring for 60 to 180 minutes with a stirring linear speed controlled within a range of 4 m/min to 12 m/min, and homogeneously mixing to obtain a slurry marked as slurry B; and
(3) coating a current collector with the slurry A to form a first active substance layer, coating the first active substance layer with the slurry B to form a second active substance layer, and then drying, cold calendering, slitting, and cutting to obtain the positive-electrode plate, and
wherein the first positive-electrode active material comprises at least one of a compound represented by Formula (I) or a compound represented by Formula (II):
Li 1+x1 Mn a1 M 1-a1 O 2-y1 A y1 Formula (I)
wherein −0.1≤x1≤0.2, 0.5≤a1≤1, 0≤y1<0.2, M comprises one or more of Ni, Fe, Cr, Co, Ti, Zn, V, Al, Zr, and Ce, and A comprises one or more of S, N, F, Cl, Br, and I;
Li 1+x2 Mn a2 N 2-a2 O 4-y2 B y2 Formula (II)
in the Formula (II), −0.1≤x2≤0.2, 1.5≤a2≤2, 0≤y2<0.5, L comprises one or more of Ni, Fe, Cr, Co, Ti, Zn, V, Al, Zr, and Ce, and B comprises one or more of S, N, F, Cl, Br, and I; and
the second positive-electrode active material having a pH value of from 10 to 12; and the pH value is measured as follows: at 25° C., adding 5 g of a purchased or self-made second positive-electrode active material into 500 ml of deionized water, stirring at a speed of 30 r/min for 2 hours by using a magnetic stirrer, placing into an ultrasonic cleaner to perform ultrasonic treatment for 2 hours, setting aside a homogeneously dispersed solution for 1 hour, and then measuring the pH value of the solution by using a pH tester; and
a specific surface area BET2 of the second positive-electrode active material is not lower than a specific surface area BET1 of the first positive-electrode active material, and 1.2≤BET2/BET1≤2.