Positive electrode active substance for all solid-state lithium secondary battery
A positive electrode active substance for an all solid-state lithium secondary battery having an operating potential of 4.5 V or more at a metal Li reference potential, wherein the surface of the present core particles composed of a spinel-type lithium manganese-containing composite oxide containing at least Li, Mn, O, and two or more elements other than these is coated with an amorphous compound containing Li, A, where A represents one element or a combination of two or more elements selected from the group consisting of Ti, Zr, Ta, Nb, Zn, W, and Al, and O. Primary particles of the present core particles are composed of a polycrystal. The D50 is 0.5-9 μm, the value of (|mode diameter−D50|/mode diameter)×100 is 0 to 25%, the value of (|mode diameter−D10|/mode diameter)×100 is 20-58%, and the value of the average primary particle diameter/D50 is 0.20-0.99.
1. A positive electrode active substance for an all solid-state lithium secondary battery, having an operating potential of 4.5 V or more at a metal Li reference potential, wherein a surface of present core particles composed of a spinel-type lithium manganese-containing composite oxide containing at least Li, Mn, O, and two or more elements other than Li, Mn, and O is coated with an amorphous compound containing Li, A, and O, where A represents one element or a combination of two or more elements selected from the group consisting of Ti, Zr, Ta, Nb, Zn, W, and Al; and primary particles of the present core particles are composed of a polycrystal;
wherein, with regard to a D50, a mode diameter, and a D10 of the positive electrode active substance according to a measurement of a volume-based particle size distribution obtained via measurements by a laser diffraction scattering-type particle size distribution measurement method, the D50 is 0.5 to 9 μm, a percentage of a ratio of the absolute value of the difference between the mode diameter and the D50 relative to the mode diameter, (|mode diameter−D50|/mode diameter)×100, is 0 to 25%, a percentage of a ratio of the absolute value of the difference between the mode diameter and the D10 relative to the mode diameter, (|mode diameter−D10|/mode diameter)×100, is 20 to 58%;
wherein a ratio, average primary particle, diameter/D50 of an average primary particle diameter of the positive electrode active substance, which is calculated from a scanning-type electron microscope (SEM) image obtained by a scanning-type electron microscope (SEM), relative to the D50 is 0.20 to 0.99;
wherein said amorphous compound contains Li in excess of 1 mol relative to 1 mol of the A element; and
wherein an amount of carbonate ions present on the surface of the positive electrode active substance is less than 2.5 wt % relative to the positive electrode active substance.
2. The positive electrode active substance for an all solid-state lithium secondary battery according to claim 1 , wherein the molar ratio, Li/A, of Li relative to the A element in the positive electrode active substance surface, as obtained by X-ray photoelectron spectroscopy (XPS), is 0.5 to 3.5.
3. The positive electrode active substance for an all solid-state lithium secondary battery according claim 2 , wherein the spinel-type lithium manganese-containing composite oxide is represented by a general formula [Li x (M1 y M2 z Mn 2-x-y-z )O 4-δ ], wherein 1.00≤≤x≤1.20, 0.20≤y≤1.20, 0<z≤0.5, 0≤δ≤0.2, M1 represents one element or a combination of two or more elements selected from the group consisting of Ni, Co, and Fe, and M2 represents one element or a combination of two or more elements selected from the group consisting of Na, Mg, Al, P, K, Ca, Ti, V, Cr, Cu, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce.
4. The positive electrode active substance for an all solid-state lithium secondary battery according claim 2 , wherein the spinel-type lithium manganese-containing composite oxide is represented by a general formula [Li x (Ni y M z Mn 2-x-y-z )O 4-δ ], wherein 1.00≤x≤1.20, 0.20≤y≤0.70, 0<z≤0.5, 0≤δ≤0.2, and M represents one element or a combination of two or more elements selected from the group consisting of Na, Mg, Al, P, K, Ca, Ti, V, Cr, Fe, Co, Cu, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce.
5. The positive electrode active substance for an all solid-state lithium secondary battery according claim 2 , wherein the mode diameter according to a measurement of a volume-based particle size distribution obtained via measurements by a laser diffraction scattering-type particle size distribution measurement method is 0.4 to 11 μm.
6. The positive electrode active substance for an all solid-state lithium secondary battery according to claim 1 , wherein the spinel-type lithium manganese-containing composite oxide is represented by a general formula [Li x (M1 y M2 z Mn 2-x-y-z )O 4-δ ], wherein 1.00≤x≤1.20, 0.20≤y≤1.20, 0<z≤0.5, 0≤δ≤0.2, M1 represents one element or a combination of two or more elements selected from the group consisting of Ni, Co, and Fe, and M2 represents one element or a combination of two or more elements selected from the group consisting of Na, Mg, Al, P, K, Ca, Ti, V, Cr, Cu, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce.
7. The positive electrode active substance for an all solid-state lithium secondary battery according claim 6 , wherein the mode diameter according to a measurement of a volume-based particle size distribution obtained via measurements by a laser diffraction scattering-type particle size distribution measurement method is 0.4 to 11 μm.
8. The positive electrode active substance for an all solid-state lithium secondary battery according to claim 1 , wherein the spinel-type lithium manganese-containing composite oxide is represented by a general formula [Li x (Ni y M z Mn 2-x-y-z )O 4-δ ], wherein 1.00≤x≤1.20, 0.20≤y≤0.70, 0<z≤0.5, 0≤δ≤0.2, and M represents one element or a combination of two or more elements selected from the group consisting of Na, Mg, Al, P, K, Ca, Ti, V, Cr, Fe, Co, Cu, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce.
9. The positive electrode active substance for an all solid-state lithium secondary battery according claim 8 , wherein the mode diameter according to a measurement of a volume-based particle size distribution obtained via measurements by a laser diffraction scattering-type particle size distribution measurement method is 0.4 to 11 μm.
10. The positive electrode active substance for an all solid-state lithium secondary battery according to claim 1 , wherein the mode diameter according to a measurement of a volume-based particle size distribution obtained via measurements by a laser diffraction scattering-type particle size distribution measurement method is 0.4 to 11 μm.
11. The positive electrode active substance for an all solid-state lithium secondary battery according to claim 1 , wherein the average primary particle diameter which is calculated from a scanning-type electron microscope (SEM) image obtained by a scanning-type electron microscope (SEM) is 0.3 to 5.0 μm.
12. The positive electrode active substance for an all solid-state lithium secondary battery according claim 1 , wherein a Dmin in a result of measuring a volume-based particle size distribution obtained via measurements by a laser diffraction scattering-type particle size distribution measurement method is 0.1 to 2.0 μm.
13. The positive electrode active substance for an all solid-state lithium secondary battery according to claim 1 , wherein, in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD), a value of a strain obtained by Rietveld analysis is 0.00 to 0.35.
14. An all solid-state lithium secondary battery, comprising the positive electrode active substance for an all solid-state lithium secondary battery according to claim 1 as a positive electrode active substance.
15. The positive electrode active substance for an all solid-state lithium secondary battery according to claim 1 , wherein the amorphous coating compound has a molar ratio, Li/A, of Li relative to the A element, as obtained by X-ray photoelectron spectroscopy (XPS), of greater than 1.0 and 2.3 or less.
16. A positive electrode active substance for an all solid-state lithium secondary battery, having an operating potential of 4.5 V or more at a metal Li reference potential, wherein a surface of present core particles composed of a spinel-type lithium manganese-containing composite oxide containing at least Li, Mn, O, and two or more elements other than Li, Mn, and O is coated with an amorphous compound containing Li, A, and O, where A represents one element or a combination of two or more elements selected from the group consisting of Ti, Zr, Ta, Nb, Zn, W, and Al; a crystallite size of the positive electrode active substance is 80 to 490 nm; and a ratio, crystallite size/average primary particle diameter, of the crystallite size relative to an average primary particle diameter of the positive electrode active substance, which is calculated from a scanning-type electron microscope (SEM) image obtained by a scanning-type electron microscope (SEM), is 0.01 to 0.32;
wherein, with regard to a D50, a mode diameter, and a D10 of the positive electrode active substance, the D50 is 0.5 to 9 μm, a percentage of a ratio of the absolute value of the difference between the mode diameter and the D50 relative to the mode diameter, (|mode diameter−D50|/mode diameter)×100, is 0 to 25%, a percentage of a ratio of the absolute value of the difference between the mode diameter and the D10 relative to the mode diameter, ((|mode diameter−D10|/mode diameter)×100, is 20 to 58%;
wherein a ratio, average primary particle, diameter/D50 of the average primary particle diameter of the positive electrode active substance relative to the D50 is 0.20 to 0.99;
wherein said amorphous compound contains Li in excess of 1 mol relative to 1 mol of the A element; and
wherein an amount of carbonate ions present on the surface of the positive electrode active substance is less than 2.5 wt % relative to the positive electrode active substance.
17. The positive electrode active substance for an all solid-state lithium secondary battery according to claim 16 , wherein the molar ratio, Li/A, of Li relative to the A element in the positive electrode active substance surface, as obtained by X-ray photoelectron spectroscopy (XPS), is 0.5 to 3.5.
18. The positive electrode active substance for an all solid-state lithium secondary battery according claim 16 , wherein the spinel-type lithium manganese-containing composite oxide is represented by a general formula [Li x (M1 y M2 z Mn 2-x-y-z )O 4-δ ], wherein 1.00≤x≤1.20, 0.20≤y≤1.20, 0<z≤0.5, 0≤δ≤0.2, M1 represents one element or a combination of two or more elements selected from the group consisting of Ni, Co, and Fe, and M2 represents one element or a combination of two or more elements selected from the group consisting of Na, Mg, Al, P, K, Ca, Ti, V, Cr, Cu, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce.
19. The positive electrode active substance for an all solid-state lithium secondary battery according claim 16 , wherein the spinel-type lithium manganese-containing composite oxide is represented by a general formula [Li x (Ni y M z Mn 2-x-y-z )O 4-δ ], wherein 1.00≤x≤1.20, 0.20≤y≤0.70, 0<z≤0.5, 0≤δ≤0.2, and M represents one element or a combination of two or more elements selected from the group consisting of Na, Mg, Al, P, K, Ca, Ti, V, Cr, Fe, Co, Cu, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce.
20. The positive electrode active substance for an all solid-state lithium secondary battery according claim 16 , wherein the mode diameter according to a measurement of a volume-based particle size distribution obtained via measurements by a laser diffraction scattering-type particle size distribution measurement method is 0.4 to 11 μm.