Positive-electrode active material for nonaqueous-electrolyte secondary cell, and nonaqueous-electrolyte secondary cell
View Patent ↗A positive-electrode active material includes a lithium transition metal composite oxide that contains at least 80 mol % of Ni in relation to the total molar amount of metal elements excluding Li. The lithium transition metal composite oxide includes secondary particles obtained by the aggregation of primary particles, at least one element A selected from Ca and Sr being present on the surface of the primary particles in an amount of 1 mol % or less in relation to the total molar amount of metal elements excluding Li, and S and at least one element B selected from Zr, Ti, Mn, Er, Pr, In, Sn, and Ba being present on the surface of the secondary particles.
1 . A positive electrode active material for a non-aqueous electrolyte secondary battery, including a lithium-transition metal composite oxide containing 80 mol % or more of Ni based on a total amount of moles of metal elements excluding Li, wherein
the lithium-transition metal composite oxide includes secondary particles formed by aggregation of primary particles,
at least one element A selected from the group consisting of Ca and Sr is present on surfaces of the primary particles in an amount of 3 mol % or less based on the total amount of moles of the metal elements excluding Li,
at least one element B selected from the group consisting of Zr, Ti, Mn, Er, Pr, In, Sn, and Ba; and S are present on surfaces of the secondary particles, and
a first coating layer including the element A and a second coating layer formed to cover the first coating layer and including the element B and S are formed on surfaces of the secondary particles.
2 . The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1 , wherein
the lithium-transition metal composite oxide contains at least one selected from the group consisting of Co, Al, and Mn, and
a content of the element A is 0.1 mol % or more and 0.5 mol % or less based on the total amount of moles of the metal elements excluding Li.
3 . The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1 , wherein the element B is at least one selected from the group consisting of Zr and Ti, and is present in an amount of 0.02 mol % or more and 0.5 mol % or less based on the total amount of moles of the metal elements excluding Li.
4 . The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1 , wherein when 1 g of the lithium-transition metal composite oxide is added to a mixed solution of 100 mL of pure water, 1 mL of a 35 mass % aqueous hydrochloric acid solution, 0.05 mL of a 46 mass % hydrofluoric acid, and 0.05 mL of a 64 mass % nitric acid, the mixed solution is stirred for 5 minutes, the mixed solution is subjected to filtration to obtain a filtrate, and the filtrate is analyzed by inductively coupled plasma mass spectroscopy to determine partial elution amounts of S and the element B in the filtrate, and when 1 g of the lithium-transition metal composite oxide is entirely dissolved to determine entire elution amounts of S and the element B similarly, each ratio of the partial elution amount to the entire elution amount ((the partial elution amount/the entire elution amount)×100) is 50% or more.
5 . The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1 , wherein when 1 g of the lithium-transition metal composite oxide is added to a mixed solution of 100 mL of pure water, 1 mL of a 35 mass % aqueous hydrochloric acid solution, 0.05 mL of a 46 mass % hydrofluoric acid, and 0.05 mL of a 64 mass % nitric acid, the mixed solution is stirred for 5 minutes, the mixed solution is subjected to filtration to obtain a filtrate, and the filtrate is analyzed by inductively coupled plasma mass spectroscopy to determine a partial elution amount of the element A in the filtrate, and when 1 g of the lithium-transition metal composite oxide is entirely dissolved to determine an entire elution amount of the element A similarly, a ratio of the partial elution amount to the entire elution amount ((the partial elution amount/the entire elution amount)×100) is 60% or more.
6 . A non-aqueous electrolyte secondary battery, comprising:
a positive electrode including the positive electrode active material according to claim 1 ;
a negative electrode; and
a non-aqueous electrolyte.
7 . A positive electrode active material for a non-aqueous electrolyte secondary battery, including a lithium-transition metal composite oxide containing 80 mol % or more of Ni based on a total amount of moles of metal elements excluding Li, wherein
the lithium-transition metal composite oxide includes secondary particles formed by aggregation of primary particles,
at least one element A selected from the group consisting of Ca and Sr is present on surfaces of the primary particles in an amount of 3 mol % or less based on the total amount of moles of the metal elements excluding Li,
at least one element B selected from the group consisting of Ti, Mn, Er, Pr, In, Sn, and Ba; and S are present on surfaces of the secondary particles, and
the element B is only present on surfaces of the secondary particles but is absent inside the secondary particles.
8 . The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 7 , wherein
the lithium-transition metal composite oxide contains at least one selected from the group consisting of Co, Al, and Mn, and
a content of the element A is 0.1 mol % or more and 0.5 mol % or less based on the total amount of moles of the metal elements excluding Li.
9 . The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 7 , wherein the element B is Ti, and is present in an amount of 0.02 mol % or more and 0.5 mol % or less based on the total amount of moles of the metal elements excluding Li.
10 . The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 7 , wherein when 1 g of the lithium-transition metal composite oxide is added to a mixed solution of 100 mL of pure water, 1 mL of a 35 mass % aqueous hydrochloric acid solution, 0.05 mL of a 46 mass % hydrofluoric acid, and 0.05 mL of a 64 mass % nitric acid, the mixed solution is stirred for 5 minutes, the mixed solution is subjected to filtration to obtain a filtrate, and the filtrate is analyzed by inductively coupled plasma mass spectroscopy to determine partial elution amounts of S and the element B in the filtrate, and when 1 g of the lithium-transition metal composite oxide is entirely dissolved to determine entire elution amounts of S and the element B similarly, each ratio of the partial elution amount to the entire elution amount ((the partial elution amount/the entire elution amount)×100) is 50% or more.
11 . The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 7 , wherein when 1 g of the lithium-transition metal composite oxide is added to a mixed solution of 100 mL of pure water, 1 mL of a 35 mass % aqueous hydrochloric acid solution, 0.05 mL of a 46 mass % hydrofluoric acid, and 0.05 mL of a 64 mass % nitric acid, the mixed solution is stirred for 5 minutes, the mixed solution is subjected to filtration to obtain a filtrate, and the filtrate is analyzed by inductively coupled plasma mass spectroscopy to determine a partial elution amount of the element A in the filtrate, and when 1 g of the lithium-transition metal composite oxide is entirely dissolved to determine an entire elution amount of the element A similarly, a ratio of the partial elution amount to the entire elution amount ((the partial elution amount/the entire elution amount)×100) is 60% or more.
12 . A non-aqueous electrolyte secondary battery, comprising:
a positive electrode including the positive electrode active material according to claim 7 ;
a negative electrode; and
a non-aqueous electrolyte.