Electrode material for lithium-ion secondary battery and method for manufacturing same
An electrode material for a lithium-ion secondary battery of the present invention includes particles which are made of LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 , have an orthorhombic crystal structure, and have a space group of Pmna, in which a mis-fit value [(1−(b2×c2)/(b1×c1))×100] of a bc plane which is computed from lattice constants b1 and c1 of the LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 and lattice constants b2 and c2 of Fe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 obtained by deintercalating Li from LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 by means of an oxidation treatment using nitrosonium tetrafluoroborate in acetonitrile is 1.32% or more and 1.85% or less.
1. An electrode material for a lithium-ion secondary battery comprising:
particles which are made of LiFe x Mn 1-w-x-y-z Mg y Ca Z A w PO 4 (wherein A represents at least one element selected from the group consisting of Co, Ni, Zn, Al, and Ga, 0.05≦x≦0.035, 0.01≦y≦0.10, 0.0001≦z≦0.001, and 0≦w≦0.002, and have an orthorhombic crystal structure with a space group of Pnma,
wherein a mis-fit value of a bc plane is 1.32% to 1.85%, wherein the mis-fit value is represented by the formula (1−(b2×c2)/(b1×c1)×100 and is calculated from lattice constants b1 and c1 of the LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 and lattice constants b2 and c2 of the Fe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 obtained by deintercalating Li from the LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 by means of an oxidation treatment using nitrosonium tetrafluoroborate in acetonitrile.
2. A lithium-ion secondary battery comprising the electrode material for a lithium-ion secondary battery according to claim 1 ,
wherein a ratio L/R of a value L of a constant electric current charge capacity of LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 at an electric current density of 3 CA and an upper limit voltage of 4.3 V, which is measured at 25° C., to a value R of the constant electric current charge capacity of LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 at an electric current density of 0.1 CA and an upper limit voltage of 4.3 V, which is measured at 25° C., is 0.55 or more.
3. The lithium-ion secondary battery according to claim 2 ,
wherein a Li diffusion coefficient computed from a peak between 3.6 V and 4.2 V of the cyclic voltammetry of LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 , which is measured at 25° C., is 1.0×10 −12 or more and 1.0×10 −10 or less.
4. A method for manufacturing the electrode material for a lithium-ion secondary battery according to claim 1 , comprising:
a step of heating a raw material slurry α including a Li source, a Fe source, a Mn source, a Mg source, a Ca source, a P source, and an A source to a temperature in a range of 150° C. or higher and 250° C. or lower, thereby synthesizing LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 particles under pressure;
a step of drying a raw material slurry β obtained by dispersing the LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 particles in a water solvent including a carbon source, granulating the raw material slurry, and then heating the raw material slurry to a temperature in a range of 500° C. or higher and 860° C. or lower, thereby coating surfaces of LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 primary particles with a carbonaceous film and obtaining an electrode material for a lithium-ion secondary battery; and
a step of mixing the electrode material for a lithium-ion secondary battery with a solution obtained by adding nitrosonium tetrafluoroborate to acetonitrile as an oxidant, thereby performing chemical Li deintercalation and setting a mis-fit value of a bc plane to 1.32% to 1.85%, wherein the mis-fit value is represented by the formula (1−(b2×c2)/(b1×c1))×100 and is calculated from lattice constants b1 and c1 of the LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 and lattice constants b2 and c2 of the Fe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 obtained by deintercalating Li from the LiFe x Mn 1-w-x-y-z Mg y Ca z A w PO 4 .