Method of producing secondary battery cathode material, and secondary battery
View Patent ↗Disclosed is a process for producing a secondary battery cathode material by calcining raw materials. The process is characterized by calcining the raw materials together with one or more substances, which are selected from the group consisting of hydrogen, water and water vapor, and conductive carbon and/or a substance, which can form conductive carbon by pyrolysis, added thereto. As crystals of the secondary battery cathode material obtained by this process have been controlled fine sizes, the secondary battery cathode material promotes movements of ions of an alkali metal led by lithium between the interiors of grains of the cathode material and an electrolyte to suppress polarization in an electrode reaction, and further, increases an area of contact between the positive material and a conductivity-imparting material to provide improved conductivity so that improvements are assured in voltage efficiency and specific battery capacity.
1. A process for producing a secondary battery cathode material, which includes an alkali metal, a transition metal and oxygen, comprising the step of:
calcining pulverized and mixed raw materials, wherein:
said calcination step includes a first stage performed at a temperature that is raised from room temperature to a first calcination temperature between 300° C. and 450° C., and a second stage performed at a temperature that is raised from room temperature to a second calcination temperature between 500° C. and 800° C., the calcination step being completed at the second temperature,
wherein the second stage is carried out after adding a substance which can form conductive carbon by pyrolysis to said raw materials, the substance being added to said raw materials after completing the first stage of said calcination step
wherein said first and second stages are performed substantially in the absence of oxygen gas, in a gas atmosphere comprising an inert gas,
and wherein one or more substances, which are selected from the group consisting of hydrogen, water and water vapor are added to the raw materials together with the inert gas at least during the second stage while the calcination temperature is 500° C. or higher.
2. The process according to claim 1 , wherein said substance which can form conductive carbon by pyrolysis is a bitumen.
3. The process according to claim 2 , wherein said bitumen is a coal pitch having a softening point in a range of from 80° C. to 350° C. and a pyrolytic weight-loss initiation temperature in a range of from 350° C. to 450° C. and capable of depositing conductive carbon by pyrolysis and calcination at a temperature of from 500° C. to 800° C.
4. The process according to claim 1 , wherein said substance which can form conductive carbon by pyrolysis is a saccharide.
5. The process according to claim 4 , wherein said saccharide undergoes decomposition in a temperature range of from 250° C. and higher but lower than 500° C., takes an at least partially fused form once in a course of heating from 150° C. to decomposition, and further, forms conductive carbon by pyrolysis and calcination in a temperature range of from 500° C. and higher but not higher than 800° C.
6. The process according to claim 1 , wherein said cathode material is a substance represented by a formula of M (1)a M (2)x A y O z wherein M (1) represents Li or Na; M (2) represents Fe(II), Co(II), Mn(II), Ni(II), V(II), or Cu (II); A represents P or S; a stands for a number selected from 0 to 3 (exclusive of 0); x stands for a number selected from 1 to 2; y stands for a number selected from 1 to 3; and z stands for a number selected from 4 to 12, or a complex thereof.
7. The process according to claim 1 , wherein said cathode material is a substance represented by a formula of Li q FePO 4 , Li q CoPO 4 or Li q MnPO 4 , wherein q stands for a number selected from 0 to 1 (exclusive of 0), or a complex thereof.
8. The process according to claim 1 , wherein said inert gas is selected from the group consisting of argon (Ar), nitorogen (N 2 ), and helium (He).
9. The process according to claim 8 , wherein said first and second stages are performed in a gas atmosphere, wherein hydrogen or water vapor is added to said inert gas, and the range of the volumetric concentration of the hydrogen or water vapor is set at 0.1% or higher but 20% or lower.