Electrode for solid electrolyte secondary battery, solid electrolyte secondary battery, and battery pack
According to one embodiment, a solid electrolyte secondary battery includes a positive electrode, a negative electrode, and a solid electrolyte layer, wherein at least one selected from the positive electrode and the negative electrode comprises active material particles, first solid electrolyte particles located the vicinity of a surface of the active material particles, and second solid electrolyte particles located a gap between the active material particles. A particle size ratio of a second solid electrolyte particle size D2 to a first solid electrolyte particle size D1 (D2/D1) satisfies the relation of 3<D2/D1<50, where D1 and D2 denote a particle size of the first and second solid electrolyte particles, respectively.
1. An electrode for a solid electrolyte secondary battery comprising a current collector, and an electrode layer formed on at least one surface of the current collector and containing active material particles, first solid electrolyte particles located the vicinity of a surface of the active material particles, and second solid electrolyte particles located a gap between the active material particles, the first solid electrolyte particles and the second solid electrolyte particles being formulated in ratios of 10 to 40% by volume of the first solid electrolyte particles and 5 to 25% by volume of the second solid electrolyte particles, wherein
a particle size ratio of a second solid electrolyte particle size D2 to a first solid electrolyte particle size D1 (D2/D1) satisfies the relation of 3<D2/D1<50, where D1 denotes the particle size of the first solid electrolyte particles having a particle size of 0.05 μm or more and 0.5 μm or less, and D2 denotes the particle size of the second solid electrolyte particles,
the first solid electrolyte and the second solid electrolyte are a solid oxide electrolyte, or a solid sulfide electrolyte,
the solid oxide electrolyte is at least one selected from the group consisting of a lithium-ion conductive oxide having a Perovskite-type structure expressed by the formula Li 3x La 2/3−x TiO 3 , where x is 0<x<2/3, a lithium-ion conductive oxide having a Garnet-type structure expressed by the formula Li 5+x La 3 M 2−x Zr x O 12 , where M is at least one of Nb and Ta, and x is 0≦x≦2, and a lithium-ion conductive oxide including oxides referred to LISICON, LIPON, and NASICON, and
the solid sulfide electrolyte is at least one selected from the group consisting of a compound expressed by (1−x−y) Li 2 S.xGeS 2 .yP 2 S 5 , where x and y are 0≦x<0.5, 0≦y<0.4, sulfides referred to as THIO-LISICON, sulfide glass ceramic, and compounds expressed by (1−x)Li 2 S −x B 2 S 3 and (1−x)Li 2 S-xGeS 2 , where x is 0.15≦x<0.5.
2. The electrode of claim 1 , wherein the active material particles have a particle size of 0.1 μm or more and 10 μm or less.
3. A solid electrolyte secondary battery comprising a positive electrode, a negative electrode, and a solid electrolyte layer, wherein
the positive electrode comprises a current collector, and an electrode layer formed on at least one surface of the current collector and containing active material particles, first solid electrolyte particles located the vicinity of a surface of the active material particles, and second solid electrolyte particles located a gap between the active material particles, the first solid electrolyte particles and the second solid electrolyte particles being formulated in ratios of 10 to 40% by volume of the first solid electrolyte particles and 5 to 25% by volume of the second solid electrolyte particles,
the negative electrode comprises a current collector, and an electrode layer formed on at least one surface of the current collector and containing active material particles, first solid electrolyte particles located the vicinity of a surface of the active material particles, and second solid electrolyte particles located a gap between the active material particles, the first solid electrolyte particles and the second solid electrolyte particles being formulated in ratios of 10 to 40% by volume of the first solid electrolyte particles and 5 to 25% by volume of the second solid electrolyte particles,
a particle size ratio of a second solid electrolyte particle size D2 to a first solid electrolyte particle size D1 (D2/D1) satisfies a relation of 3<D2/D1<50, where D1 denotes a particle size of the first solid electrolyte particles having a particle size of 0.05 μM or more and 0.5 μm or less, and D2 denotes a particle size of the second solid electrolyte particles,
the first solid electrolyte and the second solid electrolyte are a solid oxide electrolyte or a solid sulfide electrolyte,
the solid oxide electrolyte is at least one selected from the group consisting of a lithium-ion conductive oxide having a Perovskite-type structure expressed by the formula Li 3x La 2/3−x TiO 3 , where x is 0<x<2/3, a lithium-ion conductive oxide having a Garnet-type structure expressed by the formula Li 5+x M 2−x Zr x O 12 , where M is at least one of Nb and Ta, and x is 0≦x≦2, and a lithium-ion conductive oxide including oxides referred to LISICON, LIPON, and NASICON, and
the solid sulfide electrolyte is at least one selected from the group consisting of a compound expressed by (1−x−y) Li 2 S.xGeS 2 .yP 2 S 5 , where x and y are 0≦x<0.5, 0≦y<0.4, sulfides referred to as THIO-LISICON, sulfide glass ceramic, and compounds expressed by (1−x)Li 2 S −x B 2 S 3 and (1−x)Li 2 S-xGeS 2 , where x is 0.15≦x<0.5.
4. A battery pack comprising the solid electrolyte secondary battery according to claim 3 .
5. The electrode of claim 1 , wherein LISICON is Li 14 ZnGe 4 O 16 .
6. The electrode of claim 1 , wherein NASICON is Li 1+x Al x Ti 2−x (PO 4 ) 3 or Li 1+x Al x Ge 2−x (PO 4 ) 3 , where x is 0<x≦0.5.
7. The electrode of claim 1 , wherein THIO-LISICON is Li 4−x Ge 1−x P x S 4 , where x is 0.2<x≦0.9.
8. The solid electrolyte secondary battery of claim 3 , wherein LISICON is Li 14 ZnGe 4 O 16 .
9. The solid electrolyte secondary battery of claim 3 , wherein NASICON is Li 1+x Al x Ti 2−x (PO 4 ) 3 or Li 1+x Al x Ge 2−x (PO 4 ) 3 , where x is 0<x≦0.5.
10. The solid electrolyte secondary battery of claim 3 , wherein THIO-LISICON is Li 4−x Ge 1−x P x S 4 , where x is 0.2<x≦0.9.
11. The electrode of claim 1 , wherein the electrode layer further comprises a conductive agent and a binder.
12. The electrode of claim 11 , wherein the binder is a polytetrafluoroethylene, a polyvinylidene fluoride, a fluorine-based rubber, or a polyethylene oxide containing lithium salt.
13. The solid electrolyte secondary battery of claim 3 , wherein the positive electrode layer further comprises a conductive agent and a binder, and the negative electrode layer further comprises a conductive agent and a binder.
14. The solid electrolyte secondary battery of claim 13 , wherein each of the binders in the positive electrode layer and the negative electrode layer is a polytetrafluoroethylene, a polyvinylidene fluoride, a fluorine-based rubber, or a polyethylene oxide containing lithium salt.