Lithium ion secondary battery comprising an active material and solid electrolyte forming a matrix structure and method for manufacturing same
A conventional, multilayer, all-solid-state, lithium ion secondary battery where an electrode layer and an electrolyte layer are stacked has a problem that it has a high interface resistance between the electrode layer and the electrolyte layer and has a difficulty in increasing the capacity of the battery. A battery has been manufactured by applying pastes of a mixture of an active material and a solid electrolyte to form electrode layers and baking a laminate of electrode layers and electrolyte layers at a time. As a result, a matrix structure including the active material and the solid electrolyte has been formed in the electrode layers, so that a battery with a large capacity and a reduced interface resistance between the electrode layer and the electrolyte layer has been successfully achieved.
1. A multilayer, all-solid-state, lithium ion secondary battery, comprising at least a laminate of alternately stacked positive and negative electrode layers having a solid electrolyte layer interposed therebetween,
wherein at least one of the positive electrode layer or the negative electrode layer, in which an active material and a solid electrolyte form a matrix structure, consists essentially of the solid electrolyte, the active material, a collector material, and an additive,
the active material is a material that efficiently releases and adsorbs lithium ions,
the solid electrolyte is a material having low electron conductivity and high lithium ion conductivity,
the additive is a boron compound, a sintering aid, or a combination thereof,
the matrix structure is produced by baking the laminate at a temperature in a range of 600-1,100° C.,
the matrix structure is a structure in which material particles that form the matrix are in contact with one another to be three dimensionally continuous, wherein the three dimensionally continuous structure may have a discontinuous part in a two-dimensional cross-section if at least another cross-section is continuous in the structure, and
the baked laminate is a sintered laminate.
2. The lithium ion secondary battery according to claim 1 , wherein the matrix structure has the solid electrolyte supported on a matrix of the active material.
3. The lithium ion secondary battery according to claim 1 , wherein the matrix structure has the active material supported on a matrix of the solid electrolyte.
4. The lithium ion secondary battery according to claim 1 , wherein the matrix structure is a structure formed by baking a coating of a paste obtained by mixing the active material, the solid electrolyte, the collector material, the additive, at least one solvent, and at least one binder.
5. The lithium ion secondary battery according to claim 1 , wherein the matrix structure has a cross-sectional area ratio of the active material to the solid electrolyte in a range from 20:80 to 80:20.
6. The lithium ion secondary battery according to claim 2 ,
wherein the matrix structure is a structure formed by baking a coating of a paste obtained by mixing the active material, the solid electrolyte, the collector material, the additive, at least one solvent, and at least one binder.
7. The lithium ion secondary battery according to claim 3 ,
wherein the matrix structure is a structure formed by baking a coating of a paste obtained by mixing the active material, the solid electrolyte, the collector material, the additive, at least one solvent, and at least one binder.
8. The lithium ion secondary battery according to claim 1 , wherein the active material and the solid electrolyte are entangled with each other in the matrix structure.
9. The multilayer, all-solid-state, lithium ion secondary battery according to claim 1 ,
wherein the active material is at least one compound selected from the group consisting of lithium manganese complex oxide, lithium nickel complex oxide, lithium cobalt complex oxide, lithium vanadium complex oxide, lithium titanium complex oxide, manganese dioxide, titanium oxide, niobium oxide, vanadium oxide, and tungsten oxide, and
the solid electrolyte is at least one compound selected from the group consisting of lithium silicophosphate (Li 3.5 Si 0.5 P 0.5 O 4 ), lithium titanium phosphate (LiTi 2 (PO 4 ) 3 ), lithium germanium phosphate (LiGe 2 (PO 4 ) 3 ), Li 2 O—SiO 2 , Li 2 O—V 2 O 5 —SiO 2 , Li 2 O—P 2 O 5 —B 2 O 2 , and Li 2 O—GeO 2 .
10. A method for manufacturing a lithium ion secondary battery, comprising at least:
a stacking step of alternately stacking green sheets for positive and negative electrode layers with a green sheet for an electrolyte layer interposed therebetween to form a laminate of an electrolyte layer, a positive electrode layer, and a negative electrode layer; and
a step of baking the laminate at a temperature in a range of 600-1,100° C. so as to form a sintered laminate,
wherein the green sheet for at least one of the positive electrode layer or the green sheet for the negative electrode layer is formed by applying a paste obtained by mixing materials consisting essentially of an active material, a solid electrolyte, a collector material, an additive, at least one solvent, and at least one binder, to a respective sheet for the green sheet for the at least one of the positive electrode layer and baking the sheet so that at least one of the positive electrode layer or the negative electrode layer has a structure in which the active material and the solid electrolyte form a matrix structure,
the matrix structure is a structure in which material particles that form the matrix are in contact with one another to be three dimensionally continuous, wherein the three dimensionally continuous structure may have a discontinuous part in a two-dimensional cross-section if at least another cross-section is continuous in the structure,
the active material is a material that efficiently releases and adsorbs lithium ions,
the solid electrolyte is a material having low electron conductivity and high lithium ion conductivity, and
the additive is a boron compound, a sintering aid, or a combination thereof.
11. The method according to claim 10 ,
wherein
the active material is mixed in the paste in a powder form having a particle size of 3 μm or less; and
the solid electrolyte is mixed in the paste in a powder form having a particle size of 3 μm or less.
12. The method according to claim 10 ,
wherein the active material in a powder form and the solid electrolyte in a powder form are mixed in a volume ratio of 20:80 to 80:20 to form the paste.
13. A multilayer, all-solid-state, lithium ion secondary battery, comprising at least a laminate of alternately stacked positive and negative electrode layers having a solid electrolyte layer interposed therebetween,
wherein the laminate has an intermediate layer at a location between the solid electrolyte layer and the positive electrode layer or at a location between the solid electrolyte layer and the negative electrode layer,
the intermediate layer has a matrix structure that an active material and a solid electrolyte form, and that is produced by baking the laminate, wherein the baking of the laminate is performed at a temperature in a range of 600-1,100° C.,
the intermediate layer consists essentially of the solid electrolyte, the active material, a collector material, and an additive,
the active material is a material that efficiently releases and adsorbs lithium ions, the solid electrolyte is a material having low electron conductivity and high lithium ion conductivity,
the additive is a boron compound, a sintering aid, or a combination thereof,
the matrix structure is a structure in which material particles that form the matrix are in contact with one another to be three dimensionally continuous, wherein the three dimensionally continuous structure may have a discontinuous part in a two-dimensional cross-section if at least another cross-section is continuous in the structure, and
the baked laminate is a sintered laminate.
14. The lithium ion secondary battery according to claim 13 ,
wherein the active material, which forms at least one of the positive electrode layer, the negative electrode layer, or the intermediate layer, is one or more compounds selected from the group consisting of lithium manganese complex oxide, lithium nickel complex oxide, lithium cobalt complex oxide, lithium vanadium complex oxide, lithium titanium complex oxide, manganese dioxide, titanium oxide, niobium oxide, vanadium oxide, and tungsten oxide.
15. The lithium ion secondary battery according to claim 13 ,
wherein the electrolyte, which forms at least one of the positive electrode layer, the negative electrode layer, or the intermediate layer, is one or more compounds selected from the group consisting of lithium silicophosphate (Li 3.5 Si 0.5 P 0.5 O 4 ), lithium titanium phosphate (LiTi 2 (PO 4 ) 3 ), lithium germanium phosphate (LiGe 2 (PO 4 ) 3 ), Li 2 O—SiO 2 , Li 2 O—V 2 O 5 —SiO 2 , Li 2 O—P 2 O 5 —B 2 O 3 , and Li 2 O—GeO 2 .
16. The lithium ion secondary battery according to claim 13 ,
wherein the matrix structure has the solid electrolyte supported on a matrix of the active material.
17. The lithium ion secondary battery according to claim 13 ,
wherein the matrix structure has the active material supported on a matrix of the solid electrolyte.
18. The lithium ion secondary battery according to claim 13 ,
wherein the matrix structure is a structure formed by baking a coating of a paste obtained by mixing the active material, the solid electrolyte, a collector material, an additive, at least one solvent, and at least one binder.
19. The lithium ion secondary battery according to claim 13 , wherein the active material and the solid electrolyte are entangled with each other in the matrix structure.
20. A method for manufacturing a lithium ion secondary battery, comprising at least:
a stacking step of alternately stacking green sheets for positive and negative electrode layers with a green sheet for an electrolyte layer interposed therebetween to form a laminate of an electrolyte layer, a positive electrode layer, a negative electrode layer, and an intermediate layer; and
a step of baking the laminate at a temperature in a range of 600-1,100° C. so as to form a sintered laminate,
wherein a green sheet for an intermediate layer is placed at at least one of a location between the green sheet for the positive electrode layer and the green sheet for the electrolyte layer or at a location between the green sheet for the negative electrode layer and the green sheet for the electrolyte layer, and
the intermediate layer is formed by applying a paste obtained by mixing materials consisting essentially of an active material, a solid electrolyte, a collector material, an additive, at least one solvent, and at least one binder to a sheet and baking the sheet so that the intermediate layer has a structure in which the active material and the solid electrolyte form a matrix structure,
the matrix structure is a structure in which material particles that form the matrix are in contact with one another to be three dimensionally continuous, wherein the three dimensionally continuous structure may have a discontinuous part in a two-dimensional cross section if at least another cross-section is continuous in the structure,
the active material is a material that efficiently releases and adsorbs lithium ions,
the solid electrolyte is a material having low electron conductivity and high lithium ion conductivity, and
the additive is a boron compound, a sintering aid, or a combination thereof.