Lithium ion conductive crystal body and all-solid state lithium ion secondary battery

Abstract

To provide a lithium ion conductive crystal body having a high density and a large length and an all-solid state lithium ion secondary battery containing the lithium ion conductive crystal body. A Li 5 La 3 Ta 2 O 12 crystal body, which is one example of the lithium ion conductive crystal body, has a relative density of 99% or more, belongs to a cubic system, has a garnet-related type structure, and has a length of 2 cm or more. The Li 5 La 3 Ta 2 O 12 crystal body is grown by a melting method employing a Li 5 La 3 Ta 2 O 12 polycrystal body as a raw material. With the growing method, a Li 5 La 3 Ta 2 O 12 crystal body having a relative density of 100% can also be obtained. In addition, the all-solid state lithium ion secondary battery has a positive electrode, a negative electrode, and a solid electrolyte, in which the solid electrolyte contains the lithium ion conductive crystal body.

1 . A lithium ion conductive crystal body comprising:
 chemical composition represented by Li 7-3x Al x La 3 Zr 2 O 12  (0.05<x<0.50), Li 5 La 3 Ta 2 O 12 , or Li 6 BaLa 2 Ta 2 O 12 ;   having a relative density of 99% or more;   belonging to a cubic system;   having a garnet-related type structure; and   having a length of 2 cm or more.   
     
     
         2 . The lithium ion conductive crystal body according to  claim 1 , wherein
 the lithium ion conductive crystal body is grown by a melting method employing a raw material containing a polycrystal body having a chemical composition represented by Li 7 La 3 Zr 2 O 12 , belonging to a tetragonal system, and having a garnet-related type structure and at least one of an Al 2 O 3  polycrystal body and a LiAlO 2  polycrystal body, and   has a chemical composition represented by Li 7-3x Al x La 3 Zr 2 O 12  (0.05<x<0.50).   
     
     
         3 . The lithium ion conductive crystal body according to  claim 1 , wherein
 the lithium ion conductive crystal body is grown by a melting method employing a polycrystal body represented by a same chemical composition as a raw material.   
     
     
         4 . The lithium ion conductive crystal body according to  claim 1 , wherein
 the relative density is 100%.   
     
     
         5 . The lithium ion conductive crystal body according to  claim 1 , wherein the body has a
 a grating constant a is 1.28 nm≦a≦1.31 nm.   
     
     
         6 . A method for producing a lithium ion conductive crystal body having a chemical composition represented by Li 7-3x Al x La 3 Zr 2 O 12  (0.05<x<0.50), Li 5 La 3 Ta 2 O 12 , or Li 6 BaLa 2 Ta 2 O 12 , having a relative density of 99% or more, belonging to a cubic system, and having a garnet-related type structure,
 the method comprising:   melting at least a part of a raw material of a polycrystal body represented by a same chemical composition as the chemical composition of the lithium ion conductive crystal body to form a melted portion, and then moving the melted portion at a movement speed of 8 mm/h or more.   
     
     
         7 . A method for producing a lithium ion conductive crystal body having a chemical composition represented by Li 7-3x Al x La 3 Zr 2 O 12  (0.05<x<0.50), having a relative density of 99% or more, belonging to a cubic system, and having a garnet-related type structure,
 the method comprising:   melting at least a part of a raw material containing a polycrystal body having a chemical composition represented by Li 7 La 3 Zr 2 O 12 , belonging to a tetragonal system, and having a garnet-related type structure and at least one of an Al 2 O 3  polycrystal body and a LiAlO 2  polycrystal body to form a melted portion, and moving the melted portion at a movement speed of 8 mm/h or more.   
     
     
         8 . The method for producing a lithium ion conductive crystal body according to  claim 6 , wherein
 the movement speed is 8 mm/h or more and 19 mm/h or less.   
     
     
         9 . The method for producing a lithium ion conductive crystal body according to  claim 6 , wherein
 the raw material is melted while rotating the rod-shaped raw material on a plane perpendicular to a longitudinal direction at a rotation speed of 30 rpm or more.   
     
     
         10 . The method for producing a lithium ion conductive crystal body according to  claim 9 , wherein
 the rotation speed is 30 rpm or more and 60 rpm or less.   
     
     
         11 . An all-solid state lithium ion secondary battery comprising:
 a positive electrode;   a negative electrode; and   a solid electrolyte, wherein   the solid electrolyte contains the lithium ion conductive crystal body according to  claim 1 .