Multi-layer structured composite electrolyte and secondary battery using same
A multi-layer structured composite electrolyte for a secondary battery and a secondary battery using the same are provided. The multi-layer structured composite electrolyte is made by laminating two or more layers of a composite electrolyte including a small amount of a liquid electrolyte in a mixture of a polymer and a ceramic material. The multi-layer structured composite electrolyte has the same stability as a solid electrolyte and has the same or better electrochemical properties as or than the liquid electrolyte. Since the multi-layer structured composite electrolyte of the present invention can be folded arbitrarily, the multi-layer structured composite electrolyte may be used in a wearable device.
1. A multi-layer structured composite electrolyte for a lithium ion secondary battery comprising:
a first composite electrolyte layer located toward a positive electrode; and
a second composite electrolyte layer located toward a negative electrode,
wherein the first composite electrolyte layer and the second composite electrolyte layer include a polymer, an ion conductive ceramic material, and a liquid electrolyte,
the ion conductive ceramic material of the first composite electrolyte layer is 70 wt % to 99 wt % and the polymer of the first composite electrolyte layer is 1 wt % to 30 wt % when the ion conductive ceramic material of the first composite electrolyte layer and the polymer of the first composite electrolyte layer are 100 wt %,
the ion conductive ceramic material of the second composite electrolyte layer is 70 wt % to 99 wt % and the polymer of the second composite electrolyte layer is 1 wt % to 30 wt % when the ion conductive ceramic material of the second composite electrolyte layer and the polymer of the second composite electrolyte layer are 100 wt %,
the liquid electrolyte is formed by dissolving a lithium salt in a non-aqueous organic solvent,
the liquid electrolyte of the first composite electrolyte layer is contained with 5 parts by weight to 40 parts by weight with respect to 100 parts by weight of the ion conductive ceramic material of the first composite electrolyte layer and the polymer of the first composite electrolyte layer,
the liquid electrolyte of the second composite electrolyte layer is contained with 5 parts by weight to 40 parts by weight with respect to 100 parts by weight of the ion conductive ceramic material of the second composite electrolyte layer and the polymer of the second composite electrolyte layer,
the polymer of the first composite electrolyte layer is polyvinylidene fluoride (PVdF) or copolymers thereof, and the ion conductive ceramic material of the first composite electrolyte layer is a ceramic material selected from phosphates, oxides, sulfides, and mixtures thereof, and
the polymer of the second composite electrolyte layer is polyvinylidene fluoride (PVdF) or copolymers thereof, and the ion conductive ceramic material of the second composite electrolyte layer is a phosphate ceramic material.
2. A multi-layer structured composite electrolyte for a lithium ion secondary battery comprising:
a first composite electrolyte layer located toward a positive electrode; and
a second composite electrolyte layer located toward a negative electrode,
wherein the first composite electrolyte layer and the second composite electrolyte layer include a polymer, an ion conductive ceramic material, and a liquid electrolyte,
the ion conductive ceramic material of the first composite electrolyte layer is 70 wt % to 99 wt % and the polymer of the first composite electrolyte layer is 1 wt % to 30 wt % when the ion conductive ceramic material of the first composite electrolyte layer and the polymer of the first composite electrolyte layer are 100 wt %,
the ion conductive ceramic material of the second composite electrolyte layer is 70 wt % to 99 wt % and the polymer of the second composite electrolyte layer is 1 wt % to 30 wt % when the ion conductive ceramic material of the second composite electrolyte layer and the polymer of the second composite electrolyte layer are 100 wt %,
the liquid electrolyte is formed by dissolving a lithium salt in a non-aqueous organic solvent,
the liquid electrolyte of the first composite electrolyte layer is contained with 5 parts by weight to 40 parts by weight with respect to 100 parts by weight of the ion conductive ceramic material of the first composite electrolyte layer and the polymer of the first composite electrolyte layer,
the liquid electrolyte of the second composite electrolyte layer is contained with 5 parts by weight to 40 parts by weight with respect to 100 parts by weight of the ion conductive ceramic material of the second composite electrolyte layer and the polymer of the second composite electrolyte layer,
the polymer of the first composite electrolyte layer is polyvinylidene fluoride (PVdF) or copolymers thereof, and the ion conductive ceramic material of the first composite electrolyte layer is a ceramic material selected from phosphates, oxides, sulfides, and mixtures thereof, and
the polymer of the second composite electrolyte layer is polyvinylidene fluoride (PVdF) or a copolymer thereof, and the ion conductive ceramic material of the second composite electrolyte layer is an oxide ceramic material.
3. A multi-layer structured composite electrolyte for a lithium ion secondary battery comprising:
a first composite electrolyte layer located toward a positive electrode; and
a second composite electrolyte layer located toward a negative electrode,
wherein the first composite electrolyte layer and the second composite electrolyte layer include a polymer, an ion conductive ceramic material, and a liquid electrolyte,
the ion conductive ceramic material of the first composite electrolyte layer is 70 wt % to 99 wt % and the polymer of the first composite electrolyte layer is 1 wt % to 30 wt % when the ion conductive ceramic material of the first composite electrolyte layer and the polymer of the first composite electrolyte layer are 100 wt %,
the ion conductive ceramic material of the second composite electrolyte layer is 70 wt % to 99 wt % and the polymer of the second composite electrolyte layer is 1 wt % to 30 wt % when the ion conductive ceramic material of the second composite electrolyte layer and the polymer of the second composite electrolyte layer are 100 wt %,
the liquid electrolyte is formed by dissolving a lithium salt in a non-aqueous organic solvent,
the liquid electrolyte of the first composite electrolyte layer is contained with 5 parts by weight to 40 parts by weight with respect to 100 parts by weight of the ion conductive ceramic material of the first composite electrolyte layer and the polymer of the first composite electrolyte layer,
the liquid electrolyte of the second composite electrolyte layer is contained with 5 parts by weight to 40 parts by weight with respect to 100 parts by weight of the ion conductive ceramic material of the second composite electrolyte layer and the polymer of the second composite electrolyte layer,
the polymer of the first composite electrolyte layer is polyacrylonitrile (PAN) or copolymers thereof, and the ion conductive ceramic material of the first composite electrolyte layer is a ceramic material selected from phosphates, oxides, sulfides, and mixtures thereof, and
the polymer of the second composite electrolyte layer is polyacrylonitrile (PAN) or copolymers thereof, and the ion conductive ceramic material of the second conductive electrolyte layer is a sulfide ceramic material.
4. The multi-layer structured composite electrolyte of claim 1 , wherein the ion conductive ceramic material of the first composite electrolyte layer is selected from LTAP (Li 1+x Ti 2−x Al x (PO 4 ) 3 ) (0<x<2), LLZO (Li 7 La 3 Zr 2 O 12 ), Li 2 S—P 2 S 5 , and mixtures thereof, and
the ion conductive ceramic material of the second composite electrolyte layer is LAGP (Li 1+x Al x Ge 2−x (PO 4 ) 3 ) (0<x<2).
5. The multi-layer structured composite electrolyte of claim 2 , wherein
the ion conductive ceramic material of the first composite electrolyte layer is selected from LTAP (Li 1+x Ti 2−x Al x (PO 4 ) 3 ) (0<x<2), LLTO (La,Li)TiO 3 ), Li 2 S—P 2 S 5 ), and mixtures thereof, and
the ion conductive ceramic material of the second composite electrolyte layer is selected from β-Al 2 O 3 , LLZO (Li 7 La 3 Zr 2 O 12 ), and mixtures thereof.
6. The multi-layer structured composite electrolyte of claim 3 , wherein the ion conductive ceramic material of the first composite electrolyte layer is selected from LTAP (Li 1+x Ti 2−x Al x (PO 4 ) 3 ) (0<x<2), LLZO (Li 7 La 3 Zr 2 O 12 ), Li 2 S—P 2 S 5 , and mixtures thereof, and
the ion conductive ceramic material of the second composite electrolyte layer is selected from LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ), Li 2 O—SiO 2 , and mixtures thereof.
7. The multi-layer structured composite electrolyte of claim 1 , wherein the polymer of the first composite electrolyte layer is polyvinylidene fluoride (PVdF) and the ion conductive ceramic material thereof is LTAP (Li 1+x Ti 2−x Al x (PO 4 ) 3 ) (0<x<2), and the polymer of the second composite electrolyte layer is polyvinylidene fluoride (PVdF) and the ion conductive ceramic material thereof is LAGP (Li 1+x Al x Ge 2−x (PO 4 ) 3 ) (0<x<2).
8. The multi-layer structured composite electrolyte of claim 1 , wherein the polymer of the first composite electrolyte layer is polyvinylidene fluoride (PVdF) and the ion conductive ceramic material thereof is LLZO (Li 7 La 3 Zr 2 O 12 ), and the polymer of the second composite electrolyte layer is polyvinylidene fluoride (PVdF) and the ion conductive ceramic material thereof is LAGP (Li 1+x Al x Ge 2−x (PO 4 ) 3 ) (0<x<2).
9. The multi-layer structured composite electrolyte of claim 1 , wherein the polymer of the first composite electrolyte layer is polyvinylidene fluoride (PVdF) and the ion conductive ceramic material thereof is Li 2 S—P 2 S 5 , and the polymer of the second composite electrolyte layer is polyvinylidene fluoride (PVdF) and the ion conductive ceramic material thereof is LAGP (Li 1+x Al x Ge 2−x (PO 4 ) 3 ) (0<x<2).
10. The multi-layer structured composite electrolyte of claim 2 , wherein
the polymer of the first composite electrolyte layer is PVdF and the ion conductive ceramic material thereof is LTAP (Li 1+x Ti 2−x Al x (PO 4 ) 3 ) (0<x<2), and the polymer of the second composite electrolyte layer is PVdF-TrFE and the ion conductive ceramic material thereof is β-Al 2 O 3 .
11. The multi-layer structured composite electrolyte of claim 2 , wherein the polymer of the first composite electrolyte layer is PVdF and the ion conductive ceramic material thereof is LTAP (Li 1+x Ti 2−x Al x (PO 4 ) 3 ) (0<x<2), and the polymer of the second composite electrolyte layer is PVdF-TrFE and the ion conductive ceramic material thereof is LLZO (Li 7 La 3 Zr 2 O 12 ).
12. The multi-layer structured composite electrolyte of claim 2 , wherein the polymer of the first composite electrolyte layer is PVdF and the ion conductive ceramic material thereof is LLTO ((La,Li) TiO 3 ), and the polymer of the second composite electrolyte layer is PVdF-TrFE and the ion conductive ceramic material thereof is β-Al 2 O 3 .
13. The multi-layer structured composite electrolyte of claim 2 , wherein the polymer of the first composite electrolyte layer is PVdF and the ion conductive ceramic material thereof is Li 2 S—P 2 S 5 , and the polymer of the second composite electrolyte layer is PVdF-TrFE and the ion conductive ceramic material thereof is β-Al 2 O 3 .
14. The multi-layer structured composite electrolyte of claim 2 , wherein the polymer of the first composite electrolyte layer is PVdF and the ion conductive ceramic material thereof is LTAP (Li 1+x Ti 2−x Al x (PO 4 ) 3 ) (0<x<2), and the polymer of the second composite electrolyte layer is PVdF and the ion conductive ceramic material thereof is LLZO (Li 7 La 3 Zr 2 O 12 ).
15. The multi-layer structured composite electrolyte of claim 3 , wherein the polymer of the first composite electrolyte layer is polyacrylonitrile (PAN) and the ion conductive ceramic material thereof is LTAP (Li 1+x Ti 2−x Al x (PO 4 ) 3 ) (0<x<2), and the polymer of the second composite electrolyte layer is polyacrylonitrile (PAN) and the ion conductive ceramic material thereof is LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ).
16. The multi-layer structured composite electrolyte of claim 3 , wherein the polymer of the first composite electrolyte layer is polyacrylonitrile (PAN) and the ion conductive ceramic material thereof is LLZO (Li 7 La 3 Zr 2 O 12 ), and the polymer of the second composite electrolyte layer is polyacrylonitrile (PAN) and the ion conductive ceramic material thereof is Li 2 O—SiO 2 .
17. The multi-layer structured composite electrolyte of claim 3 , wherein the polymer of the first composite electrolyte layer is polyacrylonitrile (PAN) and the ion conductive ceramic material thereof is Li 2 S—P 2 S 5 , and the polymer of the second composite electrolyte layer is polyacrylonitrile (PAN) and the ion conductive ceramic material thereof is LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ).
18. The multi-layer structured composite electrolyte of claim 3 , wherein the polymer of the first composite electrolyte layer is polyacrylonitrile (PAN) and the ion conductive ceramic material thereof is LTAP (Li 1+x Ti 2−x Al x (PO 4 ) 3 ) (0<x<2), and the polymer of the second composite electrolyte layer is polyacrylonitrile (PAN) and the ion conductive ceramic material thereof is Li 2 O—SiO 2 .
19. The multi-layer structured composite electrolyte of claim 1 , wherein another layer is or multilayers are further included between the first composite electrolyte layer and the second composite electrolyte layer.
20. A lithium ion secondary battery comprising the multi-layer structured composite electrolyte for the lithium ion secondary battery of claim 1 .