Composite electrodes for lithium ion battery and method of making
A method for making a composite electrode for a lithium ion battery comprises the steps of: preparing a slurry containing particles of inorganic electrode material(s) suspended in a solvent; preheating a porous metallic substrate; loading the metallic substrate with the slurry; baking the loaded substrate at a first temperature; curing the baked substrate at a second temperature sufficient to form a desired nanocrystalline material within the pores of the substrate; calendaring the cured composite to reduce internal porosity; and, annealing the calendared composite at a third temperature to produce a self-supporting multiphase electrode. Because of the calendaring step, the resulting electrode is self-supporting, has improved current collecting properties, and improved cycling lifetime. Anodes and cathodes made by the process, and batteries using them, are also disclosed.
1 . A cathode for a lithium ion battery comprising:
a first phase comprising an inorganic energy storage material;
a second phase comprising a solid state lithium ion conductor; and,
a third phase comprising a reticulated metal structure, interspersed throughout said first and second phases, said reticulated metal forming a structural reinforcement and a current collector,
wherein said metal structure comprises from 5 to 25% of the volume of material, said first and second phases together comprise from 75 to 95% of the volume of the material, and said cathode contains no more than 30 vol. % porosity.
2 . The cathode of claim 1 wherein said inorganic energy storage material comprises a compound selected from the group consisting of:
LiMn 2−x M1 x O 4 where M1 is selected from the group consisting of Al, Sn, Zn, and Fe, and 0≦x≦0.05;
LiCo 1−x M2 x O 2 where M2 is selected from the group consisting of Ni and Al, and 0≦x≦0.5;
LiNi 1−x M3 x O 2 where M3 is selected from the group consisting of Co and Al, and 0≦x≦0.5;
LiMn x Ni y Co z Al t O 2 where x+y+z+t=1, and 0≦(x, y, z, and t)≦1;
LiM4PO 4 , where M4 is selected from the group consisting of Fe, Co, Ni, and Mn;
CuS;
CuM5S where M5 is selected from the group consisting of Fe, Sn, Mo, and Zn;
LiFePO 4 ;
Li 4 Ti 5 O 12 ;
FeS; and,
MoS.
3 . The cathode of claim 1 wherein said solid state lithium ion conductor comprises a material selected from the group consisting of: Li 2 WO 4 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Ohara glass®, LiAlGaPO 4 , Li 7−x La 3 (Zr 2−x Nb x )O 12 , LiLaTiO, and LiLaZrO.
4 . The cathode of claim 1 further comprising dispersed electronically conductive particulates selected from the group consisting of: Ti 4 O 7 (Ebonex® ceramic), carbon nanotube, carbon nanowire, carbon nano-particles, semiconductor nanowire, semiconductor nano-particles, metal nanowire, metal nano-particles and ceramic nano-particles.
5 . The cathode of claim 4 wherein said dispersed electronically conductive particles are in the range of 10 to 100 nm in size and represent about 1 to 30% by weight of the electrode material.
6 . The cathode of claim 1 wherein said reticulated metal structure comprises metal foam selected from the group consisting of: Ni and Ni alloys, stainless steel, Cu and Cu alloys, Al and Al alloys.
7 . An anode for a lithium ion battery comprising:
a first phase comprising a lithium ion storage material;
a second phase comprising a solid state lithium ion conductor; and,
a third phase comprising a reticulated metal structure, interspersed throughout said first and second phases, said reticulated metal forming a structural reinforcement and a current collector,
wherein said metal structure comprises from 5 to 25% of the volume of material, said first and second phases together comprise from 75 to 95% of the volume of the material, and said anode contains no more than 30 vol. % porosity.
8 . The anode of claim 7 , wherein said first phase comprises at least one compound selected from the group consisting of: SnO x , SnS x , Li 4 Ti 5 O 12 , LiCx, MnO x , and CoO x .
9 . The anode of claim 7 wherein said solid state lithium ion conductor comprises a material selected from the group consisting of: Li 2 WO 4 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Ohara glass®, LiAlGaPO 4 , Li 7−x La 3 (Zr 2−x Nb x )O 12 , LiLaTiO, and LiLaZrO.
10 . The anode of claim 7 further comprising dispersed electronically conductive particulates selected from the group consisting of: Ti 4 O 7 (Ebonex® ceramic), carbon nanotube, carbon nanowire, carbon nano-particles, semiconductor nanowire, semiconductor nano-particles, metal nanowire, metal nano-particles and ceramic nano-particles.
11 . The anode of claim 7 wherein said reticulated metal structure comprises metal foam selected from the group consisting of: Ni and Ni alloys, stainless steel, Cu and Cu alloys, Al and Al alloys.
12 . A lithium ion battery comprising:
a cathode comprising:
a first phase comprising an inorganic energy storage material;
a second phase comprising a solid state lithium ion conductor; and,
a third phase comprising a reticulated metal structure, interspersed throughout said first and second phases, said reticulated metal forming a structural reinforcement and a current collector,
wherein said metal structure comprises from 5 to 25% of the volume of material, said first and second phases together comprise from 75 to 95% of the volume of the material, and said cathode contains no more than 30 vol. % porosity;
an anode comprising a lithium storage material; and,
a lithium-conducting electrolyte separating said cathode from said anode.
13 . The lithium ion battery of claim 12 wherein said inorganic energy storage material comprises a compound selected from the group consisting of:
LiMn 2−x M1 x O 4 where M1 is selected from the group consisting of Al, Sn, Zn, and Fe, and 0≦x≦0.05;
LiCo 1−x M2 x O 2 where M2 is selected from the group consisting of Ni and Al, and 0≦x≦0.5;
LiNi 1−x M3 x O 2 where M3 is selected from the group consisting of Co and Al, and 0≦x≦0.5;
LiMn x Ni y Co z Al t O 2 where x+y+z+t=1, and 0≦(x, y, z, and t)≦1;
LiM4PO 4 , where M4 is selected from the group consisting of Fe, Co, Ni, and Mn;
CuS;
CuM5S where M5 is selected from the group consisting of Fe, Sn, Mo, and Zn;
LiFePO 4 ;
Li 4 Ti 5 O 12 ;
FeS; and,
MoS.
14 . The lithium ion battery of claim 12 wherein said reticulated metal structure comprises metal foam selected from the group consisting of: Ni and Ni alloys, stainless steel, Cu and Cu alloys, Al and Al alloys.
15 . The lithium ion battery of claim 12 wherein said solid state lithium ion conductor comprises a material selected from the group consisting of: Li 2 WO 4 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Ohara glass®, LiAlGaPO 4 , Li 7−x La 3 (Zr 2−x Nb x )O 12 , LiLaTiO, and LiLaZrO.
16 . The lithium ion battery of claim 12 wherein said lithium-conducting electrolyte comprises Li y Al (1−x) Ga x S(PO 4 ).
17 . The lithium ion battery of claim 12 wherein said lithium-conducting electrolyte comprises a liquid LiPF 6 solution.
18 . The lithium ion battery of claim 12 further comprising a buffer layer selected from the group consisting of: LiNbO 3 , Li x SiO y , Li-βAl 2 O 3 , Li x AlSiO y , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7−x La 3 (Zr 2−x Nb x )O 12, Li y Al (1−x) Ga x S(PO 4 ), Li 0.35 La 0.55 TiO 3 , and LiTi 2 (PO 4 ) 3 .
19 . A lithium ion battery comprising:
an anode comprising:
a first phase comprising a lithium ion storage material;
a second phase comprising a solid state lithium ion conductor; and,
a third phase comprising a reticulated metal structure, interspersed throughout said first and second phases, said reticulated metal forming a structural reinforcement and a current collector,
wherein said metal structure comprises from 5 to 25% of the volume of material, said first and second phases together comprise from 75 to 95% of the volume of the material, and said anode contains no more than 30 vol. % porosity;
a cathode comprising an energy storage material; and,
a lithium-conducting electrolyte separating said cathode from said anode.
20 . The lithium ion battery of claim 19 wherein said lithium ion storage material comprises at least one compound selected from the group consisting of: SnO x , SnS x , Li 4 Ti 5 O 12 , LiCx, MnO x , and CoO x .
21 . The lithium ion battery of claim 19 wherein said reticulated metal structure comprises metal foam selected from the group consisting of: Ni and Ni alloys, stainless steel, Cu and Cu alloys, Al and Al alloys.
22 . The lithium ion battery of claim 19 wherein said solid state lithium ion conductor comprises a material selected from the group consisting of: Li 2 WO 4 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Ohara glass®, LiAlGaPO 4 , Li 7−x La 3 (Zr 2−x Nb x )O 12 , LiLaTiO, and LiLaZrO.
23 . The lithium ion battery of claim 19 wherein said lithium-conducting electrolyte comprises Li y Al (1−x) Ga x S(PO 4 ).
24 . The lithium ion battery of claim 19 wherein said lithium-conducting electrolyte comprises a liquid LiPF 6 solution.
25 . The lithium ion battery of claim 19 further comprising a buffer layer selected from the group consisting of: LiNbO 3 , Li x SiO y , Li-βAl 2 O 3 , Li x AlSiO y , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7−x La 3 (Zr 2−x Nb x )O 12, Li y Al (1−x) Ga x S(PO 4 ), Li 0.35 La 0.55 TiO 3 , and LiTi 2 (PO 4 ) 3 .