Rapid thermal processing methods and apparatus
Methods and apparatus for fabricating separators for solid-state lithium metal batteries employ rapid thermal processing. Aspects include high temperature sintering. Temperatures, durations of heat application, and proximity of heating elements to materials undergoing sintering combine to provide separators with desirable physical characteristics, including porosity, in a batch process.
1. A process for sintering, the process comprising:
providing a stack comprising a bilayer, furniture, and a frame;
wherein the bilayer comprises a green body layer disposed on a metal layer;
wherein the furniture comprises a first plate that contacts the metal layer of the bilayer and a second plate disposed above the green body layer of the bilayer;
wherein the frame is interposed between the green body layer and the second plate;
moving the stack through a furnace at about 1050° C. to about 1250° C. for about 30 seconds to about 3 minutes;
thereby providing a sintered bilayer comprising a lithium-stuffed garnet layer on the metal layer;
wherein the sintered bilayer has a thickness of between about 10 μm and about 50 μm.
2. The process of claim 1 , comprising heating the bilayer in the furnace at about 1100° C. to about 1200° C.
3. The process of claim 1 , wherein moving the stack through the furnace comprises heating the stack in the furnace at a ramp rate of up to about 100° C. per minute; or at a ramp rate of about 5° C. per minute to about 35° C. per minute.
4. The process of claim 1 , wherein the bilayer moves through the furnace at a rate of between about 20 mm/min to about 80 mm/min.
5. The process of claim 1 , wherein the bilayer dwells in the furnace for about 1 minute to about 10 minutes.
6. The process of claim 1 , further comprising a binder burn-out step prior to sintering the bilayer, wherein the binder burn-out step comprises heating the stack to evaporate organic material from the stack.
7. The process of claim 6 , wherein the binder burn-out step occurs for about 5 seconds to about 5 minutes.
8. The process of claim 6 , wherein the bilayer, prior to the binder burn-out step, comprises at least one member selected from a solvent, a binder, a dispersant, a plasticizer, a surfactant, or a combination thereof.
9. The process of claim 1 , wherein the lithium-stuffed garnet layer is characterized by the formula Li A La B Zr C O F , Li A La B M′ C M″ D Ta E O F , or Li A La B M′ C M″ D Nb E O F , wherein 4<A<8.5, 1.5<B<4, 0≤C≤2, 0≤D≤2; 0≤E≤2.5, 10<F<13, and M′ and M″ are each, independently in each instance selected from Al, Mo, W, Nb, Ga, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta; or Li a La b Zr c Al d Me″ e O f , wherein 5<a<7.7; 2<b<4; 0≤c≤2.5; 0≤d≤2; 0≤e≤2, 10<f<13 and Me″ is a metal selected from Nb, V, W, Mo, Ta, Ga, and Sb.
10. The process of claim 1 , wherein the metal layer comprises a metal selected from the group consisting of nickel, tungsten, copper, iron, titanium, molybdenum, alloys thereof, and combinations thereof.
11. The process of claim 1 , wherein the sintered bilayer has a thickness of about 20 μm to about 40 μm.
12. The process of claim 1 , wherein the sintered bilayer has a width of between about 50 mm to about 150 mm.
13. The process of claim 1 , wherein the furnace comprises an atmospheric controller that maintains an atmosphere in the furnace that comprises argon (Ar) gas, nitrogen (N 2 ) gas, hydrogen gas, forming gas, or a mixture thereof; and wherein the atmospheric controller maintains the atmosphere in the furnace comprises less than 500 ppm O 2 ; or wherein the atmospheric controller maintains an atmosphere in the furnace comprises less than 250 ppm O 2 .
14. The process of claim 1 , wherein the first plate comprises a material selected from the group consisting of alumina (Al 2 O 3 ), zirconium toughened alumina (ZTA), mullite (3Al 2 O 32 SiO 2 or 2Al 2 O 3 SiO 2 ), aluminum nitride (AlN), and silicon carbide (SiC).
15. The process of claim 1 , wherein the second plate comprises a material selected from the group consisting of alumina (Al 2 O 3 ), zirconium toughened alumina (ZTA), mullite (3Al 2 O 3 2SiO 2 or 2Al 2 O 3 SiO 2 ), aluminum nitride (AlN), or and silicon carbide (SiC).
16. The process of claim 1 , wherein the frame comprises a material selected from the group consisting of porous alumina, zirconia, lithium aluminate, lithium tantalate, alumina, silica, cordierite, Ni, kovar, and invar.
17. The process of claim 1 , wherein the second plate is a center-less cover.
18. The method of claim 1 , wherein moving the stack through the furnace comprises moving the stack on a conveyor through the furnace, wherein the conveyor comprises a plurality of rollers, wherein the rollers contact the first plate of the stack.
19. The method of claim 1 , wherein the green body layer comprises lithium-stuffed garnet, precursors to lithium-stuffed garnet, or a combination thereof.
20. A sintered bilayer prepared by the process of claim 1 .