High-ionic conductivity ceramic-polymer nanocomposite solid state electrolyte
A ceramic-polymer film includes a polymer matrix; a plasticizer; a lithium salt; and Al x Li 7-x La 3 Zr 1.75 Ta 0.25 O 12 where x ranges from 0.01 to 1 (LLZO), wherein the LLZO are nanoparticles with diameters that range from 20 to 2000 nm and wherein the film has an ionic conductivity of greater than 1×10 −3 S/cm at room temperature. The nanocomposite film can be formed on a substrate and the concentration of LLZO nanoparticles decreases in the direction of the substrate to form a concentration gradient over the thickness of the film. The film can be employed as a non-flammable, solid-state electrolyte for lithium electrochemical cells and batteries. The LLZO serves as a barrier to dendrite growth.
1. A fire-resistant, non-flammable ceramic-polymer film that comprises: a polymer matrix; a plasticizer; a lithium salt; and Al x Li 7-x La 3 Zr 1.75 Ta 0.25 O 12 where x ranges from 0.01 to 1 (LLZO), wherein the LLZO are nanoparticles with diameters that range from 20 to 2000 nm and wherein the film has an ionic conductivity of greater than 1×10 −3 S/cm at room temperature wherein the polymer matrix comprises 10 to 50 wt % of the film wherein the polymer matrix comprises at least one of PEO, PCL, PAN, and mixtures thereof, the plasticizer comprises 10 to 60 wt % of the film, the lithium salt comprises 20 to 60 wt % of the film, and the LLZO comprises 15 to 25 wt % of the film and wherein the film is free standing and has a thickness that ranges from 100 to 900 μm and the film is thermally stable up to 150° C., and wherein the LLZO comprises a gradient along the thickness direction of the non-flammable ceramic-polymer film, wherein the non-flammable ceramic-polymer film defines a first interface configured to couple with an anode and a second interface configured to couple with a cathode, wherein the polymer matrix extends from the first interface to the second interface and the concentration of the LLZO in a region adjacent the first interface is higher than that in a region adjacent the second interface.
2. The film of claim 1 wherein the plasticizer comprises succinonitrile (SCN).
3. The film of claim 1 wherein the lithium salt comprises LITFSI or LiClO 4 .
4. The film of claim 1 wherein the LLZO comprises Al x Li 7-x La 3 Zr 1.75 Ta 0.25 O 12 where x ranges from 0.01 to 0.2.
5. The film of claim 1 wherein the polymer matrix comprises 15 to 25 wt % of the film, the plasticizer comprises 20 to 50 wt¾ of the film, and the lithium salt comprises 30 to 40 wt % of the film.
6. The film of claim 1 which has a Young's modulus that exceeds 50 MPa.
7. An electrochemical cell which comprises: an anode; a cathode; and
interposed therebetween is a solid-electrolyte which is a fire-resistant, non-flammable film which comprises:
a polymeric matrix;
a plasticizer;
a lithium salt; and
Al x Li 7-x La 3 Zr 1.75 Ta 0.25 O 12 where x ranges from 0.01 to 1 (LLZO), wherein the LLZO are nanoparticles with diameters that range from 20 to 2000 nm and wherein the polymer matrix comprises 10 to 50 wt % of the film wherein the polymer matrix comprises at least one of PEO, PCL, PAN, and mixtures thereof, the plasticizer comprises 10 to 60 wt % of the film, the lithium salt comprises 20 to 60 wt % of the film, and the LLZO comprises 15 to 25 wt % of the film and wherein the film is free standing and has a thickness that ranges from 100 to 900 μm and the film is thermally stable up to 150° C., and wherein the LLZO comprises a gradient along the thickness direction of the non-flammable film, wherein the non-flammable film defines a first interface configured to couple with the anode and a second interface configured to couple with the cathode, wherein the polymer matrix extends from the first interface to the second interface and the concentration of the LLZO in a region adjacent the first interface is higher than that in a region adjacent the second interface.
8. The electrochemical cell of claim 7 wherein the plasticizer comprises succinonitrile (SCN).
9. The film of claim 1 wherein the lithium salt comprises LITFSI or LiClO 4 .
10. The electrochemical cell of claim 7 wherein the LLZO comprises Al x Li 7-x La 3 Zr 1.75 Ta 0.25 O 12 where x ranges from 0.01 to 0.2.
11. The electrochemical cell of claim 7 wherein the polymer matrix comprises 15 to 25 wt % of the film, the plasticizer comprises 20 to 50 wt % of the film, and the lithium salt comprises 30 to 40 wt % of the film.
12. The electrochemical cell of claim 7 wherein the film has a Young's modulus that exceeds 50 MPa.
13. The electrochemical cell of claim 7 wherein the anode comprises lithium.
14. The electrochemical cell of claim 7 wherein the cathode comprises lithium iron phosphate.
15. A process for preparing an electrochemical cell which comprises:
(a) providing a cathode;
(b) providing an anode;
(c) forming a solid-electrolyte between the cathode and anode;
wherein the solid-electrolyte is a film that comprises:
a polymeric matrix;
a plasticizer;
a lithium salt; and
Al x Li 7-x La 3 Zr 1.75 Ta 0.25 O 12 where x ranges from 0.01 to 1 (LLZO), wherein the LLZO are nanoparticles with diameters that range from 20 to 2000 nm and wherein the polymer matrix comprises 10 to 50 wt % of the film wherein the polymer matrix comprises at least one of PEO, PCL, PAN, and mixtures thereof, the plasticizer comprises 10 to 60 wt % of the film, the lithium salt comprises 20 to 60 wt % of the film, and the LLZO comprises 15 to 25 wt % of the film and wherein the film is free standing and has a thickness that ranges from 100 to 900 μm and the film is thermally stable up to 150° C., and wherein the LLZO comprises a gradient along the thickness direction of the solid-electrolyte, wherein the solid-electrolyte defines a first interface configured to couple with the anode and a second interface configured to couple with the cathode, wherein the polymer matrix extends from the first interface to the second interface and the concentration of the LLZO in a region adjacent the first interface is higher than that in a region adjacent the second interface.
16. The process of claim 15 wherein the plasticizer comprises succinonitrile (SCN).
17. The process of claim 15 wherein the lithium salt comprises LiTFSI or LiClO 4 .
18. The process of claim 15 wherein the LLZO comprises Al x Li 7-x La 3 Zr 1.75 Ta 0.25 O 12 where x ranges from 0.01 to 0.2.
19. The process of claim 15 wherein the polymer matrix comprises 15 to 25 wt % of the film, the plasticizer comprises 20 to 50 wt % of the film, and the lithium salt comprises 30 to 40 wt % of the film.
20. The process of claim 15 wherein the film has a Young's modulus that exceeds 50 MPa.