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 0.2 (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 PEGDA which comprises 15 to 25 wt % of the film, the plasticizer comprises succinonitrile (SCN) which comprises 20 to 50 wt % of the film, the lithium salt comprises LiTFSI which comprises 30 to 40 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.
2. The film of claim 1 which has a Young's modulus that exceeds 50 MPa.
3. 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 0.2 (LLZO), wherein the LLZO are nanoparticles with diameters that range from 20 to 2000 nm wherein the polymer matrix comprises PEGDA which comprises 15 to 25 wt % of the film, the plasticizer comprises succinonitrile (SCN) which comprises 20 to 50 wt % of the film, the lithium salt comprises LiTFSI which comprises 30 to 40 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.
4. The electrochemical cell of claim 3 wherein the anode comprises lithium.
5. The electrochemical cell of claim 3 wherein the cathode comprises lithium iron phosphate.
6. The electrochemical cell of claim 3 wherein the film has a Young's modulus that exceeds 50 MPa.
7. 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, wherein the film has an ionic conductivity of greater than 1×10 −3 S/cm at room temperature, wherein the polymer matrix is PEO and comprises 27 wt % of the film, the lithium salt is LiTFSI and comprises 36 wt % of the film, the plasticizer is SCN and comprises 27 wt % of the film, the LLZO comprises 10 wt % of the film, 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.
8. An electrochemical cell which comprises: an anode; a cathode; and interposed therebetween a solid-electrolyte is a fire-resistant, non-flammable, and stable 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, wherein the polymer matrix is PEO and comprises 27 wt % of the film, the lithium salt is LiTFSI and comprises 36 wt % of the film, the plasticizer is SCN and comprises 27 wt % of the film, the LLZO comprises 10 wt % of the film, 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.
9. A process for preparing an electrochemical cell which comprises:
(a) providing a cathode;
(b) providing an anode;
(c) forming a sold-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 0.2 (LLZO), wherein the LLZO are nanoparticles with diameters that range from 20 to 2000 nm wherein the polymer matrix comprises PEGDA which comprises 15 to 25 wt % of the film, the plasticizer comprises succinonitrile (SCN) which comprises 20 to 50 wt % of the film, the lithium salt comprises LiTFSI which comprises 30 to 40 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.
10. The process of claim 9 wherein the film has a Young's modulus that exceeds 50 MPa.
11. A process for preparing an electrochemical cell which comprises:
(a) providing a cathode;
(b) providing an anode;
(c) forming a sold-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, wherein the polymer matrix is PEO and comprises 27 wt % of the film, the lithium salt is LiTFSI and comprises 36 wt % of the film, the plasticizer is SCN and comprises 27 wt % of the film, the LLZO comprises 10 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.