Electrode material with enhanced ionic transport properties
View Patent ↗Materials useful as electrodes for lithium batteries have very good electronic and ionic conductivities. They are fabricated from a starting mixture which includes a metal, a phosphate ion, and an additive which enhances the transport of lithium ions in the resultant material. The mixture is heated in a reducing environment to produce the material. The additive may comprise a pentavalent metal or a carbon. In certain embodiments the material is a two-phase material. Also disclosed are electrodes which incorporate the materials and lithium batteries which incorporate those electrodes.
1. A method for synthesizing an electroactive material, the method comprising:
providing a starting mixture which includes lithium, a metal M substantially all of which is in a first oxidation state, a phosphate ion, and an additive comprising one or more of V, Mo and Nb, wherein the additive enhances the transport of lithium ions in a material prepared by this method, as compared to a material prepared in the absence of the additive; and
heating the mixture in a reducing environment to produce an electroactive material comprising lithiated olivine metal phosphate, wherein substantially all of the metal M is in a second oxidation state which is lower than the first oxidation state.
2. The method of claim 1 , wherein the electroactive material comprises a single phase.
3. The method of claim 1 , wherein the electroactive material comprises more than two phases.
4. The method of claim 1 , wherein the electroactive material comprises:
a first phase comprising a lithiated olivine metal phosphate comprising the metal M;
a second phase having an ionic conductivity greater than the ionic conductivity of the first phase; and
the additive in at least one of the first and second phases;
characterized in that when incorporated into a cathode of a lithium battery, the electroactive material has a lithium ion conductivity in the range of 10 −6 S/cm to 5×10 −4 S/cm.
5. The method of claim 1 , wherein the additive substitutes for at least a portion of the phosphorous in the material.
6. The method of claim 5 , wherein at least some of the phosphate groups having the additive substituted therein are reduced.
7. The method of claim 1 , wherein the additive substitutes for a portion of the metal M in the material.
8. The method of claim 1 , wherein the additive is operative to modify the lattice structure of the material, whereby the transport of lithium ions through the modified lattice is enhanced in relation to the transport of lithium ions through the corresponding unmodified lattice.
9. The method of claim 1 , wherein M is Fe.
10. The method of claim 9 , wherein substantially all of the iron in the starting mixture is in the form of the Fe +3 ion.
11. The method of claim 9 , wherein the iron and the phosphate ion in the starting mixture are provided in the form of ferric phosphate.
12. The method of claim 1 , further comprising the step of grinding the mixture prior to heating the mixture in the reducing environment.
13. The method of claim 1 , wherein the step of heating the mixture comprises heating the mixture to a temperature in the range of 300-750° C.
14. The method of claim 1 , wherein the step of heating the mixture comprises heating the mixture to approximately 650-700° C.
15. The method of claim 1 , wherein the additive is a nucleating agent which promotes the growth of at least one component of the material.
16. An electroactive material made according to claim 1 .
17. The electroactive material of claim 16 , characterized in that when incorporated into a cathode of a lithium ion battery, the electronic conductivity of the material is in the range of 10 −7 S/cm to 10 −4 S/cm.
18. An electrode which includes the electroactive material of claim 16 .
19. A method for synthesizing an electroactive material, the method comprising:
providing a starting mixture which includes lithium, a metal M substantially all of which is in a first oxidation state, a phosphate ion, and an additive comprising one or more metals having a +5 oxidation state, but not a +6 oxidation state, wherein the additive enhances the transport of lithium ions in a material prepared by this method, as compared to a material prepared in the absence of the additive; and
heating the mixture in a reducing environment to produce an electroactive material comprising lithiated olivine metal phosphate, wherein substantially all of the metal M is in a second oxidation state which is lower than the first oxidation state.