Lithium metal fluorophosphate and preparation thereof
View Patent ↗The invention provides new and novel lithium-metal-fluorophosphates which, upon electrochemical interaction, release lithium ions, and are capable of reversibly cycling lithium ions. The invention provides a rechargeable lithium battery which comprises an electrode formed from the novel lithium-metal-fluorophosphates. The lithium-metal-fluorophosphates comprise lithium and at least one other metal besides lithium.
1. A battery, comprising:
a positive electrode comprising a lithium metal fluorophosphate compound of the formula LiMPO 4 F, wherein M is a metal with more than one oxidation state above the ground state M 0 , made by a process comprising the step of reacting a metal compound with a phosphate-containing compound and lithium fluoride to form the lithium metal fluorophosphate compound;
a negative electrode; and
an electrolyte.
2. The battery of claim 1 , wherein the metal compound is selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 , V 2 O 5 , VO 2 , MnO 2 , TiO 2 , Ti 2 O 3 , Cr 2 O 3 , CoO, Ni 3 (PO 4 ) 2 , Nb 2 O 5 , Mo 2 O 3 , V 2 O 3 , FeO, Co 3 O 4 , CrO 3 , Nb 2 O 3 , and MoO 3 .
3. The battery of claim 1 , wherein the phosphate-containing compound is selected from the group consisting of diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
4. The battery of claim 1 , wherein the step of reacting a metal compound with a phosphate-containing compound and lithium fluoride to form the lithium metal fluorophosphate comprises the steps of:
forming a mixture comprising the phosphate-containing compound, lithium fluoride and the metal compound; and
heating the mixture at a temperature and for a time sufficient to form the lithium metal fluorophosphate compound.
5. The battery of claim 4 , wherein the heating step is carried out under a reducing atmosphere.
6. The battery of claim 5 , wherein the reducing atmosphere is hydrogen gas.
7. The battery of claim 4 , wherein the mixture further comprises carbon, and the heating step is carried out under an inert atmosphere.
8. A battery, comprising:
a positive electrode comprising a lithium metal fluorophosphate compound of the formula LiMPO 4 F, wherein M is a metal with more than one oxidation state above the ground state M 0 , made by a process comprising the steps of:
reacting a metal compound with a phosphate-containing compound to form a metal phosphate precursor; and
reacting the metal phosphate precursor with lithium fluoride to form the lithium metal fluorophosphate compound;
a negative electrode; and
an electrolyte.
9. The battery of claim 8 , wherein the metal compound is selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 , V 2 O 5 , VO 2 , MnO 2 , TiO 2 , Ti 2 O 3 , Cr 2 O 3 , CoO, Ni 3 (PO 4 ) 2 , Nb 2 O 5 , Mo 2 O 3 , V 2 O 3 , FeO, Co 3 O 4 , CrO 3 , Nb 2 O 3 and MoO 3 .
10. The battery of claim 8 , wherein the phosphate-containing compound is selected from the group consisting of diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
11. The battery of claim 8 , wherein the step of reacting a metal compound with a phosphate-containing compound to form a metal phosphate precursor comprises the steps of:
forming a mixture comprising the phosphate-containing compound and the metal compound; and
heating the mixture at a temperature and for a time sufficient to form the metal phosphate precursor.
12. The battery of claim 11 , wherein the heating step is carried out under a reducing atmosphere.
13. The battery of claim 12 , wherein the reducing atmosphere is hydrogen gas.
14. The battery of claim 11 , wherein the mixture further comprises carbon, and the heating step is carried out under an inert atmosphere.
15. A battery, comprising:
a positive electrode comprising a lithium metal fluorophosphate compound of the formula LiMPO 4 F, wherein M is a metal with more than one oxidation state above the ground state M 0 , made by a process comprising the steps of:
reacting a metal compound with a phosphate-containing compound to form a metal phosphate precursor; and
reacting the metal phosphate precursor with lithium carbonate and ammonium fluoride to form the lithium metal fluorophosphate compound;
a negative electrode; and
an electrolyte.
16. The battery of claim 15 , wherein the metal compound is selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 , V 2 O 5 , VO 2 , MnO 2 , TiO 2 , Ti 2 O 3 , Cr 2 O 3 , CoO, Ni 3 (PO 4 ) 2 , Nb 2 O 5 , Mo 2 O 3 , V 2 O 3 , FeO, Co 3 O 4 , CrO 3 , Nb 2 O 3 and MoO 3 .
17. The battery of claim 15 , wherein the phosphate-containing compound is selected from the group consisting of diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
18. The battery of claim 15 , wherein the step of reacting a metal compound with a phosphate-containing compound to form a metal phosphate precursor comprises the steps of:
forming a mixture comprising the phosphate-containing compound and the metal compound; and
heating the mixture at a temperature and for a time sufficient to form the metal phosphate precursor.
19. The battery of claim 18 , wherein the heating step is carried out under a reducing atmosphere.
20. The battery of claim 19 , wherein the reducing atmosphere is hydrogen gas.
21. The battery of claim 18 , wherein the mixture further comprises carbon, and the heating step is carried out under an inert atmosphere.
22. A battery, comprising:
a positive electrode comprising a lithium mixed-metal fluorophosphate compound of the formula LiM 1-y MI y PO 4 F,wherein M and MI are each metals and 0≦y≦1, wherein at least one of M and MI has more than one oxidation state above the ground state M O made by a process comprising the steps of:
reacting a first metal compound with a phosphate-containing compound to form a first metal phosphate precursor;
reacting a second metal compound with a phosphate-containing compound to form a second metal phosphate precursor; and
reacting the first metal phosphate precursor and the second metal precursor with lithium fluoride to form the lithium mixed-metal fluorophosphate compound;
a negative electrode; and
an electrolyte.
23. The battery of claim 22 , wherein the first metal compound is selected from the group consisting of Fe 2 O 3 , Fe 3 O 4 , V 2 O 5 , VO 2 , MnO 2 , TiO 2 , Ti 2 O 3 , Cr 2 O 3 , CoO, Ni 3 (PO 4 ) 2 , Nb 2 O 5 , Mo 2 O 3 , V 2 O 3 , FeO, Co 3 O 4 , CrO 3 , Nb 2 O 3 and MoO 3 .
24. The battery of claim 22 , wherein the phosphate-containing compound is selected from the group consisting of diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
25. The battery of claim 22 , wherein the step of reacting a first metal compound with a phosphate-containing compound to form a first metal phosphate precursor comprises the steps of:
forming a mixture comprising the phosphate-containing compound and the first metal compound; and
heating the mixture at a temperature and for a time sufficient to form the first metal phosphate precursor.
26. The battery of claim 25 , wherein the heating step is carried out under a reducing atmosphere.
27. The battery of claim 26 , wherein the reducing atmosphere is hydrogen gas.
28. The battery of claim 25 , wherein the mixture further comprises carbon, and the heating step is carried out under an inert atmosphere.