ε-VOPO
The epsilon polymorph of vanadyl phosphate, ε-VOPO 4 , made from the solvothermally synthesized H 2 VOPO 4 , is a high density cathode material for lithium-ion batteries optimized to reversibly intercalate two Li-ions to reach the full theoretical capacity at least 50 cycles with a coulombic efficiency of 98%. This material adopts a stable 3D tunnel structure and can extract two Li-ions per vanadium ion, giving a theoretical capacity of 305 mAh/g, with an upper charge/discharge plateau at around 4.0 V, and one lower at around 2.5 V.
1. A lithium battery, comprising:
a cathode formed with ε-VOPO4, particles and electrically conductive carbon particles, on a current collector, wherein the ε-VOPO4 has a dual lithium ion exchange characteristic, having a capacity of at least 275 mAh/g at a discharge rate of C/20;
a lithium metal anode; and
an electrolyte adapted to operate at a charging voltage of at least 4.5 V.
2. A lithium battery, comprising:
a cathode comprising a mixture of ε-VOPO 4 , electrically conductive carbon, and a binder, on a current collector, the ε-VOPO 4 having a capacity of at least 275 mAh/g and a capacity of at least 125 mAh/g while maintaining a voltage exceeding 3.7 V, at a discharge rate of C/20;
an anode comprising lithium metal;
electrolyte; and
a solid electrolyte interphase.
3. A battery, comprising:
a cathode comprising ε-VOPO 4 , having a capacity of at least 90% of a theoretical capacity value of 305 mAh/g at a discharge rate of C/20, bound with conductive particles;
an anode; and
an electrolyte.
4. The battery according to claim 3 , further comprising a lithium salt in the electrolyte, wherein the anode comprises lithium metal, and the cathode comprises lithiated ε-VOPO 4 .
5. The battery according to claim 3 , further comprising a lithium salt in the electrolyte, wherein the anode comprises a source of lithium ions, and the cathode comprises ε-VOPO 4 configured to intercalate about two lithium ions per vanadium.
6. The battery according to claim 3 , wherein the ε-VOPO 4 is solvothermally or hydrothermally generated.
7. The battery according to claim 3 , wherein the conductive particles comprise carbon particles.
8. The battery according to claim 3 , wherein the conductive particles comprise graphene nanoplatelets or carbon nanotubes.
9. The battery according to claim 3 , wherein the cathode comprises at least 75% by weight ε-VOPO 4 , at least 5% by weight graphene nanoplatelets, and at least 5% by weight of a binder.
10. The battery according to claim 3 , wherein the conductive particles comprise graphene, and the cathode comprises between 5% and 15% by weight of the graphene.
11. The battery according to claim 3 , wherein the ε-VOPO 4 comprises a vanadium which is adapted to undergo a change in oxidation state of two between a charged state and a discharged state.
12. The battery according to claim 11 , wherein the battery has a discharge profile having voltage plateaus at about 2.1 V, 2.25 V, 2.5 V, and 3.9 V.
13. The battery according to claim 11 , wherein the ε-VOPO 4 has a capacity of at least 290 mAh/g at a discharge rate of C/20.
14. The battery according to claim 11 , wherein the ε-VOPO 4 has a capacity of 305 mAh/g at a discharge rate of C/20.
15. The battery according to claim 11 , wherein the ε-VOPO 4 has a capacity of about 125 mAh/g while maintaining a voltage exceeding 3.7 V at a discharge rate of C/20.
16. The battery according to claim 11 , wherein the ε-VOPO 4 has an energy capacity of at least 850 mWh/g.
17. The battery according to claim 11 , wherein the cathode has at least two states, comprising:
a first state in which at least 80 mol % of vanadium of the ε-VOPO 4 is oxidized in a first oxidation state and associated with two lithium ions per vanadium, and
a second state in which at least 80 mol % of the ε-VOPO 4 is oxidized in a second oxidation state which differs by two from the first oxidation state.
18. The battery according to claim 3 , wherein the anode comprises a carbonaceous material having intercalated lithium ions.
19. The battery according to claim 3 , wherein the electrolyte has an operating window comprising 4.5 V.
20. The battery according to claim 3 , wherein the electrolyte comprises a solid electrolyte.