Metal-substituted metal oxide materials for lithium ion batteries
Provided is a Li + battery comprising an anode comprising an anode active material comprising a plurality of transition metal (TM 1 )-substituted binary transition metal (TM 2 ) oxide nanocrystals, a cathode in electrical communication with the anode, a separator between the anode and the cathode, and an electrolyte in contact with the anode and the cathode. The anode active material, in a lithiated state, is characterized by a three-dimensional network of the TM 1 and nanoparticles of Li 2 O and nanoparticles of the TM 2 , both types of nanoparticles distributed throughout the network. In a delithiated state, the anode active material is characterized by the network of the TM 1 and nanoparticles of an oxide of the TM 1 and nanoparticles of an oxide of the TM 2 , both types of nanoparticles distributed throughout the network. The TM 1 -substituted binary TM 2 oxide may be characterized by a ratio of TM 2 /TM 1 of at least about 5.
1. A Li + battery comprising:
an anode comprising an anode active material comprising a plurality of transition metal (TM 1 )-substituted binary transition metal (TM 2 ) oxide nanocrystals,
a cathode in electrical communication with the anode,
a separator between the anode and the cathode, and
an electrolyte in contact with the anode and the cathode,
wherein the anode active material, in a lithiated state, is characterized by a three-dimensional network of the TM 1 and nanoparticles of Li 2 O and nanoparticles of the TM 2 , both types of nanoparticles distributed throughout the network; further wherein the anode active material, in a delithiated state, is characterized by the network of the TM 1 and nanoparticles of an oxide of the TM 1 and nanoparticles of an oxide of the TM 2 , both types of nanoparticles distributed throughout the network; and further wherein the TM 1 -substituted binary TM 2 oxide is characterized by a ratio of TM 2 /TM 1 of at least about 5.
2. The Li + battery of claim 1 , wherein the binary transition metal (TM 2 ) oxide has a spinel structure.
3. The Li + battery of claim 1 , wherein the binary transition metal (TM 2 ) oxide is selected from Fe 3 O 4 , Fe 2 O 3 , MnO 2 , NiO, CuO, CoO, and Co 3 O 4 .
4. The Li + battery of claim 3 , wherein TM 1 is selected from Cr, Mn, Co, Fe, Ni, Cu, and combinations thereof.
5. The Li + battery of claim 1 , wherein the binary transition metal (TM 2 ) oxide is Co 3 O 4 and TM 1 is selected from Cr, Mn, Co, Fe, Ni, Cu, and combinations thereof.
6. The Li + battery of claim 1 , wherein the transition metal (TM 1 )-substituted binary transition metal (TM 2 ) is Cu-substituted Co 3 O 4 .
7. The Li+ battery of claim 6 , wherein the ratio of TM 2 /TM 1 is in a range of from about 5 to about 10.
8. The Li+ battery of claim 7 , wherein the ratio of TM 2 /TM 1 is about 6.
9. The Li+ battery of claim 1 , wherein the ratio of TM 2 /TM 1 is in a range of from about 5 to about 10.
10. The Li + battery of claim 1 , wherein the nanocrystals are hexagonal in shape.
11. The Li + battery of claim 10 , wherein the nanocrystals have an average maximum edge-to-edge width of less than about 100 nm.
12. The Li + battery of claim 1 , wherein the nanocrystals of the anode active material, in a pristine state, are single-crystalline.
13. The Li + battery of claim 1 , wherein the nanocrystals of the anode active material, in a pristine state, are characterized by a random and uniform distribution of the TM 1 throughout the lattice structure of the binary transition metal (TM 2 ) oxide.
14. The Li + battery of claim 1 , wherein the anode and the anode active material are free of graphene and graphene oxide.
15. A method of using a Li + battery, the method comprising:
charging a Li + battery, the battery comprising
an anode comprising an anode active material comprising a plurality of transition metal (TM 1 )-substituted binary transition metal (TM 2 ) oxide nanocrystals,
a cathode in electrical communication with the anode,
a separator between the anode and the cathode, and
an electrolyte in contact with the anode and the cathode,
wherein the anode active material, in a lithiated state, is characterized by a three-dimensional network of the TM 1 and nanoparticles of Li 2 O and nanoparticles of the TM 2 , both types of nanoparticles distributed throughout the network; further wherein the anode active material, in a delithiated state, is characterized by the network of the TM 1 and nanoparticles of an oxide of the TM 1 and nanoparticles of an oxide of the TM 2 , both types of nanoparticles distributed throughout the network; and further wherein the TM 1 -substituted binary TM 2 oxide is characterized by a ratio of TM 2 /TM 1 of at least about 5; and
discharging the battery.