BATTERIES

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority to U.S. provisional patent application number 62/485,435 that was filed 4/14/2017, the entire contents of which are hereby incorporated by reference.

BACKGROUND

[0002] Traditional Li-ion battery electrodes, such as graphite ¹ , and Li2Mn04 ² and LiCoC ³ operate by intercalation reactions alone and typically release and reaccommodate between 0.5 and 1.0 Li ⁺ ions per transition metal ion, thereby limiting the delivered electrode capacity to about 100-170 mAh/g. On the other hand, conversion and alloying reactions occur when electrode materials, such as metal oxides, ⁴ elemental Si, Sn, ⁵ S, ⁶ and Se ⁷ are extensively lithiated and are appealing because they can involve more Li per effective element, resulting in significantly higher capacities. However, unlike intercalation/deintercalation reactions, conversion and alloying reactions induce large volume changes during charge/dis charge cycles that often lead to fracture and loss of electrical contact, among other deleterious mechanical effects of volume change. ^{73, 8} The resulting loss of electrical contact to active electrode materials is one of the main causes of capacity loss and reduced Coulombic efficiency. In addition, most electrode materials for conversion and alloying reactions are semiconductors (and even insulators) that possess relatively low electronic conductivity. Thus, improved electrical conductivity would also improve the prospects of conversion and alloying reaction materials in Li-ion and related battery applications.

SUMMARY

[0003] Provided are anode active materials for lithium ion batteries and lithium ion batteries incorporating the anode active materials.

[0004] In one aspect, lithium ion batteries are provided. In an embodiment, such a battery comprises an anode comprising an anode active material comprising a plurality of transition metal (TMi)-substituted binary transition metal (TM2) 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 TMi and nanoparticles of L12O and nanoparticles of the TM2, both types of nanoparticles distributed throughout the network. In a delithiated state, the anode active material is characterized by the network of the TMi and nanoparticles of an oxide of the TMi and nanoparticles of an oxide of the TM2, both types of nanoparticles distributed throughout the network. The TMi-substituted binary TM2 oxide may be characterized by a ratio of TM2/TM1 of at least about 5.

[0005] In another aspect, methods of using the present lithium ion batteries are provided. The methods comprising charging and discharging the battery.

[0006] Other principal features and advantages of the disclosure will become apparent to those skilled in the art upon review of the following drawings, the detailed description, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Illustrative embodiments of the present disclosure will hereafter be described with reference to the accompanying drawings.

[0008] FIGs. 1 A-1F show the results of the characterization of a Cu-substituted C03O4 (CU3/7C018/7O4) single crystal sample. FIG. 1A shows a 20 kV scanning electron microscope (SEM) image. FIG. IB shows an X-ray powder diffraction spectrum. FIG. 1C shows a bright- field scanning transmission electron microscope (STEM) image along with the selected area electron diffraction (SAED) results. FIG. ID shows the STEM-energy-dispersive X-ray spectroscopy (EDS) mapping, including Co, Cu and O maps. FIG. IE shows the atomic structure of the nonordered Cu-substituted C03O4 material, wherein Cu randomly occupies Td or Oh sites. FIG. IF shows the electrochemical cycling performance of the material and of unsubstituted C03O4 at a current density of 0.1 A g ^"1 .

[0009] FIGs. 2A-2B illustrate the lithiation of Cu-substituted C03O4 material as studied by in-situ TEM. FIG. 2A shows a pristine, single-crystal Cu-substituted C03O4 nanoparticle with hexagonal shape oriented closed to the [110] zone axis (the diffraction partem is shown as an insert). FIG. 2B shows the nanoparticle after lithiation, revealing the development of a poly crystalline morphology consisting of L12O, metal Cu and Co as determined by the inserted electron diffraction. Results which were obtained but are not shown include a Z- contrast STEM image of the lithiated nanoparticle, with an EELS (electron energy loss spectroscopy) spectrum showing both O and Co edges. Other data include nanobeam electron diffraction of the lithiated Cu-substituted C03O4, which showed single-crystal like diffraction spots of L12O and Cu, and diffuse arcs of Co (data not shown). The Cu { 111 } lattice plane was parallel to the { 111 } of L12O. Other data include a high-resolution electron microscope (HREM) image of the lithiated Cu-substituted C03O4, which showed large Cu and L12O crystals on which small Co nanoparticles are formed (data not shown). Other data include EELS maps of Co, O and Co+O along with its Z-contrast STEM image of the lithiated Cu- substituted C03O4, confirming the presence of Co nanoparticles (data not shown).

[0010] FIGs. 3A-3D illustrate the reaction front of the lithiation of a Cu-substituted C03O4 nanoparticle as studied by in-situ HREM. In particular, FIGs. 3A-3D show in-situ TEM images showing the movement of the reaction front along with the resulting volumetric expansion of the nanoparticle. Other data obtained but not shown include in-situ HREM images of the reaction interface showing the formation of intermediate and intercalated phases and the formation of large L12O and Cu crystals and Co-nanoparticles at the few nanometer scale. The {220} lattice spacing was identified by Fourier transformation. Other results include models of the intermediate and intercalated phases in the lithiation of Cu- substituted C03O4 using the Cu:Co ratio as 1 :5 for the simplicity of supercell generation in density functional theory (DFT) calculations (not shown).

[0011] FIGs. 4A-4E illustrate the structural evolution during Cu-substituted C03O4 delithiation. FIG. 4A shows a TEM image of the delithiated Cu-substituted C03O4 showing that the rhombohedral shape with straight facets is well kept after delithiation. FIG. 4B shows the SAED pattern of the delithiated particle showing CoO diffraction rings along with some sharp spots from large crystals. FIG. 4C shows X-ray photoelectron spectroscopy (XPS) spectra of lithiated and delithiated Cu-substituted C03O4 samples showing Cu and Co peaks. The oxidation of Co and partial oxidation of Cu in delithiation were confirmed. FIGs. 4D and 4E provide a schematic illustration of the reversible structural and chemical changes which take place during the charge (FIG. 4D) and discharge (FIG. 4E) cycles. Other data which were obtained but not shown include a nanobeam electron diffraction pattern showing large spots which are from Cu and CuO crystals. Other data include in-situ TEM images which show the movement of the reaction front along with volumetric expansion (data not shown). Data also include an HREM image of the delithiated sample showing CoO nanoparticles on the substrate of Cu and CuO (data not shown). Data also include a Z-contrast STEM image, a Co map and a Cu map of the delithiated sample (data not shown). CoO clusters appeared as bright spot in the STEM images. Results also include a comparison of experimental and DFT simulated voltage profiles for the first cycle of lithiation and delithiation and a comparison of experimental and DFT simulated voltage profiles for the following cycles of lithiation and delithiation (not shown).

DETAILED DESCRIPTION

[0012] Provided are anode active materials for lithium ion batteries and lithium ion batteries incorporating the anode active materials. In at least some embodiments, the anode active materials exhibit improved cyclic stability as well as higher capacities as compared to conventional anode active materials. In at least some embodiments, the anode active materials are significantly less susceptible to mechanical fractures, structural pulverization and loss of contact with the electric collector of Li ⁺ ion batteries. By way of illustration, it has been found that by incorporating even a very small amount of Cu into the lattice of spinel C03O4, a dynamic framework composed of ultrathin flakes of metal Cu can be formed which extends throughout the ternary Cu-substituted C03O4 material. This dynamic framework provides a highly-conductive support which can endure large volume changes caused by lithiation/delithiation cycles, thereby achieving cycling stability while also maintaining high capacity. Results for the illustrative ternary Cu-substituted C03O4 material, CU3/7C018/7O4, are further described in the Example, below.

[0013] The anode active materials are made by incorporating (e.g., doping) a metal element into a metal oxide compound. In the present disclosure, the metal element which is incorporated into the metal oxide compound may be referred to as the "substituent metal." The metal oxide may be a binary metal oxide, i.e., a compound of a metal and oxygen. The metal of the metal oxide may be a transition metal, e.g., a 3d transition metal such as Cr, Mn, Co, Fe, Cu or Ni. The metal oxide may be selected on the basis of its ability to undergo lithiation reactions and delithiation reactions analogous to those shown in Equations (1) and (2) below.

M _x O _y + 2yLi ⁺ + 2ye ^~ →xM ₀ + yLi ₂ O (1) xM ₀ + yli ₂ 0→M _x O _y + 2yLi ⁺ + 2ye ^~ (2)

The metal oxide may be a metal oxide having a spinel structure. An illustrative binary transition metal oxide is cobalt oxide, e.g., C03O4. Others include, but are not limited to, Fe ₃ 04, Fe ₂ 0 ₃ , MnC , NiO, CuO, CoO, etc. [0014] The metal element incorporated into the metal oxide to form the anode active material, i.e., the substituent metal, is different from the metal of the metal oxide compound. However, the substituent metal may be another transition metal, e.g., a 3d transition metal such as Cr, Mn, Co, Fe, Ni or Cu. The substituent metal may be selected on the basis of its conductivity, ductility, and malleability. Metal elements that are highly conductive, ductile and malleable are particularly useful, e.g., Cu.

[0015] Like the metal oxide compound, the anode active material (i.e., the metal- substituted metal oxide) may be characterized as being capable of undergoing the lithiation/delithiation reactions described above. An illustrative anode active material is Cu- substituted C03O4. The amount of the substituent metal being incorporated into the metal oxide may vary. This amount may be quantified as a ratio of the metal of the metal oxide/substituent metal (e.g., Co/Cu in Cu-substituted C03O4). Such ratios may be measured via EDS as described in the Example, below. The ratios may be reported as an average ratio as measured from a representative number of nanocrystals of the anode active material.

[0016] The amount/ratio of the metal of the metal oxide/substituent metal may be selected to achieve the formation of a three-dimensional (3D) network of the substituent metal upon lithiation of the anode active material. This 3D network is further described below. At the same time, the amount/ratio may be selected to achieve a desired (e.g., maximum) capacity for a Li ⁺ battery incorporating the anode active material. As noted above and further described in the Example below, it has been found that even very small amounts of a substituent metal can form the 3D network and provide Li ⁺ batteries which exhibit both high cycling stabilities and high capacities. By way of illustration, in embodiments, the anode active material is CU3/7C018/7O4 in which the ratio of Co/Cu is about 6. In embodiments, the ratio of metal of the metal oxide/substituent metal is at least about 5, at least about 6, at least about 7, at least about 8, at least about 9, at least about 10, or in the range of from about 5 to about 10. With respect to the ratio of metal of the metal oxide/substituent metal, the term "about" means within ± 10% in the present disclosure.

[0017] The anode active material may be characterized by its morphology in a pristine state, i.e., prior to undergoing lithiation/delithiation. The anode active material may be in the form of hexagonal shaped nanocrystals. By "hexagonal" it is meant that a cross-section of the nanocrystal (as determined from an SEM or TEM image) has six distinct edges arranged in the shape of a hexagon. However, the length of each edge need not be exactly the same. In addition, although edges generally meet at sharp corners, some nanocrystals may have rounded corners. An illustrative anode active material composed of hexagonal shaped nanocrystals is shown in FIGs. 1A, 1C, and 2A. The size of the nanocrystals, quantified as the maximum edge-to-edge width across the nanocrystal, may be no more than about 150 nm, or no more than about 100 nm, or in the range of from about 25 nm to about 200 nm. The size may be an average size as reported from a representative number of nanocrystals and as measured from TEM images. (See FIG. 2A.) Hexagonal shaped nanocrystals provide an indication of the quality of the nanocrystals. This includes the crystallinity of the nanocrystals (i.e., single-crystalline) and uniformity of composition of the nanocrystals (e.g., uniform distribution of the substituent metal). In addition, hexagonal shaped nanocrystals ensure that electrolyte in the Li ⁺ battery is exposed to a specific lattice plane, e.g., { 111 } for a cubic structure, of the anode active material.

[0018] The anode active material may be characterized by its crystallinity in the pristine state. The anode active material may be single-crystalline characterized by a single crystal phase. The single crystal phase may be the same crystal phase as the unsubstituted metal oxide compound. In embodiments, the single crystal phase is a spinel structure. Confirmation of single-crystallinity may be achieved via X-ray powder diffraction and comparison to the X-ray powder diffraction of the unsubstituted metal oxide. (See, e.g., FIG. IB.) As noted above, existence of a hexagonal shape also indicates a single-crystalline material.

[0019] The anode active material may be characterized by its atomic structure and the nature of the distribution of the substituent metal throughout the metal oxide compound, i.e., throughout the lattice structure of the metal oxide. The substituent metal may be randomly and uniformly distributed throughout the lattice structure of the metal oxide. The substituent metal distribution may be verified using STEM-EDS mapping. (See, e.g., FIGs, ID and IE.) The distribution of the substituent metal described in this paragraph refers to the anode active material in its pristine state.

[0020] The anode active material may be combined with other materials to form the anode of a Li ⁺ ion battery. Such other materials include conductive carbon (e.g., carbon black) and a binder (e.g., poly vinylidene fluoride (PVDF)). However, in embodiments, the anode is free of a material such as graphene or graphene oxide. By "free" it is meant that the amount of the graphene/graphene oxide is zero or so small so as to have no material effect on the properties of the anode active material. In conventional anodes for Li ⁺ ion batteries, graphene/graphene oxide has often been used as a support material and to improve the performance of the Li ⁺ ion batteries. However, as further described in the Example, below, it has been found that the present anode active materials can achieve high capacity and cycling stability even without the presence of graphene/graphene oxide.

[0021] Hydrothermal methods may be used to make the anode active materials. Such techniques involve combining a first solution (e.g., aqueous solution) of a precursor of the metal oxide compound with a second solution (e.g., aqueous solution) of a precursor of the substituent metal under conditions (e.g., relative amounts of the precursors, elevated pressure, elevated temperature, time, in the presence of an additive) to form the metal-substituted metal oxide. Organometallic compounds may be used for the precursor compounds. Illustrative precursor compounds, conditions and additives are provided in the Example, below. The conditions noted above may be adjusted to achieve a particular ratio of metal of the metal oxide/substituent metal, the hexagonal shape, single-crystal material, and/or the

random/uniform distribution of substituent metal as described above. By way of illustration, to achieve the CU3/7C018/7O4 material, these parameters should generally be within 10% of the values of these parameters used in the Example, below.

[0022] The anode active materials may be used in the anode of a Li ⁺ ion battery. The Li ⁺ ion battery may further include a cathode in electrical communication with the anode; an electrolyte disposed between the anode and the cathode; and a separator also disposed between the anode and the cathode. Known materials may be used for the cathode, the electrolyte and the separator. Illustrative cathode, electrolyte and separator materials are provided in the Example, below.

[0023] The anode active materials may be further characterized by their morphologies in the lithiated/delithiated states. As noted above and further described in the Example, below, it has been found that upon lithiation of the present anode active materials, the substituent metal can form a 3D network of the substituent metal through which other nanoparticles are distributed, including nanoparticles composed of L12O and nanoparticles composed of the metal of the metal oxide compound. In this lithiated state, the substituent metal of the network may have a cube-on-cube orientation relationship with the L12O of the L12O nanoparticles even if there is a substantial lattice mismatch (e.g., greater than 20%). Upon delithiation, the anode active material comprises the 3D network of the substituent metal and nanoparticles distributed throughout the network, including nanoparticles composed of an oxide of the substituent metal and nanoparticles composed of an oxide of the metal of the metal oxide compound. In this delithiated state, the substituent metal of the network may also have a cube-on-cube orientation relationship with the oxide of the substituent metal; again, even if there is substantial lattice mismatch (e.g., greater than 20%). Thus, the 3D network of the substituent metal is maintained during lithiation/delithiation and serves as a conductive and flexible matrix which accommodates the various chemical and structural changes that accompany lithiation/delithiation. Surprisingly, this 3D network is able to form even in the presence of very small amounts of the substituent metal, e.g., at ratios of the metal of the metal oxide/substituent metal in the range of from about 5 to about 10.

[0024] The "network of substituent metal" may be composed of nanoflakes or nanoplates of the substituent metal. By "3D network" it is meant that the network of the substituent metal extends in three-dimensions throughout the anode active material, akin to veins in a body. The average thickness of such veins (i.e., assemblies of nanoflakes/nanoplates) may be in the range of from about 10 to 100 nm or from about 20 nm to about 50 nm. The average size (i.e., diameter) of the nanoparticles of the metal of the metal oxide may be in the range of from about 1 nm to about 10 nm or from about 1 nm to about 5 nm. The average size of the L12O nanoparticles and the nanoparticles of the oxide of the substituent metal may be in the range of from about 10 to 100 nm or from about 20 nm to about 50 nm. Average

thicknesses/sizes may be determined from a representative number of nanocrystals using TEM images.

[0025] The morphologies of the anode active materials in the lithiated/delithiated states may be verified using TEM and HREM as described in the Example, below. By way of illustration, the morphologies of the lithiated/delithiated states of a Cu-substituted C03O4 (CU3/7C018/7O4) anode active material is illustrated in FIGs. 4D and 4E. In the lithiated state, the anode active material comprises a network of Cu metal and L12O nanoparticles and Co nanoparticles distributed throughout the network. In the delithiated state, the anode active material comprises the network of Cu metal and CuO nanoparticles and CoO nanoparticles distributed throughout the network. As shown in FIG. 4D, although some of the Cu metal is oxidized to CuO in the delithiated state, the oxidation is only partial so that the network of Cu is maintained. In the lithiated state, the Cu and L12O nanoparticles have a cube-on-cube orientation relationship. In the delithiated state, the Cu and CuO nanoparticles have a cube- on-cube orientation relationship.

EXAMPLE

[0026] Introduction [0027] The conversion/deconversion reactions between transitional metal oxides and lithium bears similarity to that in lithium-oxygen batteries, wherein L12O (and L12O2) is repeatedly formed in the discharge cycle and decomposed in the charging cycle. The conversion reaction:

M _x O _y + 2yLi ⁺ + 2ye ^~ → xM ₀ + yLi ₂ 0 (1) is thermodynamically feasible and has a positive electromotive force ^[10] . In discharge, however, large volume expansion due to L12O formation limits cycling stability.

[0028] The deconversion reaction: xM ₀ + yLi ₂ 0→M _x O _y + 2yLi ⁺ + lye (2) involves cleavage of stable Li-0 bonds, which is not a thermodynamically favorable process (1.98 e /atom). Thus, efficient decomposition of L12O to reduce the amount of

electrochemically inactive L12O in the charging cycle and to keep lithium ions active in cycling are important challenges. In this Example, we demonstrate Cu-substituted C03O4 as a stable conversion electrode material that exhibits both high capacity and cycling stability in a single materials system.

[0029] Experimental

[0030] Materials: Hydrothermal method was used to synthesize Cu-substituted C03O4 nanocrystals. In a typical synthesis, 0.02 mmol Co(acac)2 and 0.02 mmol Cu(acac) 2H20 was dissolved in 10 ml deionized water and stirred for lh. Then 10 ml Co ²⁺ (0.02 M) aqueous solution, 10 ml Cu ²⁺ aqueous solution and 10 ml 0.04 M NaF aqueous solution were mixed and stirred for lh. The mixed suspension was transferred into a 50 ml Teflon-lined stainless steel autoclave and kept at 160 °C for 12h. The black precipitates in the bottom were collected and washed by centrifugation for three or four times (4500 rpm, 5min) using ethanol. The power was dried at 80 °C for 12 h for the subsequent characterization and electrochemical measurements.

[0031] Characterization: Field emission scanning electron microscope (Hitachi, SU- 8030) was used to observe the microstructure of the prepared samples. Crystal structure was identified using X-ray diffraction with Cu-Κα radiation (Scintag XDS2000). Field emission high resolution transmission electron microscope (JEOL, JEM-2100F) and a dedicated scanning transmission electron microscope (Hitachi-2300 STEM) were employed to do the characterization.

[0032] Electrochemical measurements: Active materials of Cu-substituted C03O4 or C03O4 were mixed with super-P carbon black and poly vinylidene fluoride (PVDF) at weight ratio of 70:20: 10 using N-methyl-2-pyrrolidone (NMP) as solvent. The obtained slurry was then coated on tailed Cu foil and dried at 80 °C for 12 h in a vacuum oven to remove the solvent and used as the working electrodes. Half-cells were assembled in Ar-filled glove box using pure lithium metal foil as the counter electrode, and Celgard 2325 membrane as separator. The 1M L1PF6 in a mixture of ethylene carbonate and dimethyl carbonate (volume ratio = 1 : 1) was used as electrolyte.

[0033] The discharge and charge measurements of the half-cells were performed on a multi-channel battery testing system Arbin BT-2143 between the volt range from 0.01 to 3V (vs. Li/Li ⁺ ) at room temperature. The rate performance of Cu-substituted C03O4 and C03O4 are also evaluated at different current densities from 0.1 to 1.0 A/g.

[0034] In-situ TEM: Like other window-less in-situ TEM settings ^[8] the open half-cell was constructed in an in-situ electrical probing TEM holder (Nanofactory Instrument). This holder has a dual-probe design, i.e. one Au rod is used as the sample holder with a small amount of Cu-substituted C03O4 attached to its tip; on the other side a STM tungsten (W) probe driven by Piezo-motor capable of 3D positioning with a step-size of 1 nm was used to mount Li metal. The W probe tip was scratched by Li metal strip and then affixed on the TEM holder inside an Ar-filled glove box. With an airtight cover, the TEM holder was transferred to TEM column with limited exposure to air (5 s), where a layer of lithium oxide was grown on the surface of Li metal and acted as a solid electrolyte for the nano-cell Li-ion batteries.

[0035] First-principle calculations: All the first-principle calculations were conducted via the Vienna Ab-initio Simulation Package (VASP) ^[16] with the projector augmented wave (PAW) potentials. ^[17] For the exchange-correlation functional, we used the generalized gradient approximation (GGA) of Perdew-Becke-Ernzerhof (PBE) ^[18] with spin polarization considered. We used two different sets of parameters: one for lower energy configuration sampling and the other for accurate total energy determination of these lower energy configurations determined. For the coarse energy sampling calculations, a plane-wave basis set with a cutoff energy of 300 eV and Γ-centered k-meshes with the density of 2000 k-points per reciprocal atom were used. The accurate total energy calculations were performed with a plane-wave basis set cutoff energy of 520 eV and Γ-centered k-meshes with the density of 8000 k-points per reciprocal atom. DFT + U method ^[19] was used to treat the 3d electrons of Co and Cu ions with U values of 3.3 eV and 4.0 eV adopted following previous studies. ^[19_20]

[0036] Search for the non-equilibrium intermediate phases through the Li Cu-substituted C03O4 and CuO reactions: We used a non-equilibrium phase search (NEPS) method to identify the intermediate phases during the non-equilibrium lithiation process of Cu- substituted C03O4 and CuO by exploring geometrically distinct Li/vacancy configurations on possible insertions sites of Cu-substituted C03O4 and CuO structures at different

compositions (Li/vacancy ratios). (See G. L. Hart, R. W. Forcade, Phys. Rev. B 2008, 77, 224115; Q. Li, Z. Yao, J. Wu, S. Mitra, S. Hao, T. S. Sahu, Y. Li, C. Wolverton, V. P.

Dravid, Nano Energy 2017, 38, 342.) The searching is initiated by identifying all the unoccupied sites of Cu-substituted C03O4 and CuO.

[0037] For Cu-substituted C03O4, we used a supercell containing 1 Cu ²⁺ cations and 5 Co ⁺ cations and 8 O ^2" anions, which has 18 (14 tetrahedral and 4 octahedral) unoccupied sites in total for Li uptake. The primitive spinel unit cell of C03O4 contains 6 Co and 8 O atoms, and replacing one Co with a Cu ion results in a 1 :5 ratio of Cu:Co, a reasonable approximation to the observed composition. Creating a supercell with a 1 :6 ratio would require a multiple of 7 cations, resulting in a supercell that is 7 times larger than the primitive cell, which would be computationally prohibitive for the extensive lithiation simulations. The use of a 1 :5 ratio in the DFT calculations is then simple for computational efficiency. We insert the Li atoms into the unoccupied sites for a range of compositions within 0 < x < 8 for LLCuo.5C02.5O4. For CuO, we used a supercell containing 6 Cu ²⁺ cations and 6 O ^2" anions, which has 12 octahedral unoccupied sites for Li uptake. Starting from an initial structure (not shown), we insert the Li atoms into the unoccupied sites for a range of compositions within 0 < x < 2 for Li uO. Enum code was used to generate all symmetrically distinct configurations of Li on the unoccupied sites for each composition of LLCuo.5C02.5O4 and Li uO. Total energies of all these configurations were firstly sampled using coarse DFT calculations with parameters described herein. (See G. L. Hart, R. W. Forcade, Phys. Rev. B 2008, 77, 224115; G. L. Hart, R. W. Forcade, Phys. Rev. B 2009, 80, 014120; G. L. Hart, L. J. Nelson, R. W. Forcade, Comput. Mater. Sci. 2012, 59, 101 ; G. L. Hart, R. W. Forcade, Phys. Rev. B 2009, 80, 014120; G. L. Hart, L. J. Nelson, R. W. Forcade, Comput. Mater. Sci. 2012, 59, 101 ; M. Aydinol, A. Kohan, G. Ceder, K. Cho, J. Joannopoulos, Phys. Rev. B 1997, 56, 1354; M. K. Chan, C. Wolverton, J. P. Greeley, J. Am. Chem. Soc. 2012, 134, 14362.; C. Wolverton, A. Zunger, Phys. Rev. Lett. 1998, 81, 606; E. Sanville, S. D. Kenny, R. Smith, G. Henkelman, J. Comput. Chem. 2007, 28, 899; and W. Tang, E. Sanville, G. Henkelman, J. Phys. Condens. Matter. 2009, 21, 084204.) Afterward, the structures at each composition were ranked by their coarse total energies and the lowest three energy configurations are further relaxed in DFT with accurate settings described herein. We evaluated formation energies of these selected structures according to the reaction: Cuo.5C02.5O4 + xLi ⁺ → LiXuo.5C02.5O4 and CuO + xLi ⁺ → LLCuO. Convex hulls were then built with formation energies of all various stoichiometries. All the intermediate non-equilibrium phases were then identified by the compositions on the convex hull.

[0038] The (de)lithiation reaction voltage relative to Li/Li+ is given by the negative of the reaction free energy per Li, which is

where AG _f is the free energy molar change during the reaction, F is the Faraday constant, AN _Li is the amount of Li added/removed. (See M. Aydinol, A. Kohan, G. Ceder, K. Cho, J. Joannopoulos, Phys. Rev. B 1997, 56, 1354.) The enthalpic (pV _m ) contribution to G is of the order 10 μβν per Li at atmospheric pressure and can be safely ignored and the entropic contribution to the voltage can be estimated to be systematic. (See M. K. Chan, C.

Wolverton, J. P. Greeley, J. Am. Chem. Soc. 2012, 134, 14362.) We replace G with total energy E from DFT calculations in following calculations.

AE = £(Li _y Cu _{0 5} Co _{2 5} 0 ₄ ) - £(Li _x Cu _{0 5} Co _{2 5} 0 ₄ ) - ( - x)£(Li _metal ) (2a) AE = £(Li _y CuO) - £(Li _x CuO) - (y - x)£(Li _metal ) (3a)

[0039] Additionally, the realistic lithiation/delithiation reactions do not necessarily proceed strictly through two-phase reactions. Thus, the voltage profiles obtained should be viewed as approximate and very small voltage steps should not be taken as significant.

Meanwhile, the voltage drops in the voltage profile would become much more rounded at finite temperatures (i.e. room temperature) when take entropy contribution into account. (See C. Wolverton, A. Zunger, Phys. Rev. Lett. 1998, 81, 606.) Furthermore, the structures of several intermediate phases LLCuo.5C02.5O4 and LLCuO could be disordered at finite temperature, which would also affect the energies of these phases and thus influence the voltage plateaus. [0040] Predictions of the non-equilibrium lithiation process of Cu-substituted C03O4 and CuO. We investigate the non-equilibrium lithiation process of Cu-substituted C03O4/CUO by the prediction of non-equilibrium structures along the lithiation pathway based on

geometrical numerations. Four/four non-equilibrium phases (LLCuo.5C02.5O4, x = 1.0, 2.5, 5.0, 8.0 and Li uO, x = 0.67, 1.17, 1.83, 2.00) are identified constituting the Li- Cuo.5C02.5O4/CuO convex hull during the lithiation process of Cu-substituted C03O4 and CuO. Using a series of lithiation reactions with these non-equilibrium phases considered, we offer the calculated non-equilibrium lithiation voltage profiles. To confirm the sequential order of reduction, Bader charge analysis were conducted for Co and Cu ions in metastable phases. (See E. Sanville, S. D. Kenny, R. Smith, G. Henkelman, J. Comput. Chem. 2007, 28, 899; and W. Tang, E. Sanville, G. Henkelman, J. Phys. Condens. Matter. 2009, 21, 084204.)

[0041] The lithiation of Cu-substituted C03O4 initiates by Li taking the octahedral sites (x = 1.0) neighbored by Cu ions and Co ⁺ ions partially get reduced to Co ²⁺ when Bader charge of Cu decreases from to +1.27e to +1.23e. With further lithiation (x = 2.5 and 5.0), the amount of Li inserted exceeds what the octahedral can accommodate and the Li ions energetically prefer the tetrahedral sites. Cu and Co ions experience reduction Co ⁺ — > Co ²⁺ — > Co ⁰ , Cu ²⁺ — > Cu ¹⁺ with Cu ions get partially reduced to their metal states. Meanwhile, the oxygen fee framework only gets distorted slightly and the lithiation shows features of intercalation-type with overall preserved oxygen backbones. Beyond the intercalation-type reaction range (x≥ 5.0), both Cu and Co ions get partially reduced to their metal states and extruded. The lithiation now switches to the conversion-type reaction with features of phase separation. When the Cu-substituted C03O4 is fully lithiated (x = 8), Cu and Co ions have been fully reduced to Cu/Co metal and Li ions combine with O ions forming L12O.

[0042] The lithiation of CuO also initiates (x = 0.67) with the intercalation-type reaction with Li ions take the empty octahedral sites. With more Li ions inserted (x = 1.17), Cu ²⁺ ions are generally reduced to Cu ¹⁺ while oxygen backbones maintained yet Cu and Li sublattice largely distorted. Beyond intercalation-type lithiation (x > 1.83), Cu ions start to be reduced to their metal states and extruded with the onset of phase separation. When CuO is fully lithiated, the system features with layered L12O and Cu clusters.

[0043] Results and Discussion

[0044] Cu-substituted C03O4 was synthesized hydrothermally, resulting in crystals as revealed by SEM (FIG. 1 A). The crystal structure was identified to be spinel (space group: Fd-3m, No. 227), the same as C03O4, confirmed by both x-ray and electron diffraction (FIGs. 1B-1C). The elemental maps collected by x-ray energy dispersive spectroscopy (EDS) are shown in FIG. ID. The cation ratios (Cu and Co) were varied from one sample to the other around 1 :6 (as listed in Table 1, below). The phase analyses corroborate with the nominal spinel structure of C03O4, but with a shift to low angles, indicating that copper was distributed randomly and uniformly as a solid solution. The averaged lattice parameter was identified by x-ray diffraction (FIG. IB) as a = 8.5 A.

[0045] Table 1. Co/Cu atomic ratio measured by EDS from 9 pristine Cu-substituted C03O4 nanoparticles.

[0046] The cycling stability of the Cu-substituted C03O4 was greatly improved as shown by the electrochemical measurements. Coin-cell batteries using as-prepared Cu-substituted C03O4 and pure C03O4 as electrodes were fabricated and evaluated for their lithium storage properties in the potential window of 0.01-3.0 V (vs Li/Li ⁺ ) (FIG. IF). Cu-substituted C03O4 showed a high second discharge capacity of 877 mAh g ^"1 at a current density of 0.1 A g ^"1 . After 60 cycles of charging and discharging, high capacity was retained at -863 and -883 mAh g ^"1 , respectively. In contrast, pure bulk C03O4 showed a greatly reduced capacity (<200 mAhg ^'1 ) after just 20-30 cycles. Nanosizing is an effect approach to improve the cyclability. We have measured the electrochemical properties of pure C03O4 nanoparticles that are -50 nm in size (FIG. IF), which showed discharge capacity of 796 mAh g ^"1 at the second cycle. After 60 cycles at the same current density, it exhibited notably fast capacity decay, with charge and discharge capacity of 423 and 445 mAh g ^"1 , respectively. Evidently, the pure C03O4 control sample exhibits significantly inferior cycling stability compared to Cu-substituted C03O4. In addition, Cu-substituted C03O4 shows improved charge/discharge kinetics compared to C03O4. The capacity of Cu-substituted C03O4 compared to C03O4 control samples at various cycling rates ranging from 0.1 to 1.0 A g ^"1 was also measured (0.125 to 1.25 C; A C-rate is a measure of the rate at which a battery is discharged relative to its maximum capacity; for example, 1C rate means that the discharge current will discharge the entire battery in 1 hour) (data not shown). Over this range, the capacity of the Cu- substituted C03O4 electrode exceeded 400 mAh g ^"1 , whereas for the control it dropped below 100 mAh g ^"1 at the highest cycling rate.

[0047] To probe the physical mechanism underlying the improved electrochemical performance of Cu-substituted C03O4, the lithiation of Cu-substituted C03O4 was directly investigated by in-situ TEM with a pre-assembled half-cell miniature battery configuration. A representative pristine, single-crystalline Cu-substituted C03O4 nanoparticle (see FIG. 2A) oriented close to the [110] axis was chosen for examination during lithiation. The lithiation of this nanoparticle resulted in the formation of nanoscale crystallites (FIG. 2B) with overall areal expansion of about 200% (data not shown), showing large volume expansion. In the selected-area electron diffraction (SAED) pattern, shown as an inset in FIG. 2B, diffraction rings of L12O and broader diffuse scattering were observed, indicating that reaction product is a mixture of L12O, Cu and Co nanocrystals.

[0048] The orientation relationship between the formed Cu and L12O was further disclosed by nano-beam electron diffraction. Several bright diffraction spot arcs were observed along the diffuse rings, close to bright spots of L12O, as indicated by the arrowheads in the inset of FIG. 2B. In the nano-beam electron diffraction pattern obtained (not shown), alignment of the diffraction spots was evident. These spots represent the Cu { 111 } and L12O { 111 } planes, while both crystals are oriented along the [110] direction. In the partem, the Cu_(-11-1) spot and Li20_(-l l-l) spot were not superimposed due to large mismatch (-22%). However, the two spots are in the same radial line without any rotational mismatch. Such an intimate relationship was also observed for other diffraction spots, which demonstrates a cube-on-cube orientation relationship although the interface between Cu and L12O is incoherent. Both Cu and L12O showed strong single-crystalline sharp spots, indicating that the crystalline size of Cu and L12O crystals was sufficiently large, in the range -20 nm (the beam size used for nano-beam diffraction was -50 nm) or larger. Meanwhile, the size of the Co clusters was very small, -2 nm, as measured from the high-resolution electron microscopy (HREM) images. In addition, the Co clusters were likely defective and highly strained (data not shown) as indicated by the broad diffuse arcs in the nano-beam diffraction pattern (data not shown). Moreover, the Co clusters appeared as bright regions in the Z-contrast scanning transmission electron microscopy (STEM) image (data not shown). Combined with electron energy loss spectroscopy (EELS) of O and Co, the Co and O distribution was spatially revealed (data not shown), confirming that the bright clusters in the STEM image were rich in Co.

[0049] At the end of the first lithiation, there were -2 nm Co clusters distributed on the -20 nm metal Cu and L12O crystals, with the Cu and L12O crystals exhibiting a cube-on-cube orientation relationship ([100]//[100] and (100)//(100)) (data not shown). We also investigated the cycled Cu-substituted C03O4 that was taken out from the coin cells after running at different cycles. The ex-situ results obtained at the first and 10 ^th cycle by ex-situ observation (data not shown) agreed well with the in-situ TEM observations. In short, very fine Co-metal nanoclusters uniformly distributed on Cu and L12O crystals were formed at the end of the first lithiation, while Cu and L12O have the cube-on-cube orientation relationship although their lattice mismatch is large.

[0050] The Cu-substituted C03O4 lithiation was further investigated at high resolution and in conjunction with DFT simulations, to understand why L12O and Cu crystals have such an intimate and low-index cube-on-cube orientation relationship despite a large lattice mismatch. As shown in FIGs. 3A-3D, the lithiation propagates with the motion of the interface delineating the lithiated and pristine phases. A closer observation of the interface (data not shown) revealed the formation of Li intercalated and crystalline phases with a notably expanded {022} lattice spacing, from 0.28±0.1 nm of the CU3/7C018/7O4 to 0.30±0.1 nm and 0.32±0.1 nm. However, further lithiation leads to phase separation, resulting in the formation of L12O and Cu crystals as evidenced by the splitting of spots in the Fourier transformation (data not shown). The Co atoms are extruded from the nanostructures forming Co-clusters with the Co-clusters growing larger as more lithium is inserted (data not shown). Instead of forming large -20 nm Cu crystals, Co atoms tend to form small clusters -2 nm when they are extruded.

[0051] The lithiation of Cu-substituted C03O4 was simulated using DFT based non- equilibrium phase searching method, ^{[1 ]} which shows the prediction of several intermediate and metastable phases. For the simplicity of super-cell generation in DFT calculations and computational efficiency, the Cu/Co ratio was taken as 1 :5 for the original phase before lithiation. From the {220} spacing (referring to the spinel lattice), three intermediate phases predicted by DFT calculations were observed (not shown), prior to the final phase separation by the conversion reaction (not shown). Instead of direct transition from Cu-substituted C03O4 to metal Cu, Co and L12O, the intermediate and Li-intercalated LixCu3/7Cois/704 phases provide a gradual transformation pathway to the formation of nanoscale L12O and Cu, allowing them to have a close orientation relationship. This explains the experimentally observed orientation between these phases, even though they have large lattice mismatch. The reactions involved in Cu-substituted C03O4 lithiation calculated by DFT are summarized in Table 2, below.

[0052] Table 2. DFT predicted non-equilibrium lithiation and equilibrium delithiation reaction athways of Cu-substituted C03O4 during the 1 ^st discharge and charge.

[0053] In the charging cycle (delithiation), the particles being charged maintain their shape and continue to have a poly crystalline structure as shown in FIG. 4A. An unusual intimate orientation relationship between the formed CuO crystals and Cu has been disclosed while Cu is oxidized into CuO. In the SAED pattern of the delithiated sample (FIG. 4B), several diffraction rings can be identified as CoO nanocrystals. The bright diffraction spots from larger crystals can be indexed as metal Cu and CuO (data not shown). After delithiation, there are ~2 nm CoO clusters on the metal Cu and CuO crystals of -20 nm (data not shown), while Cu and the newly formed CuO crystals have a cubic-to-cubic orientation relationship (if one considers CuO as the pseudo-cubic lattice). The chemical state of both Cu and Co were identified by XPS (FIG. 4C), showing the oxidation of Co and partial oxidation of Cu during delithiation. Along with the decomposition of L12O, delithiation results in the Co nanoparticles being oxidized to CoO (and perhaps even Cu _x Co3-x04). However, only some portion of the Cu metal are oxidized to CuO, as there are still clear metallic FCC Cu peaks in the electron diffraction. By simply assuming kinematic scattering and using the intensities of the Cu(l 11) and CuO(l 10) spots, the CuO/Cu atomic ratio was estimated to be about 4.7/1, which means in the delithiation about 20% of the Cu remains as support. The reactions during delithiation are summarized in Table 2, above. CuO has higher voltages (~ 2.1 V) than that of CoO (- 1.7 V), meaning that metal Co will be oxidized first while Cu is still in the metallic form. Although it is not observed in the diffraction patterns, the presence of C03O4 cannot be excluded since the voltage reaches more than 2.5 V ^[14] .

[0054] The lithiation and delithiation reactions in the first cycle can be described as:

CU3/7C018/7O4 + 8Li ⁺ + 8e ^" → -Cu +—Co + 4Li ₂ 0 (3)

7 7 '

¾u + yCo + 4Li ₂ 0 - (4+2x+y)Li ⁺ - (4+2x+y) _e -→ xCuO + (~x)Cu + (y-y)CoO +

(f)C0304 + ( -f-x)Ll20, (4) where x is ratio of CuO/Cu to measure how much Cu has been oxidized and y is ratio of C03O4/C0O to measure how much Co ⁰ has been oxidized to Co ⁺ .

[0055] Part of the L12O formed in the first lithiation becomes inactive in the following cycles depending on how much Cu has been oxidized, which may partially contribute to the large capacity loss in the first cycle (besides the formation of SEI). In the subsequent cycles, although the Cu/CuO redox reaction tends to become more stable, the fluctuation of the amount of Cu being oxidized may eventually influence the actual capacity. This effect may explain why sometimes there is an increase in capacity, as is commonly observed in oxide electrodes.

[0056] The nanocomposites of small CoO nanoparticles uniformly distributed on a thin and stretchable metal Cu/CuO network appear robust for long duration cycling. In lithiation, Cu/CuO nanoplates and Cu/CoO interfaces provide enough sites for L12O nucleation and growth (illustrated in FIG. 4D), which enables volumetric expansion without fracture. In delithiation, the intimate contact of Cu nanoplates and Co nanoparticles may act as a catalyst for the L12O decomposition reaction (illustrated in FIG. 4E). In addition, the metal Cu nanoplates form a percolating network, enabling high electronic conductivity (data not shown). The two major products in lithiation, Cu (fee with a=3.615 A) and L12O (fee with a=4.619 A), have a simple cube-on-cube relationship, although their misfit is about 22%. In delithiation, Cu and CuO (pseudocubic structure with a=4.778 A) have also a cube-on-cube relationship although their misfit is about 24%. The cube-on-cube relationship helps not only maintain the intimate contact between L12O and Cu in lithiation, and between CuO and Cu in delithiation, but also provide an efficient way of accommodating the L12O in lithiation and CuO in delithiation. Such an electrochemically driven confinement at nano-scale prompts the reversibility of the lithiation/delithiation reactions and thus the cycling stability. Among all the advantages brought by Cu substitution, the formation of Cu support is the most salient one. In pure C03O4 without Cu substitution, Co nanoparticles formed in lithiation are on the nonconductive L12O support and may pulverize and be lost in the following cycles when L12O decomposes in delithiation. In Cu-substituted C03O4, large size Cu formed in lithiation serves as a high conductivity backbone and cohesive support to accommodate Co nanoclusters thus preventing active materials from losing mechanical integrity or electrical contact to the current collector. Meanwhile, the size of Co (in lithiation) and CoO (in delithiation) remains small due to the existence of the Cu which is immiscible with Co.

[0057] The lithiation reactions show an initial intercalation of lithium, prior to the conversion reaction. ^[15] The intermediate phases formed during the non-equilibrium intercalation are not observed in delithiation and are likely not part of the ground-state equilibrium reactions. To explore the interplay among non-equilibrium, intercalation, and conversion reactions, we have developed a computational non-equilibrium phase search method to identify intermediate phases (data not shown). The calculated voltage profiles (data not shown) based on the lithiation/delithiation reactions (listed in Table 2) fit well to the experimental curves. The lithiation and delithiation processes proceed through non- equilibrium and equilibrium reaction paths, respectively. Such a difference in reaction path have a contribution to the experimentally-observed voltage hysteresis.

[0058] Conclusion

[0059] In conclusion, the substitution of a third metallic element (Cu) into binary oxides (C03O4) alters the fundamental processes of lithiation/delithiation. Metal Cu intrinsically formed in the first lithiation cycle remains partially stable as a metallic support on which L12O+C0/C0O redox products are anchored. The Cu-based network also provides a highly conductive pathway for electrons and enables Li-ion transport. Cu and Co are immiscible which prevents the aggregation of metal clusters, leaving enough space for L12O nucleation and growth. In addition, an unusual intimate orientation relationship between the Cu crystals and L12O crystal has been identified, and small Co/CoO clusters are found to remain active on the Cu/CuO/Li20 substrate in subsequent cycles. This "adaptive architecture" accommodates the formation of L12O in the discharge cycle and underpins the catalytic activity of L12O decomposition in the charging cycle. These ternary oxides may be extended and applied to other electrochemical storage technologies, such as Li-Li20/Li202 batteries. References

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[0061] The word "illustrative" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "illustrative" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Further, for the purposes of this disclosure and unless otherwise specified, "a" or "an" means "one or more".

[0062] The foregoing description of illustrative embodiments of the disclosure has been presented for purposes of illustration and of description. It is not intended to be exhaustive or to limit the disclosure to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the disclosure. The embodiments were chosen and described in order to explain the principles of the disclosure and as practical applications of the disclosure to enable one skilled in the art to utilize the disclosure in various embodiments and with various modifications as suited to the particular use contemplated. It is intended that the scope of the disclosure be defined by the claims appended hereto and their equivalents.