Components, their manufacturing methods and uses

Abstract

Provided is a composition comprising: (a) a main phase provided by a layered mixed metal oxide having a rock salt structure belonging to the R-3m space group; the layered mixed metal oxide comprising the following constituent elements: 45 to 55 atomic % of lithium; 20 to 55 atomic % of one or more transition metals selected from chromium, manganese, iron, nickel, cobalt and combinations thereof; and 0 to 25 atomic % of one or more additional dopant elements selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, copper, ruthenium, zinc, molybdenum, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium; wherein the atomic % is expressed as % of the total atoms of the layered oxide excluding oxygen; (b) a secondary phase provided by a metal oxide that does not have the crystal structure of the layered mixed metal oxide, the secondary phase comprising one or more of the transition metals included in the layered mixed metal oxide, the transition metal being selected from chromium, manganese, iron, nickel and cobalt. Also provided is a method for preparing the composition and an electrode and a unit cell, in particular a solid-state battery, comprising the composition. The rough morphology of the crystals confers an advantage compared to smoother crystals of similar chemical composition, especially in solid-state batteries.

Description

TECHNICAL FIELD

[0001] The present invention relates to a composition comprising: a first phase provided by a layered mixed metal oxide having a rock salt structure and a second phase provided by a metal oxide not having the crystal structure of the layered mixed metal oxide. In particular, the composition may comprise Co3O4 and a crystalline oxide of lithium and cobalt, optionally comprising one or more doping elements as described herein. The present invention also relates to a method for manufacturing the composition and its use, particularly as an electrode and for use in an electrochemical unit cell, particularly a lithium ion battery. BACKGROUND ART

[0002] A lithium ion battery is a rechargeable battery in which lithium ions (Li + ) move from the negative electrode to the positive electrode during discharge and move back during charging. Compared with metallic lithium used in non-rechargeable lithium ion batteries, lithium ion batteries use lithium intercalation compounds as one of the electrode materials. An electrolyte allowing ion movement and two electrodes are the constituent components of a lithium ion battery.

[0003] Typically, a lithium ion battery consists of at least three components. Two active electrodes (negative electrode and positive electrode) are separated by an electrolyte. Each of these components is formed as a thin film and deposited sequentially on a supporting substrate. Other components such as current collectors, interface modifiers, and encapsulants may also be provided. In manufacturing, the components may be deposited, for example, in the order of positive electrode current collector, positive electrode, electrolyte, negative electrode, negative electrode current collector, and encapsulant.

[0004] In the lithium ion example, the negative electrode and the positive electrode are capable of reversibly storing lithium. Other requirements for the negative electrode and positive electrode materials are high weight and volume storage capacities achievable with low mass and volume materials, while the number of lithium ions stored per unit should be as large as possible. The materials should also exhibit acceptable electronic and ionic conductivities so that ions and electrons can move through the electrodes during battery charging and discharging.

[0005] Many devices, particularly but not limited to handheld electronic devices, use lithium ion batteries based on layered mixed metal oxides having a rock salt structure belonging to the R-3m space group. These layered mixed metal oxides are of the Li x M’ y O2 type, where M’ is a transition metal selected from chromium, manganese, iron, nickel, cobalt, and combinations thereof. In this structure, alternating layers of lithium ions and transition metal ions occupy the octahedral sites of the cubic close-packed lattice of oxide ions. The diffusion of lithium ions preferably occurs along the lithium plane.

[0006] Examples of such mixed metal oxides include Li x Mn 1-y My O2 (where M is a transition metal selected from chromium, iron, nickel, cobalt, and combinations thereof) and lithium cobalt oxide (LiCoO2). LiCoO2 has a hexagonal layered crystal structure, where Li + ions are in the octahedral sites between the O-Co-O sheets. Li + diffusion occurs by vacancy hopping within the lithium plane.

[0007] In the art, it is known that the Li + mobility and thus the electrochemical properties of LiCoO2 will depend greatly on the crystal orientation. The literature describes optimized diffusion of Li for cathodes with orientations (101), (104), and (110). As described, for example, in Bates et al. cited below and Trask et al. cited below, this lithium cobalt oxide texture is more favorable than (003), in which the diffusion of Li ions is mainly limited to the grain boundary region. The (110) orientation has lithium planes arranged perpendicular to the substrate, which is advantageous because it allows easy access of lithium ions and relatively easy removal from the structure, thus enabling rapid Li + diffusion and high lithium capacity. Compared to the (110) orientation that still allows easy Li + removal and Li + insertion into the structure, the (101) and (104) orientations have lithium planes at a small angle. The (003) orientation consists of Li + planes arranged parallel to the substrate: this orientation is less favorable because lithium ions are less accessible and are effectively trapped in the structure.

[0008] Many methods for manufacturing lithium cobalt oxide are known in the art. For example, WO 2015 / 104539 describes a vapor deposition method for preparing a crystalline lithium-containing compound including lithium cobalt oxide. When the constituent elements react on a substrate to form a crystalline material, a lithium cobalt oxide film is formed on the substrate. The deposition described in WO2015 / 104539 is carried out in a physical vapor deposition (PVD) system that has been previously described in the literature (Guerin, S. and Hayden, B.E., Journal of Combinatorial Chemistry 2006, 8, 66 - 73).

[0009] Bates et al., J. Electrochem. Soc. 2000, 147, 59-70 describe the production of lithium cobalt oxide films by sputtering a LiCoO2 target in a mixture of argon and O2 at a rate of 100-1000 nm / min using an AC voltage (RF sputtering). Bates et al. reported that very thin lithium cobalt oxide films (thickness <0.5 μm) grown (RF sputtering) tend to prefer a (003) orientation to minimize surface energy, while thicker lithium cobalt oxide films (thickness <1 μm) form a preferred (101)-(104) orientation to minimize the volumetric strain energy generated during annealing. Bates et al. describe obtaining X-ray amorphous films that crystallize by annealing. Co2O3, Co3O4, Li 1.47 Co3O4 and Pt3O4 are mentioned, but no further: it is understood that these are byproducts of the annealing process, as the films are said to be X-ray amorphous before heating. Bates et al. also discuss the effect of substrate temperature. Deposition at high temperatures results in larger grains and increased void fraction (void fraction) (i.e., the fraction of empty space in a larger material, as a fraction of the void volume to the total volume). Bates et al. do not describe any attempts to introduce Co3O4 into the film or use it as a seed layer, and no analysis of the film composition is provided.

[0010] Ceder et al., J Alloys and Compounds 2006, 417, 304-310 describe the effect of substrate on the orientation of 0.3 to 0.5 μm thick lithium cobalt oxide films grown by pulsed laser deposition (PLD). Ceder et al. describe that a stainless steel (SS) substrate can provide a film with a rough surface and random orientation, while a silicon dioxide / silicon (SiO2 / Si; SOS) substrate can provide a relatively smooth surface with a preferred (003) orientation. The electrochemistry described therein shows that the rough film deposited on SS has a higher film utilization, while the smooth film deposited on SOS has better capacity retention and structural stability.

[0011] The reference states that all non-basal peaks in the X-ray diffraction pattern are attributed to the LiCoO2 film, and impurity peaks such as Co3O4 are not visible from the XRD diffraction pattern.

[0012] Yoon et al., J. Power Sources 2013, 226, 186-190 use substrate temperature and / or a Li2O buffer layer to control the orientation of a sputtered lithium cobalt oxide layer. At 400°C, films with a preferred orientation of (110) or (101) were obtained. In addition, it is described that the Li2O buffer layer suppresses the formation of a (003) orientation and promotes a (110) orientation.

[0013] Bouwman et al., Solid-state Ionics 2002 152, 181-188 describes the fabrication of lithium cobalt oxide films using RF sputtering and PLD. It is described that RF sputtering produces films with a (110) orientation, while films deposited by PLD have a (003) orientation. The (110)-oriented films utilize almost their entire theoretical capacity during cycling, while the (003) films have a poor reversible capacity. The electrochemical properties of the (003) films can be improved by introducing defects and irregularities into the films by heat treatment, using a stainless steel substrate, or lithographic patterning techniques. According to the method described by Bouwman et al., after RF sputtering or pulsed laser deposition (PLD) from a stoichiometric LiCoO2 target, the films are annealed in situ or ex situ at 600 °C. During the annealing process, the evaporation of volatile Li2O results in the formation of Co3O4 (estimated ~5% Co3O4).

[0014] However, the extended high-temperature treatment method taught in this document does not provide any control over the morphology of the lithium cobalt oxide films. Specifically, it is taught that when LiCoO2 is deposited by PLD on an annealed RF seed layer, the existing (110) orientation does not continue, but overgrows with a preferential (00l) orientation. However, the film structure is different from that of the film grown on a blank silicon substrate, as not all (00l) reflections are observed.

[0015] Bouwman et al., J. Electrochem. Soc. 2001, 148(4), A311-A317 further describes the formation of lithium cobalt oxide films on a substrate and then annealing. It describes that some changes (precipitation) of Co3O4 occur during the annealing process at 600 °C: at elevated temperatures, volatile Li2O is released, and as a result, LiCoO2 is transformed. This process seems to be promoted by a higher oxygen flow during the annealing treatment. The maximum value of the (110) diffraction peak of LiCoO2 decreases with the increase in Co3O4 reflections. Therefore, this document teaches that the annealing time should be kept as short as possible to prevent the loss of active material.

[0016] In addition, this document describes that, in order to check the consistency of the preferred lattice orientations of films fabricated by PLD and by RF sputtering relative to each other, the PLD film was grown on a RF sputtered seed layer of 0.1 mm LiCoO2 and annealed at 600 °C for 30 minutes. As a reference, PLD was carried out simultaneously on a blank silicon substrate. This reference sample showed a typical PLD film diffraction pattern, indicating the (00l) lattice plane orientation. The PLD film deposited on the seed layer, which showed only the (110) reflection before PLD, showed distinct (006) and (0012) reflections, but no (003) and (009) reflections at all. This result indicates that the film structure is not completely determined by the deposition technique.

[0017] US 2014 / 0272560A1 describes the fabrication of lithium cobalt oxide by changing the substrate surface to alter the orientation of the sputtered film, adding a seed layer of LiCoO2 on the substrate surface and / or depositing a multilayer structure by sputtering lithium cobalt oxide under different conditions (changing the gas).

[0018] Trask et al., J Power Sources 2017, 350, 56 - 64 describe changing the oxygen / argon ratio during sputtering to determine the crystallographic texture of 10 μm LCO films. Introducing only 4% O2 inhibits the formation of the (003) orientation.

[0019] Liao et al., J Power Sources 2004, 128, 263 - 269 describe the deposition of lithium cobalt oxide films at low oxygen partial pressure. Specifically, it describes that for films deposited at working pressures other than 20 mTorr (p O2 = 5 mTorr), in addition to the HT - LiCoO2 phase, a Co3O4 second phase is also obtained. However, in the higher oxygen partial pressure region, the formation of the Co3O4 phase is due to lithium deficiency in the film.

[0020] None of the prior art documents teach a crystalline lithium cobalt oxide composition having a local aggregation (concentration) of Co3O4, nor do they teach that the presence of such a concentration would enable the fabrication of a lithium cobalt oxide having a crystal orientation that has advantageous properties in a lithium ion battery, such as capacity and cycle life. Nor does any of the prior art teach a method for fabricating a crystalline lithium cobalt oxide composition so as to form a locally aggregated Co3O4 in a controlled manner so as to enable control of the crystal orientation of the lithium cobalt oxide. Summary of the Invention

[0021] According to a first aspect of the present invention, there is provided a composition comprising:

[0022] (a) Co3O4; and

[0023] (b) Crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide;

[0024] The crystalline oxide comprises the following constituent elements:

[0025] 45 to 55 atomic % of lithium;

[0026] 20 to 55 atomic % of cobalt; and

[0027] 0 to 25 atomic % of at least one additional dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, zinc, molybdenum, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium;

[0028] wherein the atomic % is expressed as % of the total atoms of the crystalline oxide excluding oxygen;

[0029] where 0.01% to 10% of the total mass (including oxygen) of the composition is Co3O4;

[0030] where 90% to 99.99% of the total mass (including oxygen) of the composition is crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide;

[0031] where the composition has a bottom surface and a top surface;

[0032] where the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide has a crystal structure characterized by at least one of the following parameters (a) to (c):

[0033] (a) at least one crystal orientation selected from (101), (104), (110) and (012);

[0034] (b) a Raman spectrum comprising: bands at 484 cm -1 , 593 cm -1 , and at least one band selected from 690 cm -1 , 526 cm -1 and 625 cm -1 (each of the bands ±25 cm -1 );

[0035] (c) at least one X-ray powder diffraction peak selected from 2θ (±0.2°) 37.4°, 39.1°, 45.3° and 66.4°.

[0036] According to a second aspect of the present invention, there is provided a method for preparing a crystalline composition according to the first aspect of the present invention, the method comprising the following steps:

[0037] Provide separate vapor sources for the respective constituent elements of the crystalline oxide, where the constituent elements include cobalt, lithium, oxygen, and optionally at least one dopant element selected from the following: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, ruthenium, copper, molybdenum, nickel, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium;

[0038] Heat the substrate to about 30 °C to about 900 °C;

[0039] Co-deposit the respective constituent elements onto the substrate, where the constituent elements react on the substrate to form a crystalline oxide comprising one or more of lithium, cobalt, and optionally a dopant element; and

[0040] Co-deposit cobalt and oxygen onto the substrate, where cobalt and oxygen react on the substrate to form Co3O4.

[0041] According to a third aspect of the present invention, there is provided an electrode comprising the component of the first or seventh aspect of the present invention. The electrode can be a positive electrode or a negative electrode. In one embodiment, the electrode is a positive electrode.

[0042] According to a fourth aspect of the present invention, there is provided an electrochemical unit cell comprising: an electrolyte; a negative electrode; and a positive electrode; wherein the negative electrode and / or the positive electrode comprises the electrode according to the third aspect of the present invention. In one embodiment, the positive electrode comprises the electrode according to the third aspect of the present invention.

[0043] According to a fifth aspect of the present invention, there is provided a method of manufacturing a solid-state electrochemical unit cell, which comprises using the method according to the second aspect of the present invention as a layer deposition unit cell electrode for the crystalline component according to the first aspect of the present invention.

[0044] According to a sixth aspect of the present invention, there is provided an electronic device comprising the electrochemical unit cell according to the fourth aspect of the present invention.

[0045] According to a seventh aspect of the present invention, there is provided a component comprising:

[0046] (a) A main phase provided by a layered mixed-metal oxide having a rock-salt structure belonging to the R-3m space group; the layered mixed-metal oxide comprises the following constituent elements:

[0047] 45 to 55 atomic % of lithium;

[0048] 20 to 55 atomic % of one or more transition metals selected from chromium, manganese, iron, nickel, cobalt, and combinations thereof; and

[0049] 0 to 25 atomic % of one or more additional dopant elements selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, copper, ruthenium, zinc, molybdenum, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium;

[0050] Wherein the atomic % is expressed as % of the total atoms of the layered oxide excluding oxygen;

[0051] (b) A secondary phase provided by a metal oxide that does not have the crystal structure of the layered mixed metal oxide, the secondary phase including one or more of the transition metals contained in the layered mixed metal oxide, the transition metal being selected from chromium, manganese, iron, nickel, and cobalt;

[0052] Wherein the primary phase accounts for 90% to 99.5% of the total mass of the composition, and the secondary phase accounts for 0.5% to 10% of the total mass of the composition.

[0053] Effectively, the secondary phase can be considered to disrupt the crystal structure of the layered mixed metal oxide. In certain embodiments, the secondary phase can be amorphous. In other embodiments, the secondary phase can be crystalline but have a crystal structure different from that of the layered mixed metal oxide, for example, belonging to a different space group. In certain embodiments, the secondary phase can have a crystal structure belonging to the Fd-3m space group (this is the case when the secondary phase is provided by, for example, Co3O4).

[0054] According to an eighth aspect, the present invention can provide a method for preparing a composition according to the seventh aspect of the present invention, the method comprising the following steps:

[0055] Providing separate vapor sources of the constituent elements of the composition, wherein the vapor sources at least include:

[0056] · A lithium source,

[0057] · A transition metal source, the transition metal being selected from chromium, manganese, iron, nickel, and cobalt,

[0058] · An oxygen source, and

[0059] · Optionally, a source of at least one dopant element selected from the following: magnesium, calcium, strontium, titanium, zirconium, vanadium, copper, ruthenium, zinc, molybdenum, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium;

[0060] Heating the substrate to 30 °C to about 900 °C;

[0061] Delivering a stream (flux) of each of the constituent elements to the substrate, wherein the constituent elements react on the substrate to form a first phase, the first phase being provided by a layered mixed metal oxide having a rock salt structure belonging to the R-3m space group; and

[0062] Delivering a stream of at least the transition metal and oxygen to the substrate, wherein the transition metal and oxygen react on the substrate to form a second phase, the second phase being provided by a metal oxide that does not have the crystal structure of the first phase.

[0063] According to a ninth aspect, the present invention may provide a method for preparing a composition according to the seventh aspect of the present invention, wherein the method is a sputtering deposition method, which comprises:

[0064] providing a sputtering target, the sputtering target comprising a mixed metal oxide, the mixed metal oxide comprising

[0065] lithium

[0066] one or more transition metals selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof; and optionally one or more dopant elements selected from the group consisting of magnesium, calcium, strontium, titanium, zirconium, vanadium, copper, ruthenium, zinc, molybdenum, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium;

[0067] providing an additional sputtering target, the additional sputtering target comprising a metal oxide phase, the metal oxide phase comprising one or more of the transition metals contained in the first sputtering target, the transition metals being selected from chromium, manganese, iron, nickel, and cobalt;

[0068] sputtering the sputtering target and the additional sputtering target to produce a composition comprising:

[0069] a first phase provided by a layered mixed metal oxide of lithium and one or more of the transition metals, the layered mixed metal oxide being optionally doped with at least one of the dopant elements and having a rock salt structure belonging to the R-3m space group; and

[0070] and a second phase provided by a metal oxide that does not have the crystal structure of the first phase, the second phase comprising one or more of the transition metals contained in the layered mixed metal oxide, the transition metals being selected from chromium, manganese, iron, nickel, and cobalt.

[0071] According to a tenth aspect of the present invention, there is provided a method for manufacturing a solid-state electrochemical unit cell, comprising using the method according to the eighth or ninth aspect of the present invention to deposit an electrode of the unit cell as a composition according to the seventh aspect of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] Figure 1 is a schematic diagram of an exemplary apparatus suitable for implementing the method according to an embodiment of the present invention.

[0073] Figure 2 shows the number of cycles to reach 80% of the discharge capacity (5th cycle) when cycling at a rate of 1C at a temperature of 25 °C at 100% depth of discharge (DoD) versus the percentage of lithium in lithium cobalt oxide measured by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

[0074] Figure 3Shows the percentage of lithium in lithium cobalt oxide when measuring the Li:Co ratio by LA-ICP-MS with the utilisation number (capacity normalised by area and thickness) at a temperature of 25 °C.

[0075] Figure 4 Shows the Raman spectrum taken on top of a film (such as film 1 described in the examples) containing a composition according to an aspect of the present invention.

[0076] Figure 5 Shows the X-ray diffraction patterns of films 1-3 and film 4 (not according to the present invention) containing a composition according to an aspect of the present invention.

[0077] Figure 6 Shows the cross-sectional Raman spectrum of film 4 (not according to the present invention).

[0078] Figure 7 Shows the scanning electron microscopy (SEM) cross-sectional view and top view of the LCO layer of film 4 (not according to the present invention).

[0079] Figure 8 Shows the average percentage of lithium relative to cobalt in films 1-3 according to an aspect of the present invention and the top view SEM and cross-sectional Raman spectrum.

[0080] Figure 9 Shows the SEM cross-sectional view and top view of the LCO layer of film 1 according to an aspect of the present invention.

[0081] Figure 10 Shows the SEM top view and cross-sectional Raman spectrum of film 5 (according to an aspect of the present invention), which contains a Co3O4 layer in the middle of the film.

[0082] Figure 11 Shows the cross-section of a solid-state battery containing LiCoO2 (film 1) according to an aspect of the present invention.

[0083] Figure 12 Shows the SEMs of films 1 to 3 (according to an aspect of the present invention) and film 4 (not according to the present invention), the data of which are provided in Tables 2 and 3.

[0084] Advantages and surprising findings

[0085] According to aspects of the present invention, crystalline lithium cobalt oxide is grown by various methods disclosed herein, particularly but not exclusively physical vapor deposition (PVD). The lithium cobalt oxide film can be used in an electrode, for example as a film on an inert substrate, and combined with an electrolyte such as a lithium phosphorus oxynitride (LiPON) solid electrolyte for an electrochemical unit cell, particularly a solid-state battery.

[0086] Generally, a layered mixed-metal oxide can be grown, for example by PVD, which layered mixed-metal oxide contains lithium and one or more transition metals selected from chromium, manganese, iron, nickel, cobalt, and combinations thereof and has a layered rock salt structure belonging to the R-3m space group. The resulting film can be used in an electrode, for example as a film on an inert substrate, and optionally combined with an electrolyte such as a lithium phosphorus oxynitride (LiPON) solid electrolyte for an electrochemical unit cell, particularly a solid-state battery. Such layered mixed-metal oxides include, for example, Li x Mn 1-y M y O2 (where M is a transition metal selected from chromium, iron, nickel, cobalt, and combinations thereof) in addition to lithium cobalt oxide.

[0087] Conventionally, it has been considered desirable to maximize the amount of the electrochemically active material (such as lithium cobalt oxide or Li x Mn 1-y M y O2) in the electrodes of a battery, and thus it is preferred to avoid the presence of other phases that do not contribute to the overall battery capacity.

[0088] For example, cobalt oxide (Co3O4) is electrochemically inactive and is considered an impurity in the LiCoO2 composition. See, for example, Jo et al., 2009 J. Electrochem. Soc. 156(6) A430 - A434; Tintignac et al., 2012 Electrochimica Acta 60 121 - 129; Antaya et al., J. Electrochem Soc Vol. 140 No. 3 1993, each incorporated herein by reference in its entirety. The capacity of a battery having a LiCoO2 positive electrode is defined by the amount of the LiCoO2 material. Thus, adding Co3O4 to the LiCoO2 material comes at the expense of the overall battery capacity. In terms of energy density (e.g., weight energy density, which is defined as the capacity in Wh / kg by weight), any inclusion of Co3O4 contributes to the weight but does not provide any additional capacity. Thus, it is counterintuitive to deliberately add Co3O4 to the lithium oxide composition.

[0089] However, the present inventors have surprisingly found that the methods disclosed herein allow the introduction of local aggregations of Co3O4 into the crystal structure of a crystalline lithium cobalt oxide composition in a controlled manner, thereby allowing the morphology of the composition to be controlled in a more precise manner than previously possible in the art.

[0090] For example, and as discussed in more detail below, when the method of manufacturing a crystalline lithium cobalt oxide composition is a physical vapor deposition (PVD) method, it has surprisingly been found that local aggregations of Co3O4 can be introduced into the crystal structure of the composition (e.g., by varying the cobalt flow rate relative to the lithium flow rate, varying the partial pressure of the supplied gas, or cutting off the lithium supply during deposition), thereby enabling control of the morphology of the crystalline lithium cobalt oxide composition. The control of one atomic flow relative to another during deposition and the advantages conferred thereby in terms of the morphology of the composition have not previously been disclosed in the art.

[0091] Similarly, during the deposition of other layered mixed metal oxides (such as Li x Mn 1-y M y O2) by a physical vapor deposition method involving the deposition of constituent elements, it is contemplated that variations in the relative flow rates of the constituent elements (e.g., by varying the manganese flow rate relative to the lithium flow rate, varying the partial pressure of the supplied gas, or cutting off the lithium supply during deposition) will result in the formation of a unique (different) lithium-deficient phase having a crystal structure different from that of the layered oxide.

[0092] As will be apparent to those skilled in the art, the presence of such a unique phase will allow the morphology of the layered oxide to be altered (modified), which is consistent with the effects observed when Co3O4 is introduced into lithium cobalt oxide.

[0093] The present inventors have also surprisingly found that a crystalline lithium cobalt oxide composition having the crystal orientation described herein (which is typically less uniform and rougher in nature) exhibits better electrochemical behavior in both capacity and cycle life (particularly but not exclusively, when cycling at 100% depth of discharge and / or when cycling at a temperature of 25 °C) in a solid-state battery compared to a film of the same composition having a flat and smooth crystal orientation. Although the prior art may teach the application of films of lithium cobalt oxide compositions having a similar morphology to batteries using liquid electrolytes, the application of lithium cobalt oxide films having a specific morphology in batteries using solid electrolytes and the improved performance (cycle life, capacity, adhesion to the underlying layer, and control of stress, fewer cracks) when used with solid electrolytes have not previously been disclosed in the art.

[0094] In particular, contrary to what is disclosed in WO 2015 / 104539 which teaches the formation of lithium cobalt oxide with a smooth surface morphology, it has surprisingly been found that a less uniform and rougher morphology of the lithium cobalt oxide component exhibits better electrochemical behavior in terms of both capacity and cycle life, improved adhesion to the current collector and / or electrolyte layer, and less cracking in a solid-state battery as compared to a film of the same composition with a flat and smooth crystal orientation.

[0095] There are additional advantages to using the method of the present invention to tune the film morphology and control the roughness of the film surface. In a solid-state battery, it can be advantageous to introduce sufficient disorder in the film to improve Li transport properties (increased capacity and cycle life), while keeping the film smooth enough to allow only a thin solid electrolyte layer to cover the lithium cobalt oxide film. The method of the present invention also makes the morphology of the film less dependent on the substrate used. In addition, the method of the present invention can allow the growth of lithium cobalt oxide with the desired orientation at a lower temperature. Finally, depositing Co3O4 as a seed layer means that no additional source is required during the deposition process.

[0096] As will be apparent to those skilled in the art, the presence of the unique lithium-deficient phase will have a similar effect in other layered oxide materials having the same crystal structure as lithium cobalt oxide. Detailed Description

[0097] Definitions

[0098] As used herein, a range of values stated as "X to Y" or "between X and Y" includes the end values X and Y.

[0099] As used herein, the term "battery" is considered synonymous with the term "electrochemical cell" and is a device capable of generating electrical energy from a chemical reaction or facilitating a chemical reaction by introducing electrical energy.

[0100] As used herein, the term "crystalline" refers to a solid having a regular internal arrangement of atoms, ions, or molecules characteristic of a crystal, i.e., a solid having long-range order in its lattice.

[0101] As used herein, the term "layered oxide" generally refers to a layered mixed-metal oxide having a rock-salt structure belonging to the R-3m space group, which oxide includes lithium and one or more transition metals selected from chromium, manganese, iron, nickel, cobalt, and combinations thereof.

[0102] As used herein, the term "crystalline oxide" refers to a crystalline lithium cobalt oxide or a crystalline doped lithium cobalt oxide component (as opposed to the entire composition which also includes Co3O4) of the components described herein in connection with certain embodiments of the present invention. In one embodiment, the term "crystalline oxide" refers to crystalline lithium cobalt oxide, i.e., it contains only lithium, cobalt, and oxygen. In another embodiment, the term "crystalline oxide" refers to a doped crystalline doped lithium cobalt oxide, i.e., in addition to lithium, cobalt, and oxygen, it further contains at least one dopant element (selected from those listed herein).

[0103] Composition

[0104] In certain embodiments, the present invention provides a composition comprising Co3O4 and a crystalline oxide of lithium and cobalt (as defined herein) or a crystalline doped lithium cobalt oxide (as defined herein). In one embodiment, the present invention provides a composition consisting essentially of Co3O4 and a crystalline oxide of lithium and cobalt. In one embodiment, the present invention provides a composition consisting of Co3O4 and a crystalline oxide of lithium and cobalt.

[0105] In the compositions of the present invention, in one embodiment, the composition has a solid state structure comprising both Co3O4 and the crystalline oxide. In one embodiment, both Co3O4 and the crystalline oxide are introduced into the solid state structure of the composition. In one embodiment, Co3O4 is present on the surface of the solid state structure of the composition. In another embodiment, Co3O4 is introduced into the solid state structure of the composition as a layer 1 - 50 nm thick. In another embodiment, Co3O4 is introduced into the solid state structure of the composition as a seed layer.

[0106] The compositions of certain embodiments of the present invention include a crystalline oxide of lithium and cobalt (as defined herein) or a crystalline doped lithium cobalt oxide (as defined herein). In one embodiment, at least 90 wt% of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 95 wt% of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 97 wt% of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 98 wt% of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 99 wt% of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 99.5 wt% of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 99.7 wt% of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline.

[0107] In one embodiment, at least 99.8 mass % of the total mass of lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 99.9 mass % of the total mass of lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 99.95 mass % of the total mass of lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, 100 mass % of the total mass of lithium cobalt oxide or doped lithium cobalt oxide is crystalline.

[0108] As is known to those skilled in the art, crystalline lithium cobalt oxide can include a high temperature phase, a low temperature phase, or a mixture thereof. As described by Gummow et al., Material Research Bulletin, 1992, 27, 327 - 337, the high temperature phase of LiCoO2 synthesized at a higher temperature (typically 700 °C or higher, preferably 800 to 1000 °C, more preferably about 900 °C) contains Li + and Co 3+ ions in discontinuous layers between planes of closely packed oxygen ions. In contrast, the low temperature phase of LiCoO2 synthesized at a lower temperature (typically 500 °C or lower, preferably 300 to 500 °C, more preferably about 350 to 450 °C, most preferably about 400 °C) has about 6% cobalt within the lithium layer.

[0109] In one embodiment, the crystalline lithium cobalt oxide contains at least 40% of the high temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0110] In one embodiment, the crystalline lithium cobalt oxide contains at least 50% of the high temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0111] In one embodiment, the crystalline lithium cobalt oxide contains at least 60% of the high temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0112] In one embodiment, the crystalline lithium cobalt oxide contains at least 70% of the high temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0113] In one embodiment, the crystalline lithium cobalt oxide contains at least 80% of the high temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0114] In one embodiment, the crystalline lithium cobalt oxide contains at least 85% of the high temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0115] In one embodiment, the crystalline lithium cobalt oxide contains at least 90% of the high temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0116] In one embodiment, the crystalline lithium cobalt oxide comprises at least 95% of the high-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0117] In one embodiment, the crystalline lithium cobalt oxide comprises at least 97% of the high-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0118] In one embodiment, the crystalline lithium cobalt oxide comprises at least 98% of the high-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0119] In one embodiment, the crystalline lithium cobalt oxide comprises at least 99% of the high-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0120] In one embodiment, the crystalline lithium cobalt oxide comprises at least 99.5% of the high-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0121] In one embodiment, the crystalline lithium cobalt oxide comprises at least 99.7% of the high-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0122] In one embodiment, the crystalline lithium cobalt oxide comprises at least 99.9% of the high-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0123] In one embodiment, the crystalline lithium cobalt oxide comprises 100% of the high-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0124] In one embodiment, the crystalline lithium cobalt oxide comprises up to 60% of the low-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0125] In one embodiment, the crystalline lithium cobalt oxide comprises up to 50% of the low-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0126] In one embodiment, the crystalline lithium cobalt oxide comprises up to 40% of the low-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0127] In one embodiment, the crystalline lithium cobalt oxide comprises up to 30% of the low-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0128] In one embodiment, the crystalline lithium cobalt oxide comprises up to 20% of the low-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0129] In one embodiment, the crystalline lithium cobalt oxide comprises up to 15% of the low-temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0130] In one embodiment, the crystalline lithium cobalt oxide comprises up to 10% of a low temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0131] In one embodiment, the crystalline lithium cobalt oxide comprises up to 5% of a low temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0132] In one embodiment, the crystalline lithium cobalt oxide comprises up to 3% of a low temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0133] In one embodiment, the crystalline lithium cobalt oxide comprises up to 2% of a low temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0134] In one embodiment, the crystalline lithium cobalt oxide comprises up to 1% of a low temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0135] In one embodiment, the crystalline lithium cobalt oxide comprises up to 0.5% of a low temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0136] In one embodiment, the crystalline lithium cobalt oxide comprises up to 0.3% of a low temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0137] In one embodiment, the crystalline lithium cobalt oxide comprises up to 0.1% of a low temperature phase, based on the total mass of the crystalline lithium cobalt oxide.

[0138] In one embodiment, the crystalline lithium cobalt oxide comprises 45 to 90% of a high temperature phase and 10% to 55% of a low temperature phase, based on the total mass of the crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide comprises 60 to 95% of a high temperature phase and 5% to 40% of a low temperature phase, based on the total mass of the crystalline lithium cobalt oxide. The relative amounts of the low and high temperature phases of the crystalline lithium cobalt oxide can be estimated using a Raman fitting technique similar to that described by Tintignac in Electrochimica Acta, 2012, 60, 121 - 129.

[0139] Typically, most of the cobalt present in the composition is in the +3 oxidation state, such that the stoichiometry of the lithium cobalt oxide is generally represented as LiCoO2. In certain embodiments, the lithium cobalt oxide is lithium deficient, such that the stoichiometry of the lithium cobalt oxide is Li x xCoO2, where 0 < x < 1. In certain embodiments, the lithium cobalt oxide comprises a greater proportion of lithium and / or at least some of the cobalt present in the composition is in the +2 oxidation state, such that the stoichiometry of the lithium cobalt oxide is Li x xCoO2, where 1 < x ≤ 2.

[0140] The crystalline oxide according to certain embodiments of the present invention comprises 45 to 55 atomic % of lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 46 to 54 atomic % of lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47 to 53 atomic % of lithium, expressed as a percentage of the total atoms in the composition excluding oxygen. In one embodiment, the crystalline oxide comprises 47.0 to 53.0 atomic % of lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.1 to 52.0 atomic % of lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.2 to 51.0 atomic % of lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.3 to 50.0 atomic % of lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.4 to 49.5 atomic % of lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.5 to 49.1 atomic % of lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.

[0141] The crystalline oxide according to certain embodiments of the present invention comprises 20 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 22.5 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 25 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the composition excluding oxygen. In one embodiment, the crystalline oxide comprises 27.5 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the composition comprises 30 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the composition comprises 32.5 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the composition comprises 35 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 37.5 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 40 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the composition comprises 42.5 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 45 to 55 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 46 to 54 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 46.5 to 53.5 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.0 to 53 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 49.0 to 52.8 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 50.0 to 52.7 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 50.5 to 52.6 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 50.5 to 52.5 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 50.9 to 52.5 atomic % of cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.

[0142] In addition to lithium and cobalt, the crystalline oxide may further include dopant elements. As used herein, the term "doped crystalline oxide" refers to a crystalline oxide of lithium and cobalt, in which other elements (hereinafter referred to as "dopant elements") may replace lithium, cobalt, or oxygen in the crystal structure. In one embodiment, such a dopant element replaces lithium. In one embodiment, such an element replaces cobalt. In one embodiment, such a dopant element replaces lithium and cobalt. In one embodiment, such a dopant element replaces oxygen.

[0143] Examples of dopant elements that may replace lithium include sodium and potassium. Examples of dopant elements that may replace oxygen include sulfur and selenium.

[0144] In one embodiment, the dopant element that replaces cobalt is divalent (in other words, in the +2 oxidation state). In one embodiment, the dopant element that replaces cobalt is trivalent (in other words, in the +3 oxidation state). In one embodiment, the dopant element that replaces cobalt is tetravalent (in other words, in the +4 oxidation state).

[0145] Examples of dopant elements that may replace cobalt include alkaline earth metals (such as magnesium, calcium, and strontium), transition metals (such as titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, and zinc), p-block elements (such as boron, aluminum, gallium, tin, lead, and bismuth), and lanthanide elements (such as lanthanum, cerium, gadolinium, and europium).

[0146] Typically, if present, the dopant element substituting for cobalt can be present in an amount up to 25%, such as up to 20%, such as up to 15%, such as up to 12.5%, such as up to 10%, such as up to 7.5%, such as up to 5%, such as up to 4%, such as up to 3%, such as up to 2%, such as up to 1.5%, such as up to 1%, such as up to 0.9%, such as up to 0.8%, such as up to 0.7%, such as up to 0.6%, such as up to 0.5%, such as up to 0.4%, such as up to 0.3%, such as up to 0.2%, such as up to 0.15%, such as up to 0.1%, such as up to 0.09%, such as up to 0.08%, such as up to 0.07%, such as up to 0.06%, such as up to 0.05%, such as up to 0.04%, such as up to 0.03%, such as up to 0.02%, such as up to 0.01%, such as up to 0.009%, such as up to 0.008%, such as up to 0.007%, such as up to 0.006%, such as up to 0.005%, such as up to 0.004%, such as up to 0.003%, such as up to 0.002%, such as up to 0.001%, expressed as a percentage of the total atoms other than oxygen in the doped crystalline oxide.

[0147] In one embodiment, the doped crystalline oxide comprises from 0 to 25 atomic % of at least one dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the amount being expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen. In one embodiment, the doped crystalline oxide comprises from 0 to 20 atomic % of at least one dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the amount being expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen. In one embodiment, the doped crystalline oxide comprises from 0 to 15 atomic % of at least one dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the amount being expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen. In one embodiment, the doped crystalline oxide comprises from 0 to 10 atomic % of at least one dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the amount being expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen. In one embodiment, the doped crystalline oxide comprises from 0 to 5 atomic % of at least one dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the amount being expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen. In one embodiment, the doped crystalline oxide comprises from 0 to 2.5 atomic % of at least one dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the amount being expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen. In one embodiment, the doped crystalline oxide comprises from 0 to 2 atomic % of at least one element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the amount being expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen. In one embodiment, the doped crystalline oxide comprises from 0 to 1.5 atomic % of at least one element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the amount being expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.In one embodiment, the doped crystalline oxide comprises from 0 to 1 atomic % of at least one element selected from the group consisting of magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the amount being expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen. In one embodiment, the doped crystalline oxide comprises from 0 to 0.5 atomic % of at least one element selected from the group consisting of magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the amount being expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.

[0148] In one embodiment, there is provided a composition of the present invention, wherein the doped crystalline lithium cobalt oxide component has: 45 - 55 atomic % of lithium; 40 to 55 atomic % of cobalt; and 0 to 5 atomic % of at least one dopant element selected from the group consisting of magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium; the amount being expressed as % of the total atoms in the doped crystalline lithium cobalt oxide excluding oxygen.

[0149] In one embodiment, there is provided a composition of the present invention, wherein the doped crystalline lithium cobalt oxide component has: 45 - 55 atomic % of lithium; 42.5 to 55 atomic % of cobalt; and 0 to 2.5 atomic % of at least one dopant element selected from the group consisting of magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium; the amount being expressed as % of the total atoms in the doped crystalline lithium cobalt oxide excluding oxygen.

[0150] In one embodiment, there is provided a composition of the present invention, wherein the crystalline lithium cobalt oxide component consists of: 45 - 55 atomic % of lithium and 45 to 55 atomic % of cobalt; the amount being expressed as % of the total atoms in the crystalline oxide excluding oxygen.

[0151] In one embodiment, there is provided a composition of the present invention, wherein the crystalline lithium cobalt oxide component consists of: 47.0 - 53.0 atomic % of lithium and 47.0 to 53.0 atomic % of cobalt; the amount being expressed as % of the total atoms in the crystalline oxide excluding oxygen.

[0152] In one embodiment, there is provided a composition of the present invention, wherein the crystalline lithium cobalt oxide component consists of: 47.5 - 49.1 atomic % of lithium and 50.9 to 52.5 atomic % of cobalt; the amount being expressed as % of the total atoms in the crystalline oxide excluding oxygen.

[0153] In addition to the lithium, cobalt, and (optionally) dopant elements listed above, the crystalline components of embodiments of the present invention further include oxygen, which provides a source of negative ions in the crystalline components. It is understood that the components include sufficient oxygen (as oxygen ions O 2- ) to ensure that they are electrically neutral, and the exact amount of oxygen depends on the atomic percentages and oxidation states of the other elements present in the components.

[0154] A distinguishing feature of the components of embodiments of the present invention is that the crystalline structure of the components includes local aggregations of Co3O4. Surprisingly, the inventors have found that introducing local aggregations of Co3O4 into the crystal structure of a crystalline lithium cobalt oxide component allows for more precise control of the morphology of the components than was previously possible in the art. Without wishing to be bound by theory, it is believed that the locally aggregated Co3O4 can act as a seed layer for LiCoO2 microcrystals. Additionally, without wishing to be bound by theory, it is believed that the locally aggregated Co3O4 creates defects in the crystal structure of the lithium cobalt oxide, which promotes the preferred crystal orientations described herein, resulting in a rough or irregular morphology of the crystals as described herein (including, for example, large plate-like grains), and exhibits improved electrochemical properties compared to lithium cobalt oxide components known in the art.

[0155] When the component is in the form of a film, the film typically exhibits large microcrystal sizes (grain sizes) between 0.2 and 3.0 μm, preferably between 0.3 and 2.5 μm. In one embodiment, the film exhibits large microcrystal sizes between 0.7 and 2.0 μm. In one embodiment, the film exhibits large microcrystal sizes between 0.5 and 1.0 μm. In one embodiment, the film exhibits large microcrystal sizes between 0.4 and 0.9 μm. Typically, the microcrystal sizes are measured manually and / or using a scanning electron microscope (SEM) with suitable measurement tools and suitable hardware and / or software.

[0156] Generally, the film includes microcrystals having a maximum size in the plane of the film that is at least 0.2 μm, preferably at least 0.3 μm, and in certain embodiments at least 0.4 μm. Typically, the film includes microcrystals that have a maximum size in the plane of the film up to 3 μm, and in some cases up to 2 μm.

[0157] When the component is in the form of a film, the film typically exhibits an average area of larger microcrystals between 0.1 and 2 μm 2 and preferably between 0.2 and 1 μm 2 . In one embodiment, the film exhibits an average area of larger microcrystals of 0.8 μm 2 . In one embodiment, the film exhibits an average area of larger microcrystals of 0.3 μm 2The average area of the larger microcrystals. Typically, a scanning electron microscope (SEM) with suitable measurement tools and suitable hardware and / or software is used to measure the average area of the larger microcrystals.

[0158] When the composition is in the form of a film, typically, 1 to 100%, preferably 3 to 85% of the surface area of the film is covered by the larger microcrystals. In one embodiment, 70 to 90%, such as 75 to 85%, such as 79% of the surface area of the film is covered by the larger microcrystals. In one embodiment, 15 to 35%, such as 20 to 25%, such as 22% of the surface area of the film is covered by the larger microcrystals.

[0159] In one embodiment, 1 - 10%, preferably 3 - 6%, such as 4.5 - 5.4%, such as 5% of the surface area of the film is covered by the larger microcrystals. Typically, a scanning electron microscope (SEM) is used, the number and area of the larger microcrystals within the image area are used, and appropriate hardware and / or software are used to measure the proportion of the film covered by the larger microcrystals.

[0160] The term "microcrystal" is used herein to denote a region of a film in which the orientation of the lattice remains substantially constant. Thus, the boundary between adjacent microcrystals is typically indicated by a change in lattice orientation. A single microcrystal may include a plurality of sub - microcrystals, all having a lattice with substantially the same orientation. Typically, individual sub - microcrystals grow by seeding on adjacent sub - microcrystals such that the lattice orientations of the two sub - microcrystals are substantially aligned. In some cases, microcrystals as defined herein may be referred to in the art as "grains".

[0161] Techniques such as stylus profilometry can be used to measure the roughness of the surface to determine the average roughness R a , where the average roughness R a is the arithmetic mean of the filtered roughness profile (curve) determined by the deviation from the center line within the evaluation length. When the composition is in the form of a film, typically, the average surface roughness (R a ) of the film is between 10 and 200 nm, such as 20 to 150 nm, such as 40 to 120 nm. The average surface roughness (R a ) of the film can be at least 10 nm, in some cases at least 30 nm, in some cases at least 50 nm. In some cases, the average surface roughness (R a ) of the film can be up to 250 nm. In contrast, a film with a smooth surface having predominantly (003) - oriented crystals (which is generally undesirable for the present invention) has an average surface roughness R a. Typically, the average roughness is measured using a stylus profilometer, and the number R a represents the average roughness (average deviation from the mean). Typically, the average R a is calculated from three different measurements taken a few millimeters apart, and each scan is typically 2 mm long.

[0162] In embodiments where the composition takes the form of a film, the locally aggregated Co3O4 can promote the presence of the desired structure of the resulting crystalline film.

[0163] In the composition of an embodiment of the present invention, 0.01% to 10% of the total mass of the composition is Co3O4. In one embodiment, 0.01% to 5% of the total mass of the composition is Co3O4. In one embodiment, 5% to 7.5% of the total mass of the composition is Co3O4. In one embodiment, 7.5% to 10% of the total mass of the composition is Co3O4. In one embodiment, 0.01% to 0.05% of the total mass of the composition is Co3O4. In one embodiment, 0.05% to 0.1% of the total mass of the composition is Co3O4. In one embodiment, 0.1% to 0.5% of the total mass of the composition is Co3O4. In one embodiment, 0.5% to 1.0% of the total mass of the composition is Co3O4. In one embodiment, 1.0% to 1.5% of the total mass of the composition is Co3O4. In one embodiment, 1.5% to 2.0% of the total mass of the composition is Co3O4. In one embodiment, 2.0% to 3.0% of the total mass of the composition is Co3O4. In one embodiment, 3.0% to 4.0% of the total mass of the composition is Co3O4. In one embodiment, 4.0% to 5.0% of the total mass of the composition is Co3O4. The total mass represented includes all elements containing oxygen.

[0164] In one embodiment, with respect to the distribution of Co3O4 in the composition, the composition is non-uniform.

[0165] Typically, the composition is formed in the form of a film layer, especially in the form of a film layer on a substrate (as defined in more detail below). In one embodiment, the composition is a thin film layer including a top surface, a bottom surface, and a height of 1 - 50 μm. In one embodiment, the height of the layer is 1 to 30 μm. In one embodiment, the height of the layer is 2 to 20 μm. In one embodiment, the height of the layer is 3 to 12 μm. In one embodiment, the height of the layer is 5 to 10 μm. In one embodiment, the height of the layer is 6 to 7 μm.

[0166] In one embodiment, the crystalline oxide thin film layer includes a seed layer of Co3O4. In one embodiment, the seed layer is within 75% of the height from the bottom surface. In one embodiment, the seed layer is within 50% of the height from the bottom surface. In one embodiment, the seed layer is within 25% of the height from the bottom surface. In one embodiment, the seed layer is within 10% of the height from the bottom surface. In one embodiment, the seed layer is within 5% of the height from the bottom surface. In one embodiment, the seed layer is within 2.5% of the height from the bottom surface. In one embodiment, the seed layer constitutes the bottom surface of the thin film layer.

[0167] In one embodiment, the seed layer is 0.1 - 100 nm thick. In one embodiment, the seed layer is 0.1 - 50 nm thick. In one embodiment, the seed layer is 0.1 - 25 nm thick. In one embodiment, the seed layer is 0.1 - 10 nm thick. In one embodiment, the seed layer is 1 - 50 nm thick. In one embodiment, the seed layer is 1 - 25 nm thick. In one embodiment, the seed layer is 1 - 10 nm thick. In one embodiment, the seed layer is 1 - 5 nm thick.

[0168] In one embodiment, the local aggregation of Co3O4 can be defined according to the thickness of the effective layer of Co3O4. In this specification, the "effective layer" means that all Co3O4 existing in the form of local aggregation is assumed to be uniformly distributed throughout the bulk of the composition as a layer. Compared with the thickness of the crystalline oxide component of the composition, the thickness of the effective layer can be used as an estimate of the amount of Co3O4 existing in the form of local aggregation.

[0169] In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is 1 to 50 μm and the thickness of the Co3O4 effective layer is 0.1 to 5 μm. In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is 2 to 20 μm and the thickness of the Co3O4 effective layer is 0.2 to 500 μm.

[0170] Another distinguishing feature of the lithium cobalt oxide composition of the embodiments of the present invention is its crystal structure. As described above, the inventors have surprisingly found that, compared with the crystalline lithium cobalt oxide used in solid-state batteries according to the prior art, the crystalline lithium cobalt oxide composition having the morphology described herein is typically less uniform and rougher in nature, and exhibits more favorable electrochemical behavior in such solid-state batteries in terms of both capacity and cycle life compared to a film of the same composition having a flat and smooth crystal orientation.

[0171] In one embodiment, the crystal structure of a lithium cobalt oxide composition or a doped lithium cobalt oxide composition can be defined according to the Miller indices of the lattice planes. As is known to those skilled in the art, the Miller indices form a labeling system for planes in a crystal (Bravais) lattice in crystallography. In particular, a family of lattice planes is determined by three integers h, k, and l, i.e., the Miller indices. They are written as (hkl) and represent the family of planes that are orthogonal to hb1 + kb2 + lb3, where b i is the basis of the reciprocal lattice vectors. The integers are usually written in lowest terms, i.e., their greatest common divisor should be 1.

[0172] In one embodiment, at least a portion of the crystal structure of a crystalline oxide, i.e., a crystalline lithium cobalt oxide composition, a crystalline doped lithium cobalt oxide, has an orientation with Miller indices selected from: (101), (104), (110), and (012) or any mixture thereof. In one embodiment, at least a portion of the crystal structure of a crystalline oxide composition has an orientation with Miller indices selected from: (101), (104), or both.

[0173] In the compositions of the embodiments of the present invention, the crystal orientation of the crystal structure of a crystalline oxide can be defined by reference to a plane parallel to the bottom surface of the composition. Thus, in one embodiment, at least a portion of the crystal structure of a crystalline oxide has a crystal orientation selected from: (101), (104), (110), and (012) or any mixture thereof with respect to a plane parallel to the bottom surface. In one embodiment, at least a portion of the crystal structure of a crystalline oxide composition has an orientation selected from: (101), (104), or both with respect to a plane parallel to the bottom surface.

[0174] Alternatively, in the compositions of the embodiments of the present invention, the crystal orientation of the crystal structure of a crystalline oxide can be defined by reference to at least one lattice plane parallel to the bottom surface of the composition. In one embodiment, the lattice plane defined by the Miller index h is parallel to the bottom surface of the composition. In one embodiment, the lattice plane defined by the Miller index k is parallel to the bottom surface of the composition. In one embodiment, the lattice plane defined by the Miller index l is parallel to the bottom surface of the composition.

[0175] Thus, in one embodiment, at least a portion of the crystal structure of a crystalline oxide has a crystal orientation selected from: (101), (104), (110), and (012), or any mixture thereof with respect to a plane parallel to the bottom surface. In one embodiment, at least a portion of the crystal structure of a crystalline oxide composition has an orientation selected from: (101), (104), or both with respect to a plane parallel to the bottom surface.

[0176] Alternatively, in the components of the embodiments of the present invention, the crystal orientation of the crystal structure of the crystalline oxide can be defined by referring to a plane perpendicular to the growth direction of the crystal. Thus, in one embodiment, at least a part of the crystal structure of the crystalline oxide has a crystal orientation selected from the following with respect to a plane perpendicular to the growth direction of the crystal: (101), (104), (110), and (012), or any mixture thereof. In one embodiment, at least a part of the crystal structure of the crystalline oxide component has an orientation selected from the following with respect to a plane perpendicular to the growth direction of the crystal: (101), (104), or both.

[0177] Alternatively, when the components of the embodiments of the present invention are present in a lithium-ion battery, the crystal orientation of the crystal structure of the crystalline oxide can be defined by referring to a plane perpendicular to the direction of the lithium-ion path through the battery. Thus, in one embodiment, the components of the present invention are present in a lithium-ion battery and at least a part of the crystal structure of the crystalline oxide has a crystal orientation selected from the following with respect to a plane perpendicular to the direction of the lithium-ion path through the battery: (101), (104), (110), and (012), or any mixture thereof. In one embodiment, at least a part of the crystal structure of the crystalline oxide component has an orientation selected from the following with respect to a plane perpendicular to the direction of the lithium-ion path through the battery: (101), (104), or both.

[0178] Alternatively, when the components of the embodiments of the present invention are formed on a substrate, the crystal orientation of the crystal structure of the crystalline oxide can be defined by referring to a plane parallel to the substrate. Thus, in one embodiment, at least a part of the crystal structure of the crystalline oxide has a crystal orientation selected from the following with respect to a plane parallel to the substrate: (101), (104), (110), and (012), or any mixture thereof. In one embodiment, at least a part of the crystal structure of the crystalline oxide component has an orientation selected from the following with respect to a plane parallel to the substrate: (101), (104), or both.

[0179] In one embodiment, at least a portion of the crystalline structure of the crystalline oxide component of the composition has an orientation having Miller indices (101) (the orientation is optionally defined by reference to any of the above definitions). In one embodiment, at least 0.01% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 0.02% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 0.05% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 0.1% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 0.2% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 0.5% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 1% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 2% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 5% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 10% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 20% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 40% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 50% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 60% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 70% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 80% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 90% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 95% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 96% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation.In one embodiment, at least 97% by mass of the crystalline structure of the crystalline oxide is in a (101) orientation. In one embodiment, at least 98% by mass of the crystalline structure of the crystalline oxide is in a (101) orientation. In one embodiment, at least 99% by mass of the crystalline structure of the lithium cobalt oxide component is in a (101) orientation. In one embodiment, at least 99.5% by mass of the crystalline structure of the crystalline oxide is in a (101) orientation. In one embodiment, at least 99.7% by mass of the crystalline structure of the crystalline oxide is in a (101) orientation. In one embodiment, at least 99.9% by mass of the crystalline structure of the crystalline oxide is in a (101) orientation. These percentages are expressed by mass relative to the total mass of the crystalline components (i.e., over all the crystal orientations present).

[0180] In one embodiment, at least a portion of the crystalline structure of the crystalline oxide has an orientation having Miller indices (104) (the orientation is optionally defined by reference to any of the above definitions). In one embodiment, at least 0.01% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 0.02% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 0.05% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 0.1% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 0.2% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 0.5% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 1% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 2% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 5% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 10% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 20% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 40% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 50% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 60% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 70% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 80% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 90% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 95% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 96% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 97% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 98% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 99% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 99.5% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation.In one embodiment, at least 99.7 mass % of the crystalline structure of the crystalline oxide is in a (104) orientation. In one embodiment, at least 99.9 mass % of the crystalline structure of the crystalline oxide is in a (104) orientation. These percentages are expressed by mass based on the total mass of the crystalline oxide (i.e., over all present crystal orientations).

[0181] In one embodiment, at least a portion of the crystalline structure of the crystalline oxide component has an orientation with Miller indices (110) (the orientation is optionally defined by reference to any of the above definitions). In one embodiment, at least 0.01% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 0.02% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 0.05% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 0.1% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 0.2% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 0.5% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 1% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 2% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 5% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 10% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 20% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 40% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 50% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 60% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 70% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 80% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 90% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 95% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 96% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 97% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 98% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 99% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 99.5% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation.In one embodiment, at least 99.7 mass% of the crystalline structure of the crystalline oxide is in a (110) orientation. In one embodiment, at least 99.9 mass% of the crystalline structure of the crystalline oxide is in a (110) orientation. These percentages are expressed by mass of the total mass of the crystalline components (i.e., over all the crystal orientations present).

[0182] In one embodiment, at least a portion of the crystal structure of the lithium cobalt oxide composition has an orientation with Miller indices (012) (the orientation is optionally defined by reference to any of the above definitions). In one embodiment, at least 0.01% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 0.02% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 0.05% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 0.1% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 0.2% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 0.5% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 1% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 2% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 5% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 10% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 20% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 30% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 40% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 50% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 60% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 70% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 80% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 90% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 95% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 96% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 97% by mass of the crystal structure of the lithium cobalt oxide composition is in the (012) orientation. In one embodiment, at least 98% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 99% by mass of the crystal structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 99.5% by mass of the crystal structure of the crystalline oxide is in the (012) orientation.In one embodiment, at least 99.7 mass% of the crystalline structure of the crystalline oxide is in a (012) orientation. In one embodiment, at least 99.9 mass% of the crystalline structure of the crystalline oxide is in a (012) orientation. These percentages are expressed by mass based on the total mass of the crystalline oxide (i.e., over all present crystal orientations).

[0183] In one embodiment, at least a portion of the crystal structure of the crystalline oxide component has an orientation with Miller indices (003) (the orientation is optionally defined by reference to any of the above definitions). For the purposes of the present invention, the presence of only microcrystals with a (003) orientation is undesirable because the crystals with this orientation lack the roughness of the crystals with the above preferred orientations, and the solid-state battery lacks the favorable electrochemical properties of lithium cobalt oxide with those crystal orientations. In one embodiment, at most 99.9% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 99.7% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 99.5% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 99% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 97% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 95% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 90% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 80% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 70% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 60% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 50% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 40% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 30% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 20% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 10% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 5% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 4% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 3% by mass of the crystal structure of the crystalline lithium cobalt oxide is in the (003) orientation. In one embodiment, at most 2% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 1% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 0.5% by mass of the crystal structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 0.3% by mass of the crystal structure of the crystalline oxide is in the (003) orientation.In one embodiment, up to 0.1 mass % of the crystalline structure of the crystalline oxide is in a (003) orientation. These percentages are expressed by mass of the total mass of the crystalline components (i.e., over all present crystal orientations).

[0184] When the components of an embodiment of the present invention include a thin film layer (specifically but not exclusively, where the thin film layer includes a seed layer of Co3O4), in one embodiment, at least 2.5% of the top surface of the thin film layer is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 4.5% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 5% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 7.5% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 10% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 25% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 50% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 75% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 80% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 90% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 95% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, greater than 95% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, greater than 97.5% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, greater than 99% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, greater than 99.5% of the top surface is crystalline oxide, which includes a crystal orientation selected from (101), (104), (110), or a combination thereof.

[0185] Alternatively, or as an alternative, the crystalline structure of the component may be defined according to the spectral bands in the Raman spectrum. As is known to those skilled in the art, in solid state physics, Raman spectroscopy is used to characterize materials, measure temperature and determine the crystallographic orientation of samples.

[0186] Typically, a Raman spectrometer uses a laser, typically in the visible or near-infrared part of the electromagnetic spectrum (390 to 1000 nm), such as 450 to 900 nm, preferably 500 to 550 nm, more preferably 530 to 540 nm, and most preferably 532 nm. Typically, a Raman microscope has an objective lens with a range of 5X to 500X, preferably 10X to 100X. Typically, a Raman spectrometer has a spatial resolution of 0.5 to 2 μm 2 、preferably 1 μm 2 (defined as the area of the sample surface spot (light spot)).

[0187] For a given sample, depending on the amount of the substance with characteristic spectral bands, the crystal orientation and the purity, the spectral bands in the Raman spectrum can vary from the quoted (cited) wavenumbers. In one embodiment, the wavenumbers of the spectral bands in the Raman spectrum are quoted to ±25 cm -1 . In one embodiment, the wavenumbers of the spectral bands in the Raman spectrum are quoted to ±20 cm -1 . In one embodiment, the wavenumbers of the spectral bands in the Raman spectrum are quoted to ±15 cm -1 . In one embodiment, the wavenumbers of the spectral bands in the Raman spectrum are quoted to ±10 cm -1 . In one embodiment, the wavenumbers of the spectral bands in the Raman spectrum are quoted to ±5 cm -1 . In one embodiment, the wavenumbers of the spectral bands in the Raman spectrum are quoted to ±2 cm -1 . In one embodiment, the wavenumbers of the spectral bands in the Raman spectrum are quoted to ±1 cm -1 .

[0188] In one embodiment, the component shows a spectral band in the Raman spectrum at a wavenumber of 690 cm -1 (to the tolerances quoted above, in its broadest or preferred aspect). This spectral band is typically characteristic of the presence of the A 1g mode of Co3O4 in the component.

[0189] In one embodiment, the component shows a spectral band in the Raman spectrum at a wavenumber of 526 cm -1 (to the tolerances quoted above, in its broadest or preferred aspect). This spectral band is typically characteristic of the presence of the F 2g in the component.

[0190] In one embodiment, the composition shows a band in the Raman spectrum at a wavenumber of 625 cm -1 (to the tolerances cited above, in its broadest or preferred aspects) The band is typically characteristic of the presence of F in Co3O4 in the composition. 2g of.

[0191] In one embodiment, the composition shows a band in the Raman spectrum at a wavenumber of 484 cm -1 (to the tolerances cited above, in its broadest or preferred aspects).

[0192] In one embodiment, the composition shows a band in the Raman spectrum at a wavenumber of 593 cm -1 (to the tolerances cited above, in its broadest or preferred aspects).

[0193] In one embodiment, the (R-3m) crystalline structure of the lithium cobalt oxide composition shows at least one band in the Raman spectrum at a wavenumber selected from: 484 and 593 cm -1 (both to the tolerances cited above, in its broadest or preferred aspects), respectively attributed to A 1g and E g modes. The Raman bands at these wavenumbers are typically characteristic of the presence of the high-temperature phase of the lithium cobalt oxide having a crystal structure in one of the above preferred orientations.

[0194] In one embodiment, the composition shows a band in the Raman spectrum at a wavenumber of 690 cm -1 (to the tolerances cited above, in its broadest or preferred aspects) and at least one additional band at a wavenumber selected from: 484 and 593 cm -1 (to the tolerances cited above, in its broadest or preferred aspects).

[0195] Additionally, or alternatively, the crystalline structure of the composition can be defined according to its powder X-ray diffraction pattern. As is known to those skilled in the art, X-ray crystallography is a technique for determining the atomic and molecular structure of crystals, in which the crystalline atoms diffract a beam of incident X-rays in many specific directions. By measuring the angles and intensities of these diffracted beams, a crystallographer can produce a three-dimensional image of the electron density within the crystal. From this electron density, the average positions of the atoms in the crystal can be determined, as well as their chemical bonds, their disorder, and various other information.

[0196] Typically, X-ray diffraction uses a Cu Kα X-ray source. Typically, the measurements are made using the following conditions: θ1 = 11°, θ2 = 21° and scan time = 240 s.

[0197] In one embodiment, the crystalline structure of the crystalline oxide can be described based on the 2θ measurements of the peaks in the measured X-ray powder diffraction pattern. Typically, these measurements are quoted to ±0.2°, preferably ±0.1°, more preferably ±0.05°.

[0198] In one embodiment, the crystalline structure of the crystalline oxide exhibits at least one X-ray powder diffraction peak selected from: 2θ (±0.2°) 37.4°, 39.1°, 45.3° and 66.4°.

[0199] In one embodiment, the crystalline structure of the crystalline oxide shows an X-ray powder diffraction peak at 2θ (±0.2°) 37.4°. This peak is characteristic of LiCoO2 in the (101) crystal orientation.

[0200] In one embodiment, the crystalline structure of the crystalline oxide shows an X-ray powder diffraction peak at 2θ (±0.2°) 39.1°. This peak is characteristic of LiCoO2 in the (012) crystal orientation.

[0201] In one embodiment, the crystalline structure of the crystalline oxide shows an X-ray powder diffraction peak at 2θ (±0.2°) 45.3°. This peak is characteristic of LiCoO2 in the (104) crystal orientation.

[0202] In one embodiment, the crystalline structure of the crystalline oxide shows an X-ray powder diffraction peak at 2θ (±0.2°) 66.4°. This peak is characteristic of LiCoO2 in the (110) crystal orientation.

[0203] In one embodiment, the crystalline structure of the crystalline oxide can be described based on the 2θ measurements, which correspond to the distance (d) (d-spacing) between adjacent lattice planes. Typically, these measurements are quoted to preferably more preferably

[0204] In one embodiment, the crystalline structure of the crystalline oxide shows an X-ray powder diffraction peak corresponding to 2θ 37.4° of 2.399 (±0.1). This peak is characteristic of LiCoO2 in the (101) crystal orientation.

[0205] In one embodiment, the crystalline structure of the crystalline oxide shows an X-ray powder diffraction peak corresponding to 2θ 39.1° of 2.301 (±0.1). This peak is characteristic of LiCoO2 in the (012) crystal orientation.

[0206] In one embodiment, the crystal structure of the crystalline oxide shows an X-ray powder diffraction peak at 2θ 45.3° corresponding to 2.001 (±0.1). This peak is characteristic of LiCoO2 in the (104) crystal orientation.

[0207] In one embodiment, the crystal structure of the crystalline oxide shows an X-ray powder diffraction peak at 2θ 66.4° corresponding to 1.406 (±0.1). This peak is characteristic of LiCoO2 in the (110) crystal orientation.

[0208] In one embodiment, the crystalline oxide has a crystal structure showing X-ray powder diffraction as follows, the X-ray powder diffraction including peaks at 2θ selected from 37.4°, 45.3° or both 37.4° and 45.3° (corresponding to selected from or and both of ).

[0209] Those skilled in the art will understand that the crystal structure of the lithium cobalt oxide composition may include microcrystals having more than one of the above orientations, and thus more than one of the above peaks may be observed in the powder X-ray diffraction pattern of a given composition sample.

[0210] In one embodiment, the crystal structure of the lithium cobalt oxide composition shows at least one X-ray powder diffraction peak at 2θ selected from 37.4°, 45.3° (each ±0.1°) or both, and / or corresponding to 2.399, 2.001 (each ).

[0211] In one embodiment, there is provided a composition comprising a crystalline oxide of lithium and cobalt, wherein the atomic % of lithium and cobalt is defined as above in its broadest or preferred aspect, the crystal structure of the composition being characterized, in its broadest or preferred aspect, by locally aggregated Co3O4 as defined above, and the crystal structure being further characterized by at least one of the following parameters (a) to (c):

[0212] (a) Orientations selected from: (101), (104), (110) and (012);

[0213] (b) A band in the Raman spectrum at a wavenumber of 690 cm -1 (±5 cm -1 ) and at least one additional band at a wavenumber selected from 484 and 593 cm -1 (both ±5 cm -1 );

[0214] (c) at 2θ selected from 37.4°, 39.1°, 45.3° and 66.4° (each ±0.2°) and / or at 2θ corresponding to at least one X-ray powder diffraction peak at 2.399, 2.301, 2.001 or 1.406 (each ±0.1°).

[0215] In one embodiment, there is provided a composition comprising a crystalline oxide of lithium and cobalt, wherein the atomic percentages of lithium and cobalt are defined as above in their broadest or preferred aspects, and the crystalline structure of the composition is characterized, in its broadest or preferred aspect, by locally aggregated Co3O4 as defined above and an orientation selected from (101), (104), (110) and (012), preferably (101) or (104).

[0216] In one embodiment, there is provided a composition comprising a crystalline oxide of lithium and cobalt, wherein the atomic percentages of lithium and cobalt are defined as above in their broadest or preferred aspects, and the crystalline structure of the composition is characterized, in its broadest or preferred aspect, by locally aggregated Co3O4 as defined above and a band in the Raman spectrum at a wave number of 690 cm -1 (±5 cm -1 ).

[0217] In one embodiment, there is provided a composition comprising a crystalline oxide of lithium and cobalt, wherein the atomic percentages of lithium and cobalt are defined as above in their broadest or preferred aspects, and the crystalline structure of the composition is characterized, in its broadest or preferred aspect, by locally aggregated Co3O4 as defined above and at least one X-ray powder diffraction peak at: selected from 37.4°, 39.1°, 45.3° and 66.4° (each ±0.2°) and / or corresponding to a spacing 2.399, 2.301, 2.001 or 1.406, preferably (±0.1°) 37.4° or 45.3°, corresponding to a spacing 2.399 or 2.001.

[0218] Typically, lithium cobalt oxide is formed in the form of a film, especially in the form of a film on a substrate (as defined in more detail below). In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is from 1 to 30 μm. In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is from 2 to 20 μm. In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is from 3 to 12 μm. In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is from 5 to 10 μm. In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is from 6 to 7 μm.

[0219] Method

[0220] The present invention may also provide a method for preparing a composition comprising Co3O4 and a crystalline lithium cobalt oxide, particularly but not exclusively a composition according to the first aspect of the present invention. The method generally comprises providing sources of the respective constituent elements of the compound, wherein the sources comprise a lithium source, an oxygen source and a cobalt source (and optionally a source of one or more dopant elements as defined below); and depositing these onto a substrate, particularly but not exclusively a substrate heated to from about 50 °C to about 800 °C. The constituent elements from the sources react on the substrate to form a crystalline oxide of lithium and cobalt (optionally doped with one or more of the elements defined below), and the constituent elements from the sources of cobalt and oxygen react on the substrate to form Co3O4.

[0221] Typically, the method comprises: typically forming, on a substrate, a crystalline lithium cobalt oxide (or a crystalline doped lithium cobalt oxide) in the form of a film. Suitable substrates are well known to those skilled in the art and include metals (such as platinum, aluminum, titanium, chromium, iron, zinc, gold, silver, nickel, molybdenum, including their alloys, which may include non-metals such as carbon, examples of which include steels such as stainless steel), metal oxides such as alumina, particularly conductive metal oxides such as indium tin oxide), silicon, silicon dioxide, silica (including doped silica), aluminosilicate materials, glass and ceramic materials.

[0222] Contrary to the methods described in the prior art, the exemplary methods of the present invention have the distinguishing feature that one or more conditions of the method are changed such that locally aggregated Co3O4 (as defined above, in its broadest or preferred aspect) is formed, thereby enabling crystal growth of a lithium cobalt oxide composition (as defined above, in its broadest or preferred aspect) having a desired crystal structure.

[0223] In one embodiment, the method is characterized in that one or more conditions of the method are changed such that locally aggregated Co3O4 is formed as a seed layer, thereby enabling crystal growth of a composition having a desired crystal structure and a greater roughness / irregularity (as described above) than those of the prior art.

[0224] The method generally comprises providing sources of the respective constituent elements of the compound, wherein the sources comprise a lithium source, an oxygen source and a cobalt source, and optionally a source of one or more of the dopant elements listed herein. The precise nature of such sources of elements is not important for the present invention, provided that it contains the required elements.

[0225] The reaction in which the constituent elements form a compound occurs on the surface of the substrate, rather than in the gas phase before deposition on the substrate. Although not wishing to be bound by theory, it is believed that the constituent elements in vapor form collide with and adhere to the surface of the heated substrate, whereupon the atoms of the respective elements are mobile on the surface and can thus react with each other to form an oxide compound.

[0226] In one embodiment, the vapor source includes an electron beam evaporator or a Knudsen cell (K-Cell); these are well-suited for materials with low partial pressures. In both cases, the material is contained in a crucible and heated to produce an atomic stream. The Knudsen cell uses a series of heating wires around the crucible, while in an electron beam evaporator, heating is achieved by using magnets to direct a high-energy electron beam onto the material.

[0227] Typically, lithium and cobalt can be deposited from a Knudsen cell source or an electron gun (E-gun).

[0228] In one embodiment, the oxygen source is molecular oxygen. In one embodiment, the oxygen source is atomic oxygen (typically but not exclusively, produced by an oxygen plasma source). In one embodiment, the oxygen source is an ozone source.

[0229] The oxygen plasma source delivers oxygen in the plasma phase, i.e., a stream of oxygen atoms, radicals, and ions. The source can be, for example, a radio frequency (RF) plasma source or an ozone source.

[0230] If desired, a small amount of an additional gas (typically an inert gas, such as a noble gas, e.g., helium, neon, argon, krypton, and xenon; or nitrogen; preferably argon and / or nitrogen) can be added to the oxygen stream. If present, one or more additional gases are present in a total proportion of up to 10%, e.g., up to 5%, e.g., up to 3%, e.g., up to 2%, e.g., up to 1%. This is typically measured by a residual gas analyzer (RGA) and is defined as the mole percent relative to 100 mole percent oxygen, which is obtained by dividing the partial pressure of one or more additional gases by the oxygen partial pressure.

[0231] In addition to the lithium source, cobalt source, and oxygen source, there can also be a source of other dopant elements (as defined and exemplified above) that form part of the crystal structure of the predetermined composition. In one embodiment, the method further includes providing a source of one or more elements selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, ruthenium, nickel, zinc, copper, molybdenum, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, such that one or more elements form part of a crystalline component having the desired crystal structure.

[0232] Alternatively, an amorphous film can be deposited and then annealed in an amorphous form using the method of the present invention. However, this is not preferred because such a method does not exhibit the advantages of the present invention, such as directly forming a stoichiometric compound at a low substrate temperature and avoiding the requirement of post-deposition annealing at a higher temperature.

[0233] A general method used according to an embodiment of the present invention is a physical vapor deposition (PVD) method. According to this method, a crystalline lithium cobalt oxide composition is formed from the constituent elements lithium, cobalt, and oxygen as follows: providing a vapor source for each of the constituent elements of the compound and co-depositing the constituent elements from the vapor source onto a substrate, typically a heated substrate.

[0234] Thus, in this embodiment, a vapor deposition method is provided, which includes: providing a vapor source for each of the constituent elements of the compound to deliver a stream of lithium, a stream of oxygen, a stream of cobalt, and optionally a stream of the at least one dopant element, wherein the vapor source includes a lithium source, an oxygen source, and a cobalt source and optionally a source of at least one dopant element selected from the following: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, ruthenium, copper, molybdenum, nickel, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium; heating the substrate to between substantially 50°C and 800°C; depositing the constituent elements from the sources onto the heated substrate, wherein the constituent elements react on the substrate to form a crystalline oxide of lithium and cobalt, which optionally contains one or more dopant elements; characterized in that, during or prior to the co-deposition, one or more conditions of the vapor deposition method are changed such that locally aggregated Co3O4 is formed, thereby enabling crystal growth of a composition having a desired crystalline structure.

[0235] The physical vapor deposition (PVD) method according to one aspect of the present invention typically includes co-depositing the constituent elements from the vapor source onto a heated substrate. In one embodiment, the substrate is heated to about 150°C to about 700°C. In one embodiment, the substrate is heated to about 200°C to about 700°C. In one embodiment, the substrate is heated to about 300°C to about 450°C.

[0236] The physical vapor deposition (PVD) method according to one aspect of the present invention typically is carried out at a pressure of 1 x 10 -7 to 1 x 10 -4 Torr, preferably 1 x 10 -6 to 5 x 10 -5 Torr, more preferably 5 x 10 -6 to 2 x 10 -5 Torr.

[0237] Typically, the method is carried out such that the deposition rate of the film is between 0.1 and 10 μm / hour. In one embodiment, the method is carried out such that the deposition rate is between 0.2 and 5 μm / hour. In one embodiment, the method is carried out such that the deposition rate is between 0.3 and 1.6 μm / hour. In one embodiment, the method is carried out such that the deposition rate is between 0.4 and 0.8 μm / hour.

[0238] According to this aspect of the invention, one or more conditions of the chemical vapor deposition method are changed such that locally aggregated Co3O4 is formed, thereby enabling crystal growth of a component having a desired crystalline structure. In one embodiment, changing one or more conditions includes delivering cobalt and lithium at a flow rate ratio different from the flow rate ratio delivered for depositing the crystalline oxides of lithium and cobalt. Without wishing to be bound by theory, it is believed that delivering cobalt and lithium at a flow rate ratio different from the flow rate ratio delivered for depositing the crystalline lithium cobalt oxide allows for the formation of Co3O4 (typically as a seed layer) to enable crystal growth of a lithium cobalt oxide component having a desired crystalline structure.

[0239] In one embodiment, the flow rate of cobalt is between 0.1 and . In one embodiment, the flow rate of cobalt is between 0.1 and . In one embodiment, the flow rate of cobalt is between 0.4 and . In one embodiment, the flow rate of cobalt is between 0.5 and . This flow rate is typically measured at the substrate surface. Typically, the flow rate of cobalt is measured in the presence of oxygen (such that when measured in this way, the actual flow rate of cobalt oxide is measured).

[0240] In one embodiment, the flow rate of lithium is between 0.1 and . In one embodiment, the flow rate of lithium is between 0.5 and . In one embodiment, the flow rate of lithium is between 0.7 and . In one embodiment, the flow rate of lithium is between 0.8 and . This flow rate is typically measured at the substrate surface. Typically, the flow rate of lithium is measured in the presence of oxygen (such that when measured in this way, the actual flow rate of lithium oxide is measured).

[0241] When one or more of said dopant elements are present, in one embodiment, the flow rate of the dopant element is between 0.1 and . In one embodiment, the flow rate of the dopant element is between 0.1 and . In one embodiment, the flow rate of the dopant element is between 0.4 and Between. In one embodiment, the dopant element flux is between 0.5 and Between. This flux is typically measured at the substrate surface. Typically, the dopant element flux is measured in the presence of (such that when measured in this way, the flux of its corresponding oxide is actually measured).

[0242] The ability to measure the rate (ratio) of individual atomic fluxes and vary them during deposition allows control of the composition throughout the film thickness and can be used to address any changes in vapor source conditions (such as source aging or drift (gradual change)) to maintain a constant lithium-cobalt composition throughout the film or to produce a film with a changing lithium-cobalt composition during deposition. The rate of individual atomic fluxes can be measured directly at the source and / or indirectly (by measuring the oxygen partial pressure during deposition) during deposition. In one embodiment, the rate of individual atomic fluxes is measured by electron impact emission spectroscopy (EIES).

[0243] According to this aspect of the invention, generating a controlled compositional change during deposition can be effectively used to create a seed layer within the film. For example, a seed layer containing Co3O4 within the film during deposition can be achieved by varying the individual atomic fluxes by the preferred methods listed below.

[0244] In one embodiment, varying one or more conditions includes making the cobalt flux exceed the lithium flux required to deposit crystalline oxides of lithium and cobalt.

[0245] In one embodiment, the cobalt flux is increased relative to the cobalt flux level required to deposit crystalline oxides of lithium and cobalt, and the lithium flux is maintained at the lithium flux level required to deposit crystalline oxides of lithium and cobalt.

[0246] In one embodiment, the cobalt flux is maintained at the cobalt flux level required to deposit crystalline oxides of lithium and cobalt, and the lithium flux is decreased relative to the lithium flux level required to deposit crystalline oxides of lithium and cobalt.

[0247] In one embodiment, the oxygen flux is decreased. In one embodiment where oxygen is delivered together with an inert gas (as defined and exemplified above), the oxygen flux is maintained at the same level, and this control is imparted by dilution of oxygen and thus a decrease in its partial pressure.

[0248] Controlling the rate of atomic fluxes is only one method that can be used in physical vapor deposition embodiments to control the morphology of lithium cobalt oxides. Other methods that can be used to provide local aggregation of Co3O4 (such as a seed layer) can include stopping the lithium flux by closing the lithium shutter and changing the oxygen partial pressure in the chamber (by changing the oxygen flow rate or adding an additional gas such as argon).

[0249] In one embodiment, the vapor deposition method includes co-depositing constituent elements onto a heated substrate, which includes directly co-depositing the constituent elements onto the surface of the heated substrate. In one embodiment, the vapor deposition method includes co-depositing constituent elements onto a heated substrate, which includes co-depositing the constituent elements onto one or more layers supported on the substrate.

[0250] According to one example of the present invention, the vapor deposition method is the method generally described in WO 2015 / 104539, which is varied according to this aspect of the present invention to produce the desired locally aggregated Co3O4.

[0251] In one embodiment, the deposition described in WO 2015 / 104539 is carried out in a physical vapor deposition (PVD) system heated to 50 - 800 °C; for the LCO film deposited on a bare substrate or a current collector layer (excluding the thermosensitive battery layer), the temperature is preferably 300 - 450 °C, but a higher substrate temperature up to 800 °C can be used.

[0252] In one embodiment, the method further includes annealing the deposited lithium cobalt oxide film after deposition. This additional step is particularly useful when the deposition is carried out at a temperature below 400 °C. Typically, when depositing the lithium cobalt oxide film onto a previously deposited battery layer to form a stacked battery, the annealing temperature of the substrate is preferably heated to 300 - 450 °C.

[0253] It is generally believed that depositing crystalline lithium cobalt oxide by the following method allows avoiding the formation of Co3O4 (as discussed above, cobalt oxide (Co3O4) is generally considered an impurity in the LiCoO2 composition): providing separate vapor sources of lithium, oxygen, and cobalt (and optionally vapor sources of one or more dopant elements) and controlling the separate source streams to co-deposit these onto a substrate such that they react on the substrate to form a crystalline oxide. Therefore, it can be considered counterintuitive to intentionally prepare a composition including Co3O4 and crystalline lithium cobalt oxide using this method.

[0254] In an alternative, the method according to the present invention can be carried out by sputtering. As known to those skilled in the art, sputter deposition is a physical vapor deposition (PVD) method of thin film deposition by sputtering. Sputtering involves ejecting material from one or more targets that are sources of the desired elements and directing it onto a substrate such that the growth of the desired material can be achieved, typically as a film on the substrate.

[0255] Thus, in one embodiment, there is provided a method for preparing the composition of an embodiment of the present invention, wherein the method is a sputter deposition method, which includes:

[0256] Provided are at least one sputtering target, at least one sputtering target including a lithium source, at least one sputtering target including a cobalt source, and optionally one or more sputtering targets including a source of at least one dopant element selected from the group consisting of magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, ruthenium, copper, molybdenum, nickel, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the sputtering targets being the same or different; and

[0257] Sputtering the targets to produce a composition including Co3O4 and a crystalline oxide of lithium and cobalt, the crystalline oxide being optionally doped with at least one of the dopant elements.

[0258] Typically, the sputtering target providing the source of the desired element includes an oxide of the element such that the target provides both the source of the element and at least part of the oxygen source. In one embodiment, the sputtering target serving as the lithium source includes lithium oxide (Li2O). In one embodiment, the sputtering target serving as the cobalt source includes cobalt(II) oxide (CoO). In one embodiment, the sputtering target serving as the cobalt source is cobalt(III) oxide (Co2O3). In one embodiment, the sputtering target serving as the cobalt source includes Co3O4.

[0259] In one embodiment, sputtering can be carried out using a single target that provides sources of both lithium and cobalt, preferably as oxides. In this embodiment, the sputtering target providing sources of both lithium and cobalt includes LiCoO2. The target may optionally have additional lithium (e.g., Li2O) added thereto to provide a composition with a greater lithium ratio. In this embodiment, the oxygen partial pressure can be varied during the deposition of the composition to achieve locally aggregated Co3O4.

[0260] In one embodiment, sputtering can be carried out using one sputtering target and at least one different sputtering target, the one sputtering target providing a lithium source and part of the cobalt source, preferably as an oxide, more preferably LiCoO2 (optionally with Li2O added thereto), the at least one different sputtering target providing part of the cobalt source, typically including Co3O4.

[0261] When the predetermined composition includes one or more dopant elements selected from the group consisting of magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, ruthenium, copper, molybdenum, nickel, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the sputtering target typically includes an oxide of the element. The sputtering target including the oxide of the dopant element can be the same as or different from the sputtering target including an oxide of lithium and / or an oxide of cobalt.

[0262] When the sputtering targets are different, the targets can be sputtered simultaneously or sequentially.

[0263] In one embodiment, a method for preparing the components of the embodiments of the present invention is provided, wherein the method is a sputtering deposition method, which includes:

[0264] Providing a first sputtering target including cobalt oxide;

[0265] Providing a second sputtering target, the second sputtering target including a source of (a) lithium cobalt oxide or (b) lithium cobalt oxide including at least one dopant element selected from magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, ruthenium, copper, molybdenum, nickel, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium;

[0266] Sputtering the first sputtering target and the second sputtering target to produce a component including Co3O4 and a crystalline oxide of lithium and cobalt, the crystalline oxide being optionally doped with at least one of the dopant elements.

[0267] In one embodiment, a method for preparing the components of the embodiments of the present invention is provided, wherein the method is a sputtering deposition method, which includes:

[0268] Sputtering the first target to produce a thin film layer of Co3O4, and then sputtering the second target to produce a thin film crystalline oxide of lithium and cobalt, which is optionally doped with at least one of the dopant elements.

[0269] In one embodiment, a method for preparing the components of the embodiments of the present invention is provided, wherein the method is a sputtering deposition method, which includes:

[0270] Sputtering the first target to produce a thin film layer of Co3O4 having a top surface and a bottom surface; and

[0271] Sputtering the second target on the top surface of the thin film layer of Co3O4 to produce a thin film crystalline oxide of lithium and cobalt, which is optionally doped with at least one of the dopant elements.

[0272] In one embodiment, a method for preparing the components of the embodiments of the present invention is provided, wherein the method is a sputtering deposition method, which includes:

[0273] Providing a first sputtering target including Li2O and / or an oxide of lithium and cobalt and a second sputtering target including an oxide of cobalt (preferably Co3O4); and

[0274] Simultaneously sputtering the targets to produce a mixed thin film layer including Co3O4 and a crystalline oxide of lithium and cobalt.

[0275] In one embodiment, a method for preparing the components of the embodiments of the present invention is provided, wherein the method is a sputtering deposition method, which includes:

[0276] Provide a first sputtering target including Li2O and / or an oxide of lithium and cobalt, and a second sputtering target including an oxide of cobalt, preferably Co3O4; and

[0277] Sputter the second target to produce a thin film layer of Co3O4, and then sputter the first target to produce a thin film crystalline oxide of lithium and cobalt on the surface of the thin film layer of Co3O4.

[0278] Typically, the high-energy particles are gas ions. In one embodiment, the gas ions are argon ions.

[0279] Examples of types of sputter deposition include RF sputtering, DC sputtering, pulsed DC sputtering, ion beam sputtering, reactive sputtering, high target utilization sputtering (HiTUS), high power pulsed magnetron sputtering (HiPiMS), and gas flow sputtering.

[0280] The sputtering method according to this example of the present invention is typically carried out at a pressure of 1 x 10 -4 to 1 x 10 -2 torr, preferably 5 x 10 -4 to 5 x 10 -2 torr, and more preferably 1 x 10 -3 to 2 x 10 -3 torr.

[0281] In an alternative, the method according to the present invention can be carried out by chemical vapor deposition. As is known to those skilled in the art, chemical vapor deposition includes providing a vapor source of the constituent elements of the desired material, where the source includes one or more precursor compounds containing the required elements, and typically deposits the vaporized elements onto a heated substrate by spraying (coating). The constituent elements from the source react on the substrate to form the desired material.

[0282] Accordingly, there is further provided a method for preparing a crystalline lithium cobalt oxide composition (particularly but not exclusively, the composition of an embodiment of the present invention), where the method is a vapor deposition method, which includes:

[0283] Provide a source of the constituent elements of the compound, where the source includes one or more precursor compounds: at least one lithium-containing precursor compound, at least one cobalt-containing precursor compound, and at least one oxygen-containing precursor compound;

[0284] Heat the substrate to between about 200°C and about 1000°C;

[0285] Spray the precursor compounds onto the heated substrate;

[0286] where the constituent elements from the source react on the substrate to form a crystalline oxide of lithium and cobalt;

[0287] It is characterized in that one or more conditions of the method are changed so that locally aggregated Co3O4 is formed, enabling crystal growth of a component having a desired crystal structure.

[0288] In one embodiment, the substrate is heated to a temperature between 250 °C and 950 °C. In one embodiment, the substrate is heated to a temperature between 300 °C and 600 °C.

[0289] The CVD method according to this example of the present invention is typically carried out at a pressure of 0.1 to 500 Torr, preferably 1 to 100 Torr.

[0290] In one embodiment, the precursor compounds are mixed to form a sol before being sprayed onto the heated substrate.

[0291] There is no particular limitation on the precursor compounds, as long as at least one precursor compound contains lithium and at least one precursor compound contains cobalt. In one embodiment, the precursor compound containing lithium includes a lithium salt and / or the precursor compound containing cobalt includes a cobalt salt.

[0292] Electrode

[0293] The crystalline lithium cobalt oxide component according to an embodiment of the present invention is particularly useful for forming an electrode, which is typically used in a unit cell such as an electrochemical unit cell and a fuel unit cell.

[0294] Therefore, according to another aspect, the present invention also provides an electrode comprising the crystalline lithium cobalt oxide component according to an embodiment of the present invention (as defined above, in its broadest aspect or preferred aspect).

[0295] Typically, in the electrode according to an embodiment of the present invention, the crystalline lithium cobalt oxide component is supported on a carrier (support). In one embodiment, the crystalline lithium cobalt oxide component forms a layer on the carrier.

[0296] Typically, the carrier is a substrate on which a current collector material is supported. In one embodiment, the current collector material is a metal or a conductive metal oxide. In one embodiment, the current collector material is selected from: platinum, aluminum, titanium, chromium, iron, zinc, gold, silver, nickel, molybdenum, tin oxide, indium tin oxide, and stainless steel.

[0297] Typically, the substrate is an inert substrate. In one embodiment, the substrate is selected from: silicon, silicon oxide, aluminum oxide, aluminosilicate material, doped silicon oxide, glass, metal, and ceramic material.

[0298] In one embodiment, the substrate is a silicon substrate. In one embodiment, the silicon substrate is covered by one or more passivation layers. In one embodiment, at least one passivation layer comprises silicon dioxide. In one embodiment, at least one additional passivation layer comprises silicon nitride.

[0299] In one embodiment, an adhesion layer is present between the current collector and the substrate. In one embodiment, the adhesion layer is selected from metals and metal oxides. In one embodiment, the adhesion layer is selected from: titanium oxide, titanium, zirconium, and chromium.

[0300] Electrochemical unit cell

[0301] The crystalline lithium cobalt oxide composition of embodiments of the present invention can be effectively used in unit cells, particularly in electrochemical unit cells.

[0302] Accordingly, in another aspect of the present invention, there is provided an electrochemical unit cell comprising: an electrolyte; a negative electrode; and a positive electrode; wherein the negative electrode and / or the positive electrode comprises an electrode according to the present invention.

[0303] It has been found that the lithium cobalt oxide composition of embodiments of the present invention is particularly suitable for use at the positive electrode of such unit cells.

[0304] Accordingly, the present invention also provides an electrochemical unit cell as defined above, wherein the positive electrode comprises an electrode according to the present invention.

[0305] The unit cell can be a solid-state unit cell (also referred to as a solid-state battery).

[0306] Typically, the unit cell is a lithium-ion battery. As defined above, in a lithium-ion battery, lithium ions (Li + ) move from the negative electrode to the positive electrode during discharge and move back during charging. Accordingly, the present invention also provides a lithium-ion battery as defined above, wherein the positive electrode comprises an electrode according to the present invention.

[0307] The electrolyte can be any electrolyte typically used in an electrochemical unit cell. However, particularly preferably, the electrolyte is a solid electrolyte. The application of the lithium cobalt oxide composition of embodiments of the present invention in a battery using a solid electrolyte confers improved performance (particularly cycle life, capacity, adhesion to the underlying layer, and stress control), which has not been previously disclosed in the art.

[0308] Examples of solid electrolytes include the following:

[0309] · Lithium phosphorus oxynitride (LiPON)

[0310] · Lithium borosilicate (as described in WO2017 / 216532, WO2015 / 104540, and WO2015 / 104538)

[0311] · Sulfide-based vitreous and glass-ceramic electrolytes, such as LPS (xLi2S-yP2S5), Li2-SiS2

[0312] · Garnet-type solid electrolytes such as Li5La3M2O 12 or LLZO (Li7La3Zr2O 12 )

[0313] · Argyrodite-type such as Li6PS5X (where X is a halogen, such as Cl, Br, I)

[0314] · Oxide-based perovskite-type solid electrolytes such as LLTO (Li 0.5 La 0.5 TiO3)

[0315] · LISICON-type such as Li 10 GeP2S 12 、NASICON-type such as Li1.4[Al 0.4 Ge 1.6 (PO4)3], LATP (Li 1+ x Al x Ti 2-x (PO4)3

[0316] · Solid polymer electrolytes such as polyethylene oxide (PEO)

[0317] In one embodiment, the electrolyte comprises lithium phosphorus oxynitride (LiPON).

[0318] A method of manufacturing a solid-state unit cell is also provided, the method comprising depositing an electrode of the unit cell using a layer of crystalline lithium cobalt oxide composition according to the method of the present invention as an embodiment of the present invention.

[0319] After depositing the lithium cobalt oxide composition, a gas deposition technique such as physical vapor deposition or sputtering is used to deposit additional layers of the solid-state battery to produce a multi-layer structure. The production of solid-state batteries by PVD alone has been previously described in WO2015 / 104538.

[0320] Preferred layers of the solid-state battery and their manufacturing methods are shown below. However, as is known to those skilled in the art, the layers and manufacturing methods of solid-state batteries are not limited to those listed below.

[0321]

[0322] In one embodiment, the electrochemical unit cell is a fuel cell. As is known to those skilled in the art, a fuel cell is an electrochemical unit cell that converts the chemical energy from a fuel (typically hydrogen or a simple organic compound such as methanol or formic acid) into electricity through an electrochemical reaction with oxygen or other oxidants. A fuel cell differs from a storage battery in that it requires a continuous source of fuel and oxygen (usually from air) to sustain the chemical reaction, whereas in a storage battery, the chemical energy comes from chemicals already present in the battery. As long as fuel and oxygen are supplied, the fuel cell can continuously generate electricity.

[0323] Accordingly, in another aspect of the present invention, there is provided a fuel cell comprising:

[0324] a negative electrode; a positive electrode; and an electrolyte; wherein the negative electrode and / or the positive electrode comprises the crystalline oxide material of an embodiment of the present invention.

[0325] The fuel cell typically also includes a fuel supply or is connected to a fuel supply. In one embodiment, the fuel is hydrogen. In one embodiment, the fuel is an organic compound, typical examples of which include methane, methanol, ethanol, formic acid, and acetic acid.

[0326] The fuel cell typically also includes an oxidant supply or is connected to an oxidant supply. In one embodiment, the oxidant is molecular oxygen. In one embodiment, the oxidant is an oxidant known to those skilled in the art, examples of which are known.

[0327] There is also provided an electronic device comprising the electrochemical unit cell (particularly a lithium-ion battery) according to the present invention. Examples of such electronic devices are well known to those skilled in the art and include handheld electronic devices such as mobile phones.

[0328] Examples

[0329] Figure 1 FIG. shows a schematic diagram of an exemplary apparatus 10 for a physical vapor deposition embodiment suitable for practicing the method of the present invention. Deposition is carried out within a vacuum system 12, which may be an ultra-high vacuum system. A substrate 14 of a desired material (depending on the intended purpose of the deposited material) is mounted within the vacuum system 12 and heated above room temperature using a heater 16. Also within the vacuum system are a plurality of vapor sources, one source for each of the constituent elements in the desired thin film compound. The first vapor source 18 includes a source of atomic oxygen, such as an oxygen plasma source. The second vapor source 20 includes a source of lithium vapor. The third vapor source 22 includes a source of cobalt vapor.

[0330] During the deposition process, a controlled flow of each constituent element is released from its respective vapor source onto the heated substrate 14, co-depositing the various elements. The elements react on the substrate 14 to form a thin film layer 29 of crystalline lithium cobalt oxide.

[0331] A significant advantage of the described physical deposition method is that directly depositing the components of the compound from the elements allows for direct control of the composition and structure of the compound via the deposition rates of the constituent elements. The flow of each element can be independently controlled by appropriate operation of its respective vapor source, such that if desired, the chemical composition of the deposited compound can be adjusted according to precise requirements.

[0332] During deposition, the rates of the lithium and cobalt flows are monitored, and if necessary, the corresponding vapor sources are appropriately adjusted. The deposition rates of both the lithium flow and the cobalt flow can be measured, for example, using a quartz crystal microbalance (QCM) or electron impact emission spectroscopy (EIES). The cobalt flow can also be indirectly monitored by using a residual gas analyzer (RGA) or an ionization gauge to monitor the stability of the oxygen pressure in the deposition chamber; the reactivity of cobalt with oxygen means that when the cobalt flow changes, an inverse (opposite) change in the oxygen pressure is observed. The gases present in the vacuum system, namely oxygen, nitrogen, argon, carbon dioxide (trace amounts), and carbon monoxide (trace amounts), can be monitored using a residual gas analyzer (RGA), and the total pressure can be measured using an ionization gauge.

[0333] The pressure of the gas introduced into the system can be changed by varying the gas flow rate into the chamber. In addition, during the deposition process, the growth of the film can be monitored, for example, by ellipsometry and other optical techniques.

[0334] It can be advantageous to prepare a film with a non-constant composition / including a seed layer because it can allow control of the structure and morphology of the film, for example, by introducing defects that can act as nucleation sites for crystal growth. Controlling the composition of the film in this way can also affect the properties of the film, such as the adhesion to surrounding layers, and help balance the stress within the film. Such precise control of the film composition and the ability to make adjustments during the deposition process, thereby controlling the properties of the final film, gives the method of the present invention an advantage over other techniques such as pulsed laser deposition (PLD) (which may suffer from preferential loss of lighter elements such as lithium, making control of the composition in the final film more difficult).

[0335] According to this method, a LiCoO2 film with a thickness of 1 - 30 μm can be deposited for use in a solid-state battery. Before depositing the LiCoO2 for the solid-state battery, a thinner (<1 μm (typically ~250 nm)) test LiCoO2 layer is deposited using the same method, and the structure and composition of these test layers are analyzed by Raman spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

[0336] When a suitable test sample is obtained, the conditions are repeated during a longer deposition process to obtain a thicker LiCoO2 film for use in a solid-state battery.

[0337] Due to the different crystal structures that provide Raman fingerprints, Raman spectroscopy is a powerful technique for the microstructural analysis of LiCoO2. Two Raman bands are expected to be observed for the R-3m (high-temperature) phase (HT-LCO), and four Raman bands for the low-temperature (Fd3m) (LT-LCO). Additionally, Raman spectroscopy is able to detect the secondary product Co3O4, even at trace / impurity levels, due to the strong scattering intensity of this oxide. Raman spectroscopy is a particularly effective method for studying these materials.

[0338] The Raman spectrometer used in these examples is a Horiba XploRA Plus, which is equipped with a 532 nm (green) laser and 10X, 50X, and 100X microscope objectives. For the 532 nm laser with a 0.90 NA / 100X objective, this would imply a spatial resolution of 361 nm. However, the optical processes that occur during Raman microscopy are much more complex than for standard light microscopy. Many factors can reduce this resolution. Thus, the typical Raman spatial resolution is usually quoted as 1 μm (although this can be improved under ideal conditions).

[0339] Raman spectroscopy measurements are performed according to the acquisition parameters shown in Table 1. Top-down measurements use an objective 50X, slit 50, aperture 100, and filter 2%. Cross-section measurements use the same settings as above, however with an objective 100X and a cumulative count of 2, using lines with a spacing of 1 μm, and the number of points covering the entire sample.

[0340] Table 1

[0341] Material <![CDATA[Collection range / cm -1 > Grating Collection time / s Accumulation Lithium cobalt oxide 300 to 1200 2400T 30 4

[0342] Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is used to determine the lithium-cobalt ratio present in the film. In a preferred aspect, a lithium cobalt oxide film can be formed that is slightly lithium-deficient in composition, such as a lithium:cobalt ratio of 47.5 - 49.1% lithium and 52.5 - 50.9% cobalt (expressed as a percentage of the total metal atoms excluding oxygen).

[0343] However, the properties and performance of the as-prepared films vary, indicating that although composition plays a role in influencing these properties, it is not the only important factor. Figure 2The cycle life of many of these films is shown, and it is shown that within the Li:Co composition range of 47.5 - 49.1 atomic % Li, for different films with the same Li:Co composition, both high cycle life and low cycle life can be achieved (under the same cycling conditions). The same is true for the utilization number (capacity normalized by area and thickness). Figure 3 shows a wide distribution of utilization numbers within the interesting composition range.

[0344] The crystalline nature of the deposited LiCoO2 films is demonstrated by both Raman spectroscopy and X-ray diffraction. Raman spectroscopy shows that the deposited films have the HT-LiCoO2 phase (R-3m)( Figure 4 ), and due to the nature of this synthesis method that allows the deposition of crystalline lithium-containing materials at a substrate temperature lower than that typically described in WO 2015 / 104539, this high-temperature phase is obtained at a relatively low substrate temperature of 400 °C. The hexagonal R-3m phase consists of an ordered layered structure composed of cobalt layers alternating with lithium layers (e.g., as described in Porthault et al., Vibrational Spec 62(2012)152 - 158).

[0345] The X-ray diffraction (XRD) pattern of the deposited film( Figure 5 ) shows that the film is mainly (00l) oriented, where the (003) peak at 18.9° is the strongest peak. Additionally, for some embodiments, peaks are observed at 37.4° (101), 38.4° (006), 39.1° (012), and 45.3° (104), indicating the presence of microcrystals with other orientations. Cross-sectional Raman spectroscopy has been performed on these films to confirm the changes in the films resulting from small variations during the deposition process: these changes can be related to the morphology of the films.

[0346] Figure 6 An example of a film (film 4) (not prepared according to the present invention) is shown, where the deposition conditions are kept constant throughout the deposition time: it can be seen that the Raman spectrum is constant throughout the film, indicating that the same phase and composition exist for the entire film thickness.

[0347] The prepared film is smooth and flat, containing only small microcrystals( Figure 7 ), and X-ray diffraction (XRD) shows that the film is preferentially oriented in the (003) direction, where only peaks at 18.9 and 38.4° corresponding to the (003) and (006) orientations are observed( Figure 5)。The (00l) orientation of LiCoO2 has layers with an R-3m structure formed parallel to the substrate surface. The two-dimensional lithium diffusion plane parallel to the substrate makes this orientation non-ideal for the electrochemical insertion of lithium because lithium needs to travel a long path, thus limiting the rate at which lithium insertion can occur and has also been shown to have a yield lower than the theoretical capacity (Bouwman et al., Solid-state Ionics 152 (2002) 181-188). In fact, film 4 (not according to the present invention) which was observed to be strongly (003) oriented, when cycled at 25 °C under the same cycling conditions as the other films discussed, provided only 20% of its theoretical capacity (13 μAh cm -1 -2μm -1 ) by the fifth discharge cycle.

[0348] The closely packed and dense morphology of these films consists of narrow columnar microcrystals with a width of 100 - 300 (±50) nm and a length of 0.1 - 7 μm arranged perpendicular to the substrate surface (up to the entire film thickness (6700 nm)) and is essentially uniform, producing a smooth surface for the film. When viewed from above, the SEM image of the top surface only shows small microcrystals with a size less than 350 nm ( Figure 7 ). In some cases, these films have been shown to be prone to cracking, which can be detrimental to solid-state batteries.

[0349] Figure 8 Three examples of films according to embodiments of the present invention are shown, where the deposition conditions are changed during film deposition. The deposition begins as follows: Co and Li fluxes that are balanced (formulated) to produce a film having only two Raman spectral bands related to the R-3m LiCoO2 phase. During the deposition process, the Li flux is varied relative to the Co flux to slightly increase the amount of Co in the film: This is seen in the Raman spectrum by the appearance of an additional spectral band at 690 cm -1 which is known to be related to the Co3O4A 1g mode of the cobalt oxide phase. The timing and magnitude of this change can affect the final morphology of the film and allow for the adjustment of the morphology. The amount of additional cobalt added to the film is small, with the average composition of the entire LCO film remaining in the region of 47 - 49.5% lithium.

[0350] As can be seen from Figure 8 , small changes in the deposition conditions during film deposition result in deviations in the morphology of the deposited film. For example, larger plate-like microcrystals with sizes ranging from 0.4 to 2 μm in length (typically >0.3 μm) are observed within the film: These microcrystals cover more than 4% of the surface area of the film but can cover up to 80% of the surface area when viewed from above (Table 2), with the remainder of the film consisting of the above-mentioned small microcrystals (typically <0.3 μm).

[0351] Table 2 provides a comparison of the microcrystalline sizes in the LiCoO2 films described herein and Figure 12 shown in (films 1 to 3 are according to embodiments of the present invention, and film 4 is not according to the present invention). Microcrystals are not generally observed in film 4 because it is very smooth. Note that the sample of film 3 has many large particles on it, making it difficult to calculate the average roughness.

[0352] Table 2

[0353] Film 1 2 3 4 Large microcrystalline size / μm 0.7-2.0 0.5-1.0 0.4-0.9 - <![CDATA[Average area of larger microcrystals / μm 2 > 1.2 0.8 0.3 - Surface area covered by larger microcrystals / % 79 22 5 0 <![CDATA[Average surface roughness (R a ) / nm]]> 110 59 See above 4

[0354] The XRD patterns of these films show that due to the emergence of (101) and (104) orientations, the films become less preferentially oriented in the (003) orientation with peaks at 37.4 and 45.3°, and the intensities of these peaks become greater as the films have a higher surface area of larger microcrystals ( Figure 5 ). The observed morphological changes are thought to be because the addition of Co3O4 as a minor (minority) species acts as a seed layer for inoculating the growth of microcrystals with orientations ((101) and (104)) different from the orientation (003) of the bulk of the film.

[0355] Adding microcrystals with different orientations will produce Li diffusion paths through the film that are not arranged parallel to the substrate, which is advantageous for use in lithium-ion batteries because this will produce materials with improved capacity (utilization number) and better rate performance. Moreover, making the film less uniform will reduce film stress and increase the film's adhesion properties.

[0356] The cross-sectional images of the films show that near the substrate, the film is composed of densely packed microcrystals with a width of 100 - 300 (±50) nm, which are arranged perpendicular to the surface of the substrate and have the same structure as observed in film 4 (as described above). Once the film deposition conditions are changed to provide the minor species Co3O4 that can act as a seed layer, the structure deviates from the regular small microcrystal structure, and larger, less regular crystals with a size range of 300 - 2500 nm grow ( Figure 9 ). Figure 9 The cross-sectional image of film 1 is shown and shows that once the film reaches a thickness of 3000 nm, the morphology inside the film changes, which corresponds to the change seen in the Raman cross-section and can be related to the change in deposition conditions where the ratio of Co flow to Li flow changes.

[0357] Figure 10 Another embodiment (according to an embodiment of the present invention) shown in shows film 5; film 5 has a Co-rich region grown in the center of the film, as known to be related to Co3O4 at 690 cm -1As shown by the peak at [location], although the Co-rich regions are small relative to the entire film thickness, the SEM image shows that the film morphology consists of large microcrystals covering the vast majority of the film surface, thus indicating that Co3O4 has served as a seed layer, after which lithium cobalt oxide was deposited to form large plate-like microcrystals. The film contains 47 atomic % lithium (expressed as the proportion of the total atoms excluding oxygen in the crystalline oxide).

[0358] The above examples show how changing the ratio of Co and Li relative to each other during the deposition of lithium cobalt oxide can be used to control the film morphology, and that only a minor species such as Co3O4 needs to serve as a seed layer. Only a small amount of Co3O4 is needed because Co3O4 is not a cathode material, and thus its presence will reduce the capacity of the lithium cobalt oxide film.

[0359] Other methods that can be used to produce a similar effect include depositing a seed layer at the start of the lithium cobalt oxide deposition, which includes: briefly stopping the Li flow during deposition to produce a thin layer of Co3O4, rather than having Co3O4 (a more extreme form of film 5) dispersed as a minor species within the lithium cobalt oxide film; briefly or for up to several days interrupting the lithium cobalt oxide deposition, changing the substrate temperature during deposition; using additional elements at the start or during deposition to produce a seed layer.

[0360] When measured using a liquid electrolyte, it has been shown that similar irregularities in prior art pulsed laser deposition (PLD) films increase the lithium insertion rate and the capacity of the film (Bouwman et al., Solid-state Ionics 152 (2002) 181 - 188). However, when using a liquid electrolyte, the higher insertion rate and capacity for films with a higher surface area are often attributed to a rougher surface, which means a larger surface area in contact with the liquid electrolyte, which is beneficial for Li insertion and deinsertion (Jung et al., Thin Solid Films 546 (2013) 414 - 417).

[0361] Since the measurements described herein were performed on solid unit cells that do not contain a liquid electrolyte, the same trends cannot be extrapolated when using a solid electrolyte that does not wet the electrode surface in the same way as a liquid electrolyte. A liquid electrolyte can enter the voids between the microcrystals and can thus make full use of the increased surface area generated by the electrode having a rougher electrode surface. However, a solid electrolyte is deposited as a film on top of the electrode, and thus it can be expected that for solid unit cells, a smoother film will be preferred (as described in WO 2015 / 104538). Thus, although the morphology of LiCoO2 allows for easier Li insertion and an increased capacity of LiCoO2, this does not automatically result in an increased capacity in solid unit cells. In addition, irregular LiCoO2 films were previously considered unsuitable for research due to their inhomogeneity (Bouwman et al. (2002) above).

[0362] Here, LiCoO2 films were tested in solid unit cells consisting of: a platinum current collector, a LiCoO2 positive electrode, a LiPON electrolyte, and a Si negative electrode arranged in the form Pt / LiCoO2 / LiPON / Si / Pt as shown in the figure, and a package ( Figure 11 ) that is not shown in the figure.

[0363] It is shown that the presence of larger microcrystals (>0.3 μm) in the LiCoO2 film improves the utilization number (capacity) in solid unit cells compared to the mere presence of small microcrystals (<0.3 μm). However, surprisingly, a further increase in the size or surface coverage of the microcrystals within the investigated range has no significant effect on the achieved utilization number (rate).

[0364] It has been reported that less capacity decay accompanies cycling when a solid electrolyte covers the surface of LiCoO2 compared to LiCoO2 tested with a liquid electrolyte: without wishing to be bound by theory, this is thought to be related to the deterioration (degradation) of the liquid electrolyte (Tintignac et al., Electrochimica Acta 60 (2012) 121-129).

[0365] Surprisingly, films according to embodiments of the invention (films 1-3) having irregular microcrystals show a greatly improved cycle life compared to films not according to the invention (film 4) having only small, uniform microcrystals. As shown in Tables 2 and 3, this effect was confirmed even for films containing only a small amount (4.5% of the surface area) of larger microcrystals (0.4 - 0.9 μm).

[0366] Table 3 shows the number of cycles to reach 80% of the 5th cycle discharge capacity for a solid state unit cell containing a LiCoO2 film with the presented morphology when cycled at a temperature of 25 °C with a 100% depth of discharge.

[0367] Table 3

[0368] Film 1 2 3 4 Number of cycles to reach 80% discharge capacity 750 650 820 190 <![CDATA[Using number / μAh cm -2 μm -1 > 33.3 36.4 35.1 13.2

[0369] In fact, the films in Table 3 measured to cycle to 820 and 190 cycles have the same Li:Co composition (48.25 atomic % Li), yet they exhibit different film morphologies, which confirms the importance of the desired morphology.

[0370] The effect of the morphology of LiCoO2 on cycle life has not been widely reported. It has been reported in the literature that although (003)-oriented LiCoO2 thin films produce lower capacities compared to films with other (101) or (104) orientations, they also show more stable cycling with less capacity fade (Kim et al., J. Electrochem. Soc. 151 (2004) A1062 / Jung et al., Thin Solid Films 546 (2013) 414 - 417). Thus, contrary to what is shown in the present invention, it was originally expected that smoother films with smaller crystallites having a greater degree of (003) orientation would have a longer cycle life.

[0371] Additional surface roughness measurements

[0372] Additional surface roughness measurements were made on the films according to embodiments of the present invention (Examples A - D) and Comparative Example E (not according to the present invention). These measurements are given in terms of root mean square surface roughness (i.e., the root mean square average of the profile height deviations from the surface mean line). The results are listed in Table 4.

[0373] Table 4

[0374] <![CDATA[Root mean square surface roughness (R q ) / nm]]> Example A 84 Example B 147 Example C 184 Example D 83 Comparative Example E 6

[0375] All publications mentioned in the above specification are incorporated herein by reference. Various modifications and variations of the methods and systems described in the present invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the claimed invention should not be unduly limited to these specific embodiments. Indeed, various changes to the described modes for carrying out the invention that are obvious to those skilled in the chemical and materials science or related fields are intended to be within the scope of the appended claims.

Claims

1. A method for preparing a composition, the composition comprising: (a) Co3O4; and (b) crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide; the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising the following constituent elements: 45 to 55 atomic % of lithium; 20 to 55 atomic % of cobalt; and 0 to 25 atomic % of at least one additional dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, zinc, molybdenum, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium; wherein the atomic % is expressed as % of the total atoms of the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide excluding oxygen; where 0.01% to 10% of the total mass of the composition is Co3O4; where 90% to 99.99% of the total mass of the composition is crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide; where the composition has a bottom surface and a top surface; where the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide has a crystalline structure characterized by at least one of the following parameters (a) to (c): (a) at least a portion of the crystalline structure has a crystal orientation selected from (101), (104), (110), and (012) with respect to a plane parallel to the bottom surface; (b) including the following Raman spectrum: at 484 cm -1 ±25 cm -1 , 593 cm -1 ±25 cm -1 bands, and at least one band selected from 690 cm -1 ±25 cm -1 , 526 cm -1 ±25 cm -1 and 625 cm -1 ±25 cm -1 ; (c) at least one X-ray powder diffraction peak selected from 2θ 37.4° ± 0.2°, 39.1° ± 0.2°, 45.3° ± 0.2°, and 66.4° ± 0.2° measured using a CuKα X-ray source, the method comprising the steps of: providing separate vapor sources of the constituent elements of the composition, wherein the vapor sources at least include a cobalt source, a lithium source, an oxygen source, and optionally a source of at least one dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, ruthenium, copper, molybdenum, nickel, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium; heating a substrate to between 30°C and 900°C; co-depositing the constituent elements onto the substrate, wherein the constituent elements react on the substrate to form crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide, the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising one or more of lithium, cobalt, and optionally a dopant element and having a top surface and a bottom surface; and co-depositing cobalt and oxygen onto the substrate, wherein cobalt and oxygen react on the substrate to form Co3O4.

2. The method according to claim 1, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises: 45 to 55 atomic % of lithium; 40 to 55 atomic % of cobalt; and 0 to 5 atomic % of at least one dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium; wherein the atomic % is expressed as % of the total atoms of the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide excluding oxygen.

3. The method according to claim 1, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises: 45 to 55 atomic % of lithium; 42.5 to 55 atomic % of cobalt; and 0 to 2.5 atomic % of at least one dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium; wherein the atomic % is expressed as % of the total atoms excluding oxygen of the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide.

4. The method according to claim 1, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises: 45 to 55 atomic % of lithium; and 45 to 55 atomic % of cobalt; wherein the atomic % is expressed as % of the total atoms excluding oxygen of the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide.

5. The method according to claim 1, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises: 47.0 to 53.0 atomic % of lithium; and 47.0 to 53.0 atomic % of cobalt; wherein the atomic % is expressed as % of the total atoms excluding oxygen of the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide.

6. The method according to claim 1, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises: 47.5 to 49.1 atomic % of lithium; and 50.9 to 52.5 atomic % of cobalt; wherein the atomic % is expressed as % of the total atoms excluding oxygen of the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide.

7. The method according to claim 1, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide has the formula Li1Co 1-2y Mn y Ni y O2.

8. The method according to any one of claims 1 - 6, wherein 0.5% to 10% of the total mass of the composition is Co3O4.

9. The method according to any one of claims 1 - 6, wherein 1.0% to 10% of the total mass of the composition is Co3O4.

10. The method according to any one of claims 1 - 6, wherein 2.5% to 10% of the total mass of the composition is Co3O4.

11. The method according to any one of claims 1 - 7, wherein at least one of the top surface and the bottom surface has an average surface roughness (R a ) between 10 and 250 nm.

12. The method according to any one of claims 1 - 6, wherein 0.01% to 5% of the total mass of the composition is Co3O4.

13. The method according to any one of claims 1 - 6, wherein 5% to 7.5% of the total mass of the composition is Co3O4.

14. The method according to any one of claims 1 - 6, wherein 7.5% to 10% of the total mass of the composition is Co3O4.

15. The method according to any one of claims 1 - 6, wherein 0.01% to 0.05% of the total mass of the composition is Co3O4.

16. The method according to any one of claims 1 - 6, wherein 0.05% to 0.1% of the total mass of the composition is Co3O4.

17. The method according to any one of claims 1 - 6, wherein 0.1% to 0.5% of the total mass of the composition is Co3O4.

18. The method according to any one of claims 1 - 6, wherein 0.5% to 1.0% of the total mass of the composition is Co3O4.

19. The method according to any one of claims 1-6, wherein 1.0% to 1.5% of the total mass of the components is Co3O4.

20. The method according to any one of claims 1-6, wherein 1.5% to 2.0% of the total mass of the components is Co3O4.

21. The method according to any one of claims 1-6, wherein 2.0% to 3.0% of the total mass of the components is Co3O4.

22. The method according to any one of claims 1-6, wherein 3.0% to 4.0% of the total mass of the components is Co3O4.

23. The method according to any one of claims 1-6, wherein 4.0% to 5.0% of the total mass of the components is Co3O4.

24. The method according to any one of claims 1-7, wherein the component is a thin film layer including the top surface, the bottom surface, and a height of 1-50 μm.

25. The method according to any one of claims 1-7, wherein the component is a thin film layer including the top surface, the bottom surface, and a height of 1-50 μm, and the thin film layer includes a seed layer of Co3O4.

26. The method according to claim 25, wherein the seed layer is within 75% of the height from the bottom surface.

27. The method according to claim 25, wherein the seed layer is within 50% of the height from the bottom surface.

28. The method according to claim 25, wherein the seed layer is within 25% of the height from the bottom surface.

29. The method according to claim 25, wherein the seed layer is within 10% of the height from the bottom surface.

30. The method according to claim 25, wherein the seed layer is within 5% of the height from the bottom surface.

31. The method according to claim 25, wherein the seed layer is within 2.5% of the height from the bottom surface.

32. The method according to claim 25, wherein the seed layer constitutes the bottom surface of the thin film layer.

33. The method according to claim 25, wherein the seed layer is 0.1-100 nm thick.

34. The method according to claim 25, wherein the seed layer is 0.1-50 nm thick.

35. The method according to claim 25, wherein the seed layer is 0.1-25 nm thick.

36. The method according to claim 25, wherein the seed layer is 0.1-10 nm thick.

37. The method according to claim 25, wherein the seed layer is 1-50 nm thick.

38. The method according to claim 25, wherein the seed layer is 1-25 nm thick.

39. The method according to claim 25, wherein the seed layer is 1-10 nm thick.

40. The method according to claim 25, wherein the seed layer is 1-5 nm thick.

41. The method according to claim 25, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises any one, two, or all three crystal orientations selected from (101), (104), or (110).

42. The method according to claim 25, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises a (101) crystal orientation.

43. The method according to claim 25, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises a (104) crystal orientation.

44. The method according to claim 25, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises a (110) crystal orientation.

45. The method according to claim 25, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises (101) and (104), (101) and (110), or (104) and (110) crystal orientations.

46. The method according to claim 25, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises a (101) orientation, a (104) orientation, a (110) orientation, a (101) and (104) crystal orientation, a (101) and (110) crystal orientation, or a (104) and (110) crystal orientation.

47. The method according to any one of claims 1-7, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide has a crystalline rhombohedral structure, space group R-3m(166).

48. The method according to claim 25, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprises an irregular columnar crystal structure and a top surface, the top surface comprising randomly oriented plates or cluster-shaped pyramids.

49. The method according to any one of claims 1-7, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide has a crystalline structure exhibiting an X-ray powder diffraction pattern that includes X-ray powder diffraction peaks measured using a Cu Kα X-ray source at 2θ selected from: 37.4° ± 0.2°, 45.3° ± 0.2°, or both 37.4° ± 0.2° and 45.3° ± 0.2°.

50. The method according to any one of claims 1-7, wherein the method comprises: depositing Co3O4 as a seed layer on the substrate; and depositing a layer of crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising one or more of lithium and cobalt and optionally a dopant element over the Co3O4 seed layer, wherein the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising lithium and cobalt has a crystal orientation selected from (101), (104), (110), or a combination thereof with respect to a plane parallel to the bottom surface of the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide.

51. The method according to any one of claims 1-7, wherein the method comprises the following steps: depositing a first layer of the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising one or more of lithium, cobalt, and optionally a dopant element on the substrate; Deposit the Co3O4 as a seed layer on a first layer comprising crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising lithium and cobalt; and Deposit a second layer of crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising lithium, cobalt and optionally one or more dopant elements on the Co3O4 seed layer, wherein the second layer of crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising lithium and cobalt has a crystal orientation selected from (101), (104), (110) or a combination thereof with respect to the bottom surface of the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide.

52. The method according to any one of claims 1-7, comprising co-depositing Co3O4 with a crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising lithium, cobalt and optionally one or more dopant elements, and forming a mixed layer comprising Co3O4 and a crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising lithium, cobalt and optionally one or more dopant elements.

53. The method according to claim 52, comprising depositing the mixed layer on an existing layer of crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising lithium, cobalt and optionally one or more dopant elements.

54. The method according to claim 52, comprising depositing a layer of crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising lithium, cobalt and optionally one or more dopant elements on top of the mixed layer, the mixed layer comprising Co3O4 and a crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising lithium and cobalt, wherein the layer of crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising lithium, cobalt and optionally one or more dopant elements on top of the mixed layer has a top surface and a bottom surface, and has a crystal orientation selected from (101), (104), (110) or a combination thereof with respect to a plane parallel to the bottom surface.

55. The method according to any one of claims 1-7, wherein the method is a vapor deposition method and comprises the steps of: (a) Providing separate vapor sources for each of the constituent elements of the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide, wherein the separate vapor sources for each of the constituent elements comprise a lithium source, an oxygen source, a cobalt source, and optionally a source of at least one dopant element selected from: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, ruthenium, copper, molybdenum, nickel, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium; (b) Heating a substrate to between 30 °C and 900 °C; (c) Conveying a stream of lithium, a stream of oxygen, and a stream of cobalt and optionally a stream of at least one of the dopant elements; (d) Co-deposit the lithium, the oxygen, the cobalt, and optionally the at least one dopant from the source onto a heated substrate, and react the constituent elements on the substrate to form a crystalline lithium cobalt oxide or a crystalline doped lithium cobalt oxide of lithium and cobalt, the crystalline lithium cobalt oxide or the crystalline doped lithium cobalt oxide optionally containing at least one of the dopant elements and having a top surface and a bottom surface; and (e) During or prior to the co-deposition of (d), co-deposit the cobalt and the oxygen from the source onto a heated substrate, and react the constituent elements from the source to form Co3O4.

56. The method according to claim 55, wherein the crystalline lithium cobalt oxide or the crystalline doped lithium cobalt oxide includes a crystal orientation selected from (101), (104), (110), or a combination thereof with respect to a plane parallel to the bottom surface.

57. The method according to claim 55, wherein the substrate is heated to 150 °C to 700 °C.

58. The method according to claim 56, wherein the substrate is heated to 200 °C to 700 °C.

59. The method according to claim 56, wherein the substrate is heated to 200 °C to 500 °C.

60. The method according to claim 59, wherein the substrate is heated to 300 °C to 500 °C.

61. The method according to claim 55, wherein the method includes a step of changing the flow of one or more of the constituent elements to increase the amount of Co3O4 formed.

62. The method according to claim 61, including a step of reducing or eliminating the lithium flow.

63. The method according to claim 62, including a step of reducing the lithium flow.

64. The method according to claim 61, including increasing the cobalt flow.

65. The method according to claim 61, including reducing the oxygen flow.

66. The method according to claim 61, including delivering oxygen together with nitrogen or a noble gas.

67. The method according to claim 61, wherein the cobalt flow is increased relative to the cobalt flow level required for depositing the crystalline oxide of lithium and cobalt, and the lithium flow is maintained at the lithium flow level required for depositing the crystalline oxide of lithium and cobalt.

68. The method according to claim 61, wherein the cobalt flow is increased to the cobalt flow level required for depositing a mixture of the crystalline oxide of lithium and cobalt and Co3O4, and the lithium flow is maintained at the lithium flow level required for depositing the crystalline oxide of lithium and cobalt.

69. The method according to claim 61, wherein the cobalt flow is maintained at the cobalt flow level required for depositing the crystalline oxide of lithium and cobalt, and the lithium flow is reduced relative to the lithium flow level required for depositing the crystalline oxide of lithium and cobalt.

70. The method according to claim 61, wherein the cobalt flow is maintained at the cobalt flow level required for depositing the crystalline oxide of lithium and cobalt, and the lithium flow is maintained at the level required for depositing a mixture of the crystalline oxide of lithium and cobalt and Co3O4.

71. The method according to any one of claims 1-7, wherein the crystalline lithium cobalt oxide or the crystalline doped lithium cobalt oxide is HT-LiCoO2.

72. A vapor deposition method, wherein in the method according to any one of claims 1-70, co-depositing constituent elements onto a heated substrate includes co-depositing the constituent elements onto one or more layers of material supported on the substrate.

73. An electrode, which comprises a component prepared by the method according to any one of claims 1-70 or the vapor deposition method according to claim 72.

74. The electrode according to claim 73, wherein the electrode further comprises a current collecting material between the component and the substrate.

75. The electrode according to claim 74, wherein the current collecting material is a metal or a conductive metal oxide.

76. The electrode according to claim 75, wherein the current collecting material is selected from: platinum, aluminum, titanium, chromium, iron, zinc, gold, silver, nickel, molybdenum, tin oxide, indium tin oxide, and stainless steel.

77. The electrode according to claim 73, wherein the substrate is selected from: silicon, silicon oxide, aluminum oxide, aluminosilicate material, doped silicon oxide, glass, metal, and ceramic material.

78. The electrode according to claim 77, wherein the aluminum oxide is sapphire.

79. The electrode according to claim 73, wherein the electrode comprises one or more passivation layers between the substrate and the electrode.

80. The electrode according to claim 79, wherein at least one passivation layer comprises silicon dioxide.

81. The electrode according to claim 79 or 80, wherein at least one passivation layer comprises silicon nitride.

82. The electrode according to claim 74, wherein an adhesion layer exists between the current collecting material and the substrate.

83. The electrode according to claim 82, wherein the adhesion layer is selected from metals and metal oxides.

84. The electrode according to claim 83, wherein the adhesion layer is selected from: titanium oxide, titanium, zirconium, and chromium.

85. An electrochemical unit cell, comprising: an electrolyte; a negative electrode; and a positive electrode; wherein the positive electrode comprises the electrode according to any one of claims 73 to 84.

86. The electrochemical unit cell according to claim 85, wherein the electrolyte comprises a lithium phosphorus oxynitride, a lithium phosphorus sulfide, a lithium silicon sulfide Li2-SiS2, a thio-LISICON type ion conductor, a garnet type solid electrolyte, a lithium borosilicate, Li 0.5 La 0.5 TiO3, a phosphate-based LISICON type solid electrolyte, or a solid polymer electrolyte.

87. The electrochemical unit cell according to any one of claims 85-86, wherein the electrochemical unit cell is an all-solid-state electrochemical unit cell.

88. A method for manufacturing a solid-state electrochemical unit cell, comprising depositing the electrodes of the unit cell using the method according to any one of claims 1-70 or the vapor deposition method according to claim 72.

89. An electronic device, which comprises the electrochemical unit cell according to any one of claims 85-86.

90. An electrochemical unit cell, which comprises the electrode according to any one of claims 73-84 and an electrolyte.

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