Composition, method for producing the same, and use thereof

Abstract

To provide a lithium cobalt oxide with a crystal orientation with advantageous properties in lithium-ion batteries, such as capacity and cycle life.SOLUTION: A composition comprises: (a) a principal phase that is provided by a layered mixed metal oxide having a rocksalt structure belonging to the R-3m space group; the layered mixed metal oxide comprising the following component elements: 45 to 55 atomic% lithium; 20 to 55 atomic% of transition metals selected from chromium, manganese, iron, nickel, and cobalt; and 0 to 25 atomic % of additional dopant elements selected from magnesium, calcium, strontium, titanium, zirconium, vanadium, copper, ruthenium, zinc, molybdenum, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium; (b) a minor phase that is provided by a metal oxide that does not have the crystal structure of the layered mixed metal oxide, the minor phase comprising chromium, manganese, iron, nickel, and cobalt contained in the layered mixed metal oxide.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition having 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. More specifically, the composition may contain Co3O4 and a crystalline oxide of lithium and cobalt, and optionally contain one or more doping elements. The present invention also relates to a method for producing the composition and its use, particularly its use as an electrode in an electrochemical cell, particularly a lithium-ion battery.

Background Art

[0003] , , , , , , , , , + , , , ) move from the negative electrode to the positive electrode during discharge and move in the reverse direction during charging. In a non-rechargeable lithium-ion battery, metallic lithium is used, whereas in a lithium-ion battery, an intercalation compound of lithium is used as one of the electrode materials. The components of a lithium-ion battery are an electrolyte that allows the movement of ions and two electrodes.

[0002] Typically, a lithium-ion battery is composed of at least three components. Two active electrodes (anode and cathode) are separated by an electrolyte. These components are formed as thin films sequentially deposited on a support substrate. Additional components such as current collectors, interface modifiers, and sealants can also be provided. During manufacturing, these components can be deposited, for example, in the order of cathode current collector, cathode, electrolyte, anode, anode current collector, and sealant.​​​​​​​​​​​​​​​​​​​​​​​​​​

[0004] In the case of lithium ions, the anode and cathode can reversibly store lithium. Another property required of the anode material and cathode material is to obtain as much storage capacity as possible in terms of weight and volume from a material with low mass and volume, and to increase the number of stored lithium ions per unit as much as possible. These materials need to have acceptable electronic conductivity and ionic conductivity so that ions and electrons can move through the electrodes during the charging and discharging processes of the battery.

[0005] Many devices, particularly portable electronic devices, use lithium-ion batteries based on layered mixed-metal oxides having a rock-salt structure belonging to the R-3m space group. This layered mixed-metal oxide has the formula Li x M′ y O2 (M′ is a transition metal selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof). In this structure, the layers of lithium ions and the layers of transition-metal ions alternately occupy the octahedral portions of the cubic closest-packed lattice of oxide ions. Lithium ions preferentially diffuse along the lithium planes.

[0006] Examples of such mixed-metal oxides include Li x Mn 1-y M y O2 (M is a transition metal selected from the group consisting of chromium, iron, nickel, cobalt, and combinations thereof) and lithium cobalt oxide (LiCoO2). Li CoO2 has a hexagonal layered crystal structure, and Li + ions are located in the octahedral sites between the O-Co-O sheets. There is an "on". Li diffuses by vacancy hopping within the lithium plane. +

[0007] Li + The mobility of Li, and thus the electrochemical properties of LiCoO₂, are known to strongly depend on the crystal orientation in the art. Optimal diffusion of Li occurs in the cathodes with orientations (101), (104), and (110) as reported in the literature. These structures of lithium cobaltate are reported in, for example, Non-Patent Document 2 cited below and Non-Patent Document 7 cited below, where the diffusion of Li ions is mainly restricted to the grain boundary region ( 003), which is more preferable. The (110) orientation has a lithium plane arranged perpendicular to the substrate. This orientation allows easy access to lithium ions and relatively easy extraction from the structure, making it preferable for enabling high-speed diffusion of Li and a high lithium storage capacity. The (101) orientation and the (104) orientation have a slightly inclined lithium plane compared to the (110) orientation, but Li can be easily extracted and introduced into the structure. The (003) orientation consists of a Li plane arranged parallel to the substrate. This orientation is less preferable because it is difficult for lithium ions to access and is effectively trapped in the structure. Li + Li + plane and can be introduced into the structure. The (003) orientation + consists of a Li plane arranged parallel to the substrate. This orientation is less preferable because it is difficult for lithium ions to access and is effectively trapped in the structure.

[0008] Many manufacturing methods of lithium cobaltate are known in the art. For example, Patent Document 1 describes a vapor deposition method for producing crystalline lithium-containing compounds such as lithium cobaltate. When component elements react on a substrate to form a crystalline material, a lithium cobaltate film is formed on the substrate. The deposition method described in Patent Document 1 is described in the literature (Non- Patent Document 1).​​​​​​​​ It is carried out in a physical vapor deposition (PVD) system reported in Patent Document 1).

[0009] Non-Patent Document 2 describes the production of a lithium cobalt oxide film by sputtering (RF sputtering) using an alternating voltage at a rate of 100 ~1000 nm / min from a LiCoO2 target in a mixed gas of argon and O2. Non-Patent Document 2 states that in a very thin lithium cobalt oxide film (film thickness less than 0.5 μm), the (003) orientation tends to grow preferentially (RF sputtering) to minimize the surface energy, whereas in a thick lithium cobalt oxide film (film thickness less than 1 μm), a preferred (101)-(104) orientation occurs to minimize the volume strain energy generated during the annealing process. Non-Patent Document 2 reports that an X-ray amorphous film crystallized by annealing can be obtained. In some films, Co2O3, Co3O4, Li1 Co3O4, and Pt3O4 are observed in the X-ray diffraction pattern, but there is no further description about them. Since it is described that the film before heating is X-ray amorphous, these can be considered as by-products of the annealing process. Non-Patent Document 2 also discusses the influence of the substrate temperature. During high-temperature deposition, the crystal grains become larger and the proportion of voids increases (i.e., the proportion of the empty space in the material increases as the volume ratio of voids to the total volume). Non-Patent Document 2 does not describe attempts to introduce Co3O4 into the film or use it as a seeding layer, nor does it perform an analysis of the film composition. .47 Co3O4, and Pt3O4 are observed, but there is no further description about them. Since it is described that the film before heating is X-ray amorphous, these can be considered as by-products of the annealing process. Non-Patent Document 2 also discusses the influence of the substrate temperature. During high-temperature deposition, the crystal grains become larger and the proportion of voids increases (i.e., the proportion of the empty space in the material increases as the volume ratio of voids to the total volume). Non-Patent Document 2 does not describe attempts to introduce Co3O4 into the film or use it as a seeding layer, nor does it perform an analysis of the film composition. At high-temperature deposition, the crystal grains become larger and the proportion of voids increases (i.e., the proportion of the empty space in the material increases as the volume ratio of voids to the total volume). Non-Patent Document 2 does not describe attempts to introduce Co3O4 into the film or use it as a seeding layer, nor does it perform an analysis of the film composition. Non-Patent Document 2 does not describe attempts to introduce Co3O4 into the film or use it as a seeding layer, nor does it perform an analysis of the film composition.

[0010] Non-Patent Document 3 describes a film with a thickness of 0.3 - 0.5 μm grown by pulsed laser deposition (PLD).​​​​​​ It describes the influence of the substrate on the orientation of the lithium cobalt oxide film. Non-Patent Document 3 states that on a stainless steel (SS) substrate, a film with a rough and random surface orientation can be obtained, while on a silica / silicon (SiO2 / Si; SOS) substrate, a relatively smooth surface with a preferred (003) orientation can be obtained. The electrochemical properties (electroc hemistry) described in the same document indicate that the rough film deposited on SS has a high utilization rate, while the smooth film deposited on SOS has a high capacity retention ability and is structurally stable. The same document reports that all peaks other than those of the substrate in the X-ray diffraction pattern are due to the LiCoO2 thin film, and no impurity peaks such as Co3O4 are observed in the XRD diff ractogram.

[0011] Non-Patent Document 4 controls the orientation of the lithium cobalt oxide layer formed by sputtering using the substrate temperature and / or the Li2O buffer layer. A film with a preferred (1 10) or (101) orientation can be obtained at 400 °C. Also, the same document describes that the Li2O buffer layer suppresses the formation of the (003) orientation and promotes the (110) orientation.

[0012] Non-Patent Document 5 describes the preparation of lithium cobalt oxide films using RF sputtering and PLD. It is described in the same document that a film with a (110) orientation can be obtained by RF sputtering, and a film deposited by P LD has a (003) orientation. The (110) orientation film utilizes the theoretical capacity almost fully during the cycle, while the (003) film has a low reversible capacity. The electrochemical properties of the (003) film can be improved by heat treatment, using a stainless steel substrate, or lithography It can be improved by introducing defects and unevenness into the film by any of the patterning methods. According to the method described in Non-Patent Document 5, after using either RF sputtering or pulsed laser deposition (PLD) from a stoichiometric composition LiCoO2 target, the film is annealed at 600 °C either in situ or ex situ. During the annealing process, volatile Li2O volatilizes and Co3O4 is generated (Co3O4 is estimated to be about 5% degree). However, the method by long-time high-temperature treatment taught in the same document does not control the morphology of the lithium cobalt oxide film. Specifically, when LiCoO2 is deposited by PLD on an annealed RF seed layer, the existing (110) orientation is not inherited and it is taught that the preferential (001) orientation grows excessively. However, since not all

[0013] (001) reflections are observed, the structure of this film is different from that of the film grown on a bulk silicon (blank silicon) substrate. (110) orientation is not inherited, and the preferential (001) orientation grows excessively. However, since not all (001) reflections are observed, the structure of this film is different from that of the film grown on a bulk silicon (blank silicon) substrate. (blank silicon) substrate.

[0014] Non-Patent Document 6 further describes the formation of a lithium cobalt oxide film on a substrate and the subsequent annealing. The same document states that Co3O4 is slightly generated during annealing at 600 °C, that is, volatile Li2O volatilizes at high temperature and as a result LiCoO2 is converted. This process seems to be promoted by increasing the oxygen flow during the annealing process. The maximum value of the (110) diffraction peak of LiCoO2 decreased with the increase in the reflection of Co3 O4. Thus, the same document teaches that in order to prevent loss of the active material, it is necessary to make the annealing time as short as possible. O4. Thus, the same document teaches that in order to prevent loss of the active material, it is necessary to make the annealing time as short as possible.

[0015] Furthermore, in order to examine the coherence of the preferred lattice orientations facing each other between the film formed by PLD and the film formed by RF sputtering, the literature reports that a PLD film was grown on a 0.1 mm LiCoO2 seed layer formed by RF sputtering and annealed at 600 °C for 30 minutes. For comparison, PLD was also carried out on a bulk silicon substrate at the same time. This comparative sample showed the lattice plane orientation of (001), which is a typical diffraction pattern of a PLD film. 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 were observed at all. This result indicates that the film structure is not completely determined by the deposition method. Furthermore, in order to examine the coherence of the preferred lattice orientations facing each other between the film formed by PLD and the film formed by RF sputtering, the literature reports that a PLD film was grown on a 0.1 mm LiCoO2 seed layer formed by RF sputtering and annealed at 600 °C for 30 minutes. For comparison, PLD was also carried out on a bulk silicon substrate at the same time. This comparative sample showed the lattice plane orientation of (001), which is a typical diffraction pattern of a PLD film. 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 were observed at all. This result indicates that the film structure is not completely determined by the deposition method. Furthermore, in order to examine the coherence of the preferred lattice orientations facing each other between the film formed by PLD and the film formed by RF sputtering, the literature reports that a PLD film was grown on a 0.1 mm LiCoO2 seed layer formed by RF sputtering and annealed at 600 °C for 30 minutes. For comparison, PLD was also carried out on a bulk silicon substrate at the same time. This comparative sample showed the lattice plane orientation of (001), which is a typical diffraction pattern of a PLD film. 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 were observed at all. This result indicates that the film structure is not completely determined by the deposition method. Furthermore, in order to examine the coherence of the preferred lattice orientations facing each other between the film formed by PLD and the film formed by RF sputtering, the literature reports that a PLD film was grown on a 0.1 mm LiCoO2 seed layer formed by RF sputtering and annealed at 600 °C for 30 minutes. For comparison, PLD was also carried out on a bulk silicon substrate at the same time. This comparative sample showed the lattice plane orientation of (001), which is a typical diffraction pattern of a PLD film. 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 were observed at all. This result indicates that the film structure is not completely determined by the deposition method. Furthermore, in order to examine the coherence of the preferred lattice orientations facing each other between the film formed by PLD and the film formed by RF sputtering, the literature reports that a PLD film was grown on a 0.1 mm LiCoO2 seed layer formed by RF sputtering and annealed at 600 °C for 30 minutes. For comparison, PLD was also carried out on a bulk silicon substrate at the same time. This comparative sample showed the lattice plane orientation of (001), which is a typical diffraction pattern of a PLD film. 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 were observed at all. This result indicates that the film structure is not completely determined by the deposition method. Furthermore, in order to examine the coherence of the preferred lattice orientations facing each other between the film formed by PLD and the film formed by RF sputtering, the literature reports that a PLD film was grown on a 0.1 mm LiCoO2 seed layer formed by RF sputtering and annealed at 600 °C for 30 minutes. For comparison, PLD was also carried out on a bulk silicon substrate at the same time. This comparative sample showed the lattice plane orientation of (001), which is a typical diffraction pattern of a PLD film. 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 were observed at all. This result indicates that the film structure is not completely determined by the deposition method. Furthermore, in order to examine the coherence of the preferred lattice orientations facing each other between the film formed by PLD and the film formed by RF sputtering, the literature reports that a PLD film was grown on a 0.1 mm LiCoO2 seed layer formed by RF sputtering and annealed at 600 °C for 30 minutes. For comparison, PLD was also carried out on a bulk silicon substrate at the same time. This comparative sample showed the lattice plane orientation of (001), which is a typical diffraction pattern of a PLD film. 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 were observed at all. This result indicates that the film structure is not completely determined by the deposition method. Furthermore, in order to examine the coherence of the preferred lattice orientations facing each other between the film formed by PLD and the film formed by RF sputtering, the literature reports that a PLD film was grown on a 0.1 mm LiCoO2 seed layer formed by RF sputtering and annealed at 600 °C for 30 minutes. For comparison, PLD was also carried out on a bulk silicon substrate at the same time. This comparative sample showed the lattice plane orientation of (001), which is a typical diffraction pattern of a PLD film. 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 were observed at all. This result indicates that the film structure is not completely determined by the deposition method. Furthermore, in order to examine the coherence of the preferred lattice orientations facing each other between the film formed by PLD and the film formed by RF sputtering, the literature reports that a PLD film was grown on a 0.1 mm LiCoO2 seed layer formed by RF sputtering and annealed at 600 °C for 30 minutes. For comparison, PLD was also carried out on a bulk silicon substrate at the same time. This comparative sample showed the lattice plane orientation of (001), which is a typical diffraction pattern of a PLD film. 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 were observed at all. This result indicates that the film structure is not completely determined by the deposition method.

[0016] Patent Document 2 describes the production of lithium cobalt oxide, the change in the orientation of the sputtered film by modifying the substrate surface, the addition of a LiCoO2 seed layer on the substrate surface, and / or the deposition of a multilayer structure by sputtering lithium cobalt oxide under different conditions (change in gas species). Patent Document 2 describes the production of lithium cobalt oxide, the change in the orientation of the sputtered film by modifying the substrate surface, the addition of a LiCoO2 seed layer on the substrate surface, and / or the deposition of a multilayer structure by sputtering lithium cobalt oxide under different conditions (change in gas species). Patent Document 2 describes the production of lithium cobalt oxide, the change in the orientation of the sputtered film by modifying the substrate surface, the addition of a LiCoO2 seed layer on the substrate surface, and / or the deposition of a multilayer structure by sputtering lithium cobalt oxide under different conditions (change in gas species). Patent Document 2 describes the production of lithium cobalt oxide, the change in the orientation of the sputtered film by modifying the substrate surface, the addition of a LiCoO2 seed layer on the substrate surface, and / or the deposition of a multilayer structure by sputtering lithium cobalt oxide under different conditions (change in gas species).

[0017] Non-Patent Document 7 describes the determination of the crystallographic texture of a 10 μm LiCo film by changing the oxygen / argon ratio during sputtering. The formation of the (003) orientation is suppressed by the introduction of only 4% O2. Non-Patent Document 7 describes the determination of the crystallographic texture of a 10 μm LiCo film by changing the oxygen / argon ratio during sputtering. The formation of the (003) orientation is suppressed by the introduction of only 4% O2. Non-Patent Document 7 describes the determination of the crystallographic texture of a 10 μm LiCo film by changing the oxygen / argon ratio during sputtering. The formation of the (003) orientation is suppressed by the introduction of only 4% O2.

[0018] Non-Patent Document 8 describes the deposition of a lithium cobalt oxide film under low oxygen partial pressure. Specifically, the working pressure other than 20 mTorr (p = 5 mTorr). Non-Patent Document 8 describes the deposition of a lithium cobalt oxide film under low oxygen partial pressure. Specifically, the working pressure other than 20 mTorr (p = 5 mTorr). O2 = 5 mTorr) In the film deposited under (re), in addition to the HT-LiCoO2 phase, a second phase of Co3O4 is obtained as described. However, in the region where the oxygen partial pressure is high, due to Li deficiency in the film the Co3O4 phase is formed.

Prior Art Documents

Patent Documents

[0019]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0020]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

Non-Patent Document 5

Non-Patent Document 6

Non-Patent Document 7

[0021] None of the conventional documents teach a crystalline lithium cobalt oxide composition having a localized concentration of Co3O4, and the presence of such a concentration also does not teach that it is possible to produce a crystalline lithium cobalt oxide having a crystal orientation with advantageous properties in a lithium ion battery such as capacity and cycle life. Further, none of the prior arts teach a method for producing a crystalline lithium cobalt oxide composition in which the localized concentration of Co3O4 is introduced in a controlled manner so as to control the crystal orientation of lithium cobalt oxide. None of them teach a method for producing a crystalline lithium cobalt oxide composition in which the localized concentration of Co3O4 is introduced in a controlled manner so as to control the crystal orientation of lithium cobalt oxide. None of them teach a method for producing a crystalline lithium cobalt oxide composition in which the localized concentration of Co3O4 is introduced in a controlled manner so as to control the crystal orientation of lithium cobalt oxide. None of them teach a method for producing a crystalline lithium cobalt oxide composition in which the localized concentration of Co3O4 is introduced in a controlled manner so as to control the crystal orientation of lithium cobalt oxide. None of them teach a method for producing a crystalline lithium cobalt oxide composition in which the localized concentration of Co3O4 is introduced in a controlled manner so as to control the crystal orientation of lithium cobalt oxide. [Means for Solving the Problems]

[0022] According to a first aspect of the present invention, (a) Co3O4 and (b) crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide, and the crystalline oxide contains, as component elements, in atomic % of all atoms excluding oxygen in the crystalline oxide when represented, 45 to 55 atomic % of lithium, 20 to 55 atomic % of cobalt, 0 to 25 atomic % of magnesium, calcium, strontium, titanium, zirconium ium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, zinc, molybdenum denum, N, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium at least one additional dopant selected from the group consisting of terbium, europium element, and 0.01% to 10% of the total mass of the composition is Co3O4, 90% to 99.99% of the total mass (including oxygen) of the composition is crystalline lithium cobaltate um or crystalline doped lithium cobaltate, the composition has a bottom surface and a top surface, the crystalline lithium cobaltate or crystalline doped lithium cobaltate has the following parameters (a)-(c) (a) at least one crystal orientation selected from the group consisting of (101), (104), (110), and (012) (b) a band at 484 cm (b) a band at 484 cm -1 and a band at 593 cm -1 and a band at 690 cm -1 52 6 cm -1 and a band at 625 cm -1 selected from the group consisting of (for each of the bands, ±25 cm of each of the bands) -1 ) having a Raman spectrum, (c) at least one X-ray powder diffraction peak selected from the group consisting of 2θ (±0.2°) of 37.4°, 39.1°, 45.3°, and 66.4° (c) at least one X-ray powder diffraction peak selected from the group consisting of 2θ (±0.2°) of 37.4°, 39.1°, 45.3°, and 66.4° A composition is provided having a crystal structure characterized by at least one of them.

[0023] According to a second aspect of the present invention, there is provided a method for producing a crystalline composition according to the first aspect of the present invention, the method comprising providing a vapor source for each component element of the crystalline oxide, wherein each component element is cobalt, lithium, oxygen, and optionally magnesium, calcium, element is cobalt, lithium, oxygen, and optionally magnesium, calcium, Strontium, titanium, zirconium, vanadium, chromium, manganese, iron, ruthenium M, copper, molybdenum, nickel, zinc, boron, aluminum, gallium, tin, lead, bismuth Selected from the group consisting of lanthanum, cerium, gadolinium, and europium And a step of heating the substrate at about 30 ° C to about 900 ° C; A step of heating the substrate at about 30 ° C to about 900 ° C; A step of co-depositing each component element on the substrate, wherein the component elements react on the substrate To form a crystalline oxide optionally containing one or more of lithium, cobalt, and the dopant element Step; A step of co-depositing the cobalt and the oxygen on the substrate, wherein the cobalt and The oxygen reacts on the substrate to produce Co3O4.

[0024] According to a third aspect of the present invention, an electrode comprising the composition of the first aspect or the seventh aspect of the present invention Is provided. The electrode may be a positive electrode or a negative electrode. In one embodiment, the electrode is positive Pole.

[0025] According to a fourth aspect of the present invention, An electrolyte, An anode, A cathode, and An electrochemical cell is provided in which the anode and / or the cathode comprises an electrode according to the third aspect of the present invention . In one embodiment, the cathode comprises an electrode according to the third aspect of the present invention Pole.

[0026] According to a fifth aspect of the present invention, a method for manufacturing a solid electrochemical cell is provided, the method comprising: using the method according to the second aspect of the present invention, as a layer of the crystalline composition according to the first aspect of the present invention And and a step of depositing an electrode of the cell.

[0027] According to a sixth aspect of the present invention, an electronic device including the electrochemical cell according to the fourth aspect of the present invention is provided.

[0028] According to a seventh aspect of the present invention, (a) a main phase provided by a layered mixed metal oxide having a rock salt structure belonging to the R-3m space group, wherein when the layered mixed metal oxide represents atomic% with respect to all atoms excluding oxygen in the layered oxide, 45 to 55 atomic% of lithium, 20 to 55 atomic% of one or more transition metals selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof, and 0 to 25 atomic% of one or more additional 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, and a main phase containing the same; (b) a secondary phase provided by a metal oxide having no crystal structure of the layered mixed metal oxide and containing one or more of the transition metals selected from the group consisting of chromium, manganese, iron, nickel, and cobalt contained in the layered mixed metal oxide, and a composition is provided in which the main phase provides 90% to 99.5% of the total mass of the composition and the secondary phase provides 0.5% to 10% of the total mass of the composition.

[0029] Actually, the secondary phase is considered to disrupt the crystal structure of the layered mixed metal oxide. ​​​​​​​​​​In certain embodiments, the secondary phase may be amorphous. In another embodiment, the secondary phase is crystalline but has a crystal structure different from that of the layered mixed metal oxide, for example, a crystal structure belonging to a different space group In certain embodiments, the secondary phase may have a crystal structure belonging to the Fd-3m space group (when the secondary phase is provided by, for example, Co3O4) .

[0030] According to an eighth aspect, the present invention provides a method for producing the composition according to the seventh aspect of the present invention , the method comprising - a source of lithium, - a source of a transition metal selected from the group consisting of chromium, manganese, iron, nickel, and cobalt , - a source of oxygen, - optionally, a source of at least one dopant element 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 , providing a vapor source for each component element of the composition, comprising at least heating a substrate at about 30 °C to about 900 °C supplying a flux of each of the component elements onto the substrate, wherein the component elements react on the substrate to form a first phase provided by a layered mixed metal oxide having a rock salt structure belonging to the R-3m space group , supplying a flux of at least the transition metal and the oxygen onto the substrate, wherein the transition metal and the oxygen react on the substrate to form a second phase provided by a metal oxide having no crystal structure of the first phase .

[0031] According to a ninth aspect, the present invention provides a method for producing the composition according to the seventh aspect of the present invention, wherein the method comprises: lithium and 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; providing a sputtering target containing a mixed metal oxide containing; providing a further sputtering target containing a metal oxide phase containing one or more of the transition metals selected from the group consisting of chromium, manganese, iron, nickel, and cobalt contained in the first sputtering target; and sputtering the sputtering target and the further sputtering target to produce a composition, which is a sputtering deposition method, and the composition is provided by a layered mixed metal oxide of lithium and one or more of the transition metals, optionally doped with at least one of the dopant elements, and has a first phase having a rock salt structure belonging to the R-3m space group, and a second phase provided by a metal oxide having no crystal structure of the first phase and containing one or more of the transition metals selected from the group consisting of chromium, manganese, iron, nickel, and cobalt contained in the layered mixed metal oxide.

[0032] According to a tenth aspect of the present invention, there is provided a method for manufacturing a solid electrochemical cell, the method comprising: depositing an electrode of the cell as a layer of a composition according to the seventh aspect of the present invention using the method according to the eighth or ninth aspect of the present invention. It has the step of depositing. BRIEF DESCRIPTION OF THE DRAWINGS

[0033]

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Mode for Carrying Out the Invention

[0034] [Advantages and Surprising Findings] According to one aspect of the present invention, various methods disclosed herein, but not limited to , in particular, crystalline lithium cobaltate is grown by physical vapor deposition (PVD). The lithium cobaltate film can be used for an electrochemical cell, particularly a solid - state battery, for example, as a film on an inert substrate and combined with an electrolyte such as lithium phospho - oxynitride (LiPON) solid electrolyte and used as an electrode.

[0035] Generally, a layered mixed metal oxide containing lithium and one or more transition metals selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof and having a layered rock - salt structure belonging to the R - 3m space group may be grown, for example, by PVD. The obtained film can be used for an electrochemical cell, particularly a solid - state battery, for example, as a film on an inert substrate and optionally combined with an electrolyte such as lithium phospho - oxynitride (LiPON) solid electrolyte and used as an electrode. Such layered mixed metal oxides include, for example, lithium cobaltate, and in addition, Li Mn M x Mn 1-y M y O2 (where M is chromium, iron, nickel, cobalt (transition metals selected from the group consisting of Balt and combinations thereof).

[0036] Conventionally, it has been desirable to maximize the amount of electrode active material (such as lithium cobaltate or Li x Mn 1-y M y O2 etc.) in the electrode of the battery. For this reason, it has been considered preferable to prevent the presence of other phases that do not contribute to the total capacity of the battery.

[0037] For example, cobalt oxide (Co3O4) has been considered electrochemically inert and an impurity within the LiCoO2 composition. For example, see 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 31993. These documents are hereby incorporated by reference in their entirety into this specification. The capacity of a battery equipped with a cathode of LiCoO2 is defined by the amount of the LiCo O2 material. Therefore, adding Co3O4 to the LiCoO2 material will result in a decrease in the total capacity of the battery. Considering the energy density (e.g., the weight energy density that defines the capacity per unit weight (Wh / kg)), the addition of Co3O4 contributes to the weight but does not increase the capacity. Therefore, the intentional addition of Co3 O4 to the lithium oxide composition seems disadvantageous at first glance. However, by the method disclosed in this specification, it is possible to introduce Co3O4 into the crystal structure of the crystalline lithium cobaltate composition in a method with controlled concentration localization of Co3O4, and unexpectedly

[0038] ​​​, thereby enabling more precise control of the morphology of the composition than was possible with the prior art The inventors have found that this is the case.

[0039] As an example, as described in detail below, when the method for producing a crystalline lithium cobalt oxide composition is a physical vapor deposition (PVD) method, (for example, by changing the cobalt flux relative to the lithium flux, by changing the partial pressure of the feed gas, or by stopping the supply of lithium during deposition,) by introducing a concentration localization of Co3O4 into the crystal structure of the composition, it has unexpectedly been found that the morphology of the crystalline lithium cobalt oxide composition can be controlled. During deposition, controlling the flux of one atom relative to the flux of another atom, and the advantages that this control provides to the morphology of the constituent, are not disclosed in the prior art

[0040] Similarly, by a physical vapor deposition method of depositing constituent elements, another layered mixed metal oxide (Li x Mn 1-y M y O2, etc.) during deposition, by changing the relative fluxes of the constituent elements (for example, changing the manganese flux relative to the lithium flux, changing the partial pressure of the feed gas, or stopping the supply of lithium during deposition, etc.), it is conceivable that separate lithium-deficient phases with different crystal structures are formed in the layered oxide.

[0041] As will be apparent to those skilled in the art, in accordance with the effects observed when Co3O4 is introduced into lithium cobalt oxide, the presence of this separate phase can modify the morphology of the layered oxide.

[0042] ​​​​​​​​​Also, typically, the crystalline lithium cobaltate composition having the crystal orientation described herein is low in uniformity and coarse in nature exhibits excellent electrochemical behavior, both in terms of capacity and cycle life (although not limited to, in particular, when cycled at 100% depth of discharge and / or when cycled at a temperature of 25°C), as compared to a film of the same composition having a flat and smooth crystal orientation in a solid-state battery. Although the application of a film of a lithium cobaltate composition having a similar morphology to a battery using a liquid electrolyte may be taught in the prior art, the application of a lithium cobaltate film having a predetermined morphology in a battery using a solid electrolyte, and the improvement of properties (cycle life, capacity, adhesion to the underlying layer, stress control, crack reduction) when used in combination with a solid electrolyte are not disclosed in the prior art. in both capacity and cycle life, as compared to a film of the same composition having a flat and smooth crystal orientation in a solid-state battery. Although the application of a film of a lithium cobaltate composition having a similar morphology to a battery using a liquid electrolyte may be taught in the prior art, the application of a lithium cobaltate film having a predetermined morphology in a battery using a solid electrolyte, and the improvement of properties (cycle life, capacity, adhesion to the underlying layer, stress control, crack reduction) when used in combination with a solid electrolyte are not disclosed in the prior art. in both capacity and cycle life, as compared to a film of the same composition having a flat and smooth crystal orientation in a solid-state battery. Although the application of a film of a lithium cobaltate composition having a similar morphology to a battery using a liquid electrolyte may be taught in the prior art, the application of a lithium cobaltate film having a predetermined morphology in a battery using a solid electrolyte, and the improvement of properties (cycle life, capacity, adhesion to the underlying layer, stress control, crack reduction) when used in combination with a solid electrolyte are not disclosed in the prior art. in both capacity and cycle life, as compared to a film of the same composition having a flat and smooth crystal orientation in a solid-state battery. Although the application of a film of a lithium cobaltate composition having a similar morphology to a battery using a liquid electrolyte may be taught in the prior art, the application of a lithium cobaltate film having a predetermined morphology in a battery using a solid electrolyte, and the improvement of properties (cycle life, capacity, adhesion to the underlying layer, stress control, crack reduction) when used in combination with a solid electrolyte are not disclosed in the prior art. in both capacity and cycle life, as compared to a film of the same composition having a flat and smooth crystal orientation in a solid-state battery. Although the application of a film of a lithium cobaltate composition having a similar morphology to a battery using a liquid electrolyte may be taught in the prior art, the application of a lithium cobaltate film having a predetermined morphology in a battery using a solid electrolyte, and the improvement of properties (cycle life, capacity, adhesion to the underlying layer, stress control, crack reduction) when used in combination with a solid electrolyte are not disclosed in the prior art. in both capacity and cycle life, as compared to a film of the same composition having a flat and smooth crystal orientation in a solid-state battery. Although the application of a film of a lithium cobaltate composition having a similar morphology to a battery using a liquid electrolyte may be taught in the prior art, the application of a lithium cobaltate film having a predetermined morphology in a battery using a solid electrolyte, and the improvement of properties (cycle life, capacity, adhesion to the underlying layer, stress control, crack reduction) when used in combination with a solid electrolyte are not disclosed in the prior art. in both capacity and cycle life, as compared to a film of the same composition having a flat and smooth crystal orientation in a solid-state battery. Although the application of a film of a lithium cobaltate composition having a similar morphology to a battery using a liquid electrolyte may be taught in the prior art, the application of a lithium cobaltate film having a predetermined morphology in a battery using a solid electrolyte, and the improvement of properties (cycle life, capacity, adhesion to the underlying layer, stress control, crack reduction) when used in combination with a solid electrolyte are not disclosed in the prior art. in both capacity and cycle life, as compared to a film of the same composition having a flat and smooth crystal orientation in a solid-state battery. Although the application of a film of a lithium cobaltate composition having a similar morphology to a battery using a liquid electrolyte may be taught in the prior art, the application of a lithium cobaltate film having a predetermined morphology in a battery using a solid electrolyte, and the improvement of properties (cycle life, capacity, adhesion to the underlying layer, stress control, crack reduction) when used in combination with a solid electrolyte are not disclosed in the prior art. in both capacity and cycle life, as compared to a film of the same composition having a flat and smooth crystal orientation in a solid-state battery. Although the application of a film of a lithium cobaltate composition having a similar morphology to a battery using a liquid electrolyte may be taught in the prior art, the application of a lithium cobaltate film having a predetermined morphology in a battery using a solid electrolyte, and the improvement of properties (cycle life, capacity, adhesion to the underlying layer, stress control, crack reduction) when used in combination with a solid electrolyte are not disclosed in the prior art.

[0043]

[0044]

[0044] It is advantageous to introduce sufficient disorder into the above-mentioned film. Further, the method of the present invention reduces the substrate dependence of the morphology of the film. Furthermore, in the method of the present invention, lithium cobaltate having a desired orientation can be grown at a lower temperature. Finally, since Co3O4 is deposited as a seeding layer, there is no need to add an additional source during the deposition process. Similarly, for other layered oxide materials having the same crystal structure as lithium cobaltate, it will be apparent to those skilled in the art that similar effects can be obtained by providing a separate lithium-deficient phase.

[0045] In other layered oxide materials having the same crystal structure as lithium cobaltate, it will be apparent to those skilled in the art that similar effects can be obtained by providing a separate lithium-deficient phase.

[0046] [Definitions] As used herein, the range of values described herein as "X to Y" or "between X and Y" includes the terminal values X and Y.

[0047] As used herein, the term "battery" is synonymous with the term "cell" and refers to a device that can generate electrical energy from a chemical reaction or promote a chemical reaction by the introduction of electrical energy.

[0048] As used herein, the term "crystal" means a solid having a regular internal arrangement of atoms, ions, or molecules characteristic of a crystal, i.e., having long-range order in its lattice.

[0049] 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 and containing lithium and one or more transition metals selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof. ​​​​​​​​​​​​

[0050] As used herein, the term "crystalline oxide" is in the context of certain embodiments of the present invention refers to the crystalline lithium cobaltate or crystalline doped lithium cobaltate component of the compositions described herein (and does not mean the entire composition including Co3O4). In one embodiment the term "crystalline oxide" means crystalline lithium cobaltate, i.e. it means containing only lithium, cobalt and oxygen. In another embodiment, the term " crystalline oxide" means doped crystalline doped lithium cobaltate, i.e. in addition to lithium, cobalt and oxygen, it also refers to those containing at least one dopant element (selected from those listed herein) .

[0051] [Composition] 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 cobaltate of lithium (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. In the compositions of the present invention, in one embodiment, the composition has a solid structure containing both Co3O4 and a crystalline oxide. In one embodiment, both Co3O4 and the crystalline oxide are incorporated into the solid structure of the composition. In one embodiment, Co3O4 is present on the surface of the solid structure of the composition. In another embodiment, Co3O4 has a film thickness of 1 - 50 nm

[0052] As a layer, it is incorporated into the solid structure of the composition. In another embodiment, Co3O4 is incorporated into the solid structure of the composition as a seed layer.

[0053] The composition of a particular embodiment of the present invention comprises lithium and cobalt crystalline oxide (as defined herein), or crystalline doped lithium cobaltate (as defined herein). In one embodiment, at least 90% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline. In one embodiment, at least 95% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline. In one embodiment, at least 97% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline. In one embodiment, at least 98% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline. In one embodiment, at least 99% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline. In one embodiment, at least 99.5% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline. In one embodiment, at least 99.7% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline. In one embodiment, at least 99.8% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline. In one embodiment, at least 99.9% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline. In one embodiment, at least 99.95% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline. In one In an embodiment, 100% by mass of the total mass of lithium cobaltate or doped lithium cobaltate is crystalline.

[0054] As is known to those skilled in the art, crystalline lithium cobaltate may include a high-temperature phase, a low-temperature phase, or a mixture thereof. As described in Gummow et al., Material Research Bulletin, 1992, 27, 327-337, in the high-temperature phase of LiCoO2 synthesized at a high temperature (typically 700 °C or higher, preferably 800-1000 °C, more preferably about 900 °C), Li ions and Co ions are included in separate layers between the planes of the most closely packed oxygen ions. In contrast, in the low-temperature + phase of LiCoO2 synthesized at a low temperature (typically 500 °C or lower, preferably 300-500 °C, more preferably about 350-4 3+ 50 °C, most preferably about 400 °C), about 6% cobalt is included in the lithium layer.

[0055] In one embodiment, the crystalline lithium cobaltate includes at least 40% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate includes at least 50% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate includes at least 60% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate includes at least 70% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate includes at least 80% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate includes at least 80% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate includes at least 90% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate includes at least 95% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. The μ contains at least 85% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at least 90% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains at least 95% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at least 97% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at least 98% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains at least 99% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at least 99.5% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at least 99.7% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains at least 99.9% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains 100% by mass of the high-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at most 60% by mass of the low-temperature phase with respect to the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains at most 50% by mass of the low-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at most 40% by mass of the low-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at most 30% by mass of the low-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at most 20% by mass of the low-temperature phase with respect to the total mass of the crystalline lithium cobaltate.

[0056] In one embodiment, the crystalline lithium cobaltate contains at most 10% by mass of the low-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at most 5% by mass of the low-temperature phase with respect to the total mass of the crystalline lithium cobaltate. . In one embodiment, the crystalline lithium cobaltate contains at most 1% by mass of the low-temperature phase with respect to the total mass of the crystalline lithium cobaltate. Then, the crystalline lithium cobaltate contains a low-temperature phase of up to 4 0 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 30 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 20 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 15 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 10 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 5 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 3 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 2 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 1 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 0.5 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 0.3 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 0.1 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 0.5 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 0.3 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 0.1 mass% based on the total mass of the crystalline lithium cobaltate. In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 0.1 mass% based on the total mass of the crystalline lithium cobaltate.

[0057] In one embodiment, the crystalline lithium cobaltate contains a low-temperature phase of up to 0.1 mass% based on the total mass of the crystalline lithium cobaltate. In contrast, it has a high-temperature phase of 45 to 90% by mass and a low-temperature phase of 10 to 55% by mass. In one embodiment crystalline lithium cobaltate has a high-temperature phase of 60 to 9 5% by mass and a low-temperature phase of 5 to 40% by mass with respect to the total mass of the crystalline lithium cobaltate. The low relative amounts of the temperature phase and the high-temperature phase of the crystalline lithium cobaltate can be estimated using the Raman fitting method similar to that described in Tintignac Electrochimica Acta, 2012, 60, 121-129.

[0058] Typically, most of the cobalt present in the composition is in the +3 oxidation state, and the stoichiometric composition of lithium cobaltate is generally represented by LiCoO2. In certain embodiments, lithium cobaltate is in a lithium-deficient state, and the stoichiometric composition of such lithium cobaltate is Li xCoO2 (0 < x < 1). In certain embodiments, lithium cobaltate x contains lithium in a high proportion and / or at least a portion of the cobalt present in the composition is in the +2 oxidation state, and the stoichiometric composition of such lithium cobaltate is Li xCoO2 (1 < x ≦ 2). x

[0059] The crystalline oxide according to a particular embodiment of the present invention contains 45 to 55 atomic% of lithium when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment the crystalline oxide contains 46 to 54 atomic% of lithium when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 47 to 53 atomic% of lithium when expressed as a percentage of all atoms excluding oxygen in the composition. In one embodiment, the crystalline oxide contains 47.0 to 53.0 atomic % of lithium when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 47.1 to 52.0 atomic % of lithium when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 47.2 to 51.0 atomic % of lithium when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 47.3 to 50.0 atomic % of lithium when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 47.4 to 49.5 atomic % of lithium when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 47.5 to 49.1 atomic % of lithium when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 20 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 22.5 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the composition contains 25 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 27.5 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the composition contains 30 to 5

[0060] The crystalline oxide according to a specific embodiment of the present invention contains 20 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment the crystalline oxide contains 22.5 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment the crystalline oxide contains 25 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment the crystalline oxide contains 27.5 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment the composition contains 30 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment the crystalline oxide contains 32.5 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment the composition contains 35 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment the composition contains 37.5 to 55 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment It contains 5 atomic% of cobalt. In one embodiment, the composition contains 32.5 - 55 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the composition contains 35 - 55 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 37.5 - 55 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 40 - 55 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the composition contains 42.5 - 55 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 45 - 55 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 46 - 54 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 46.5 - 53.5 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 47.0 - 53 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 49.0 - 52.8 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide contains 49.0 - 52.8 atomic% of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. , contains 50.0 to 52.7 atomic % of cobalt. In one embodiment, the crystalline oxide is The crystalline oxide contains 5 0.5 to 52.6 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide is contains 50.5 to 52.5 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide. In one embodiment, the crystalline oxide is contains 50.9 to 52.5 atomic % of cobalt when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide.

[0061] In addition, the crystalline oxide may also contain a dopant element in addition to lithium and cobalt. As used herein, the term "doped crystalline oxide" means a crystalline oxide of lithium, cobalt or oxygen in the crystal structure may be substituted with other elements (hereinafter "dopant elements"). In one embodiment, lithium is such a dopant element. In one embodiment, cobalt is substituted with such a dopant element. In one embodiment, lithium and cobalt are substituted with such a dopant element. In one embodiment, oxygen is substituted with such a dopant element.

[0062] Examples of dopant elements that can substitute lithium include sodium and potassium. Examples of dopant elements that can substitute oxygen include sulfur and selenium.

[0063] In one embodiment, the dopant element substituting cobalt is divalent (in other words, in the +2 oxidation state ). In one embodiment, the dopant element substituting cobalt is trivalent (in other words, +3​​​​ in an oxidized state. In one embodiment, the dopant element that replaces cobalt is tetravalent (in other words, in the +4 oxidation state).

[0064] Examples of dopant elements that can replace cobalt include alkaline earth metals (such as magnesium, calcium, strontium, etc.), transition metals (such as titanium, zirconium, barium, sodium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, etc.), p-block elements (such as boron, aluminum, gallium, tin, lead, bismuth, etc.), and lanthanoids (such as lanthanum, cerium, gadolinium, europium, etc.).

[0065] When a dopant element that replaces cobalt is present, the doped atoms, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide, are typically at most 25%, for example at most 20%, for example at most 15%, for example at most 12.5%, for example at most 10%, for example at most 7.5%, for example at most 5%, for example at most 4%, for example at most 3%, for example at most 2%, for example at most 1.5%, for example at most 1%, for example at most 0.9%, for example at most 0.8%, for example at most 0.7%, for example at most 0.6%, for example at most 0.5%, for example at most 0.4%, for example at most 0.3%, for example at most 0.2%, for example at most 0.15%, for example at most 0.1%, for example at most 0.09%, for example at most 0.08%, for example at most 0.07%, for example at most 0.06%, for example at most 0.05%, for example at most 0.04%, for example at most 0.03%, for example at most 0. 02%, for example at most, 0.01%, for example at most 0.009%, for example at most 0.008%, for example at most 0.007%, for example at most 0.006%, for example at most 0.005%, for example at most 0.007%, for example at most 0.006%, for example at most 0.005%, for example at most Greater than 0.004%, for example, up to 0.003%, for example, up to 0.002%, for example, up to 0.0 It may be present in an amount of 01%.

[0066] In one embodiment, the doped crystalline oxide, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide, is 0 to 25 atomic% of magnesium, calcium, stron tium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, and contains at least one dopant element selected from the group consisting of. In one embodiment, the doped crystalline oxide, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide, is 0 to 20 atomic% of magnesium, calcium, strontium, titanium, zirconium, vanadium, chro mium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium, and contains at least one dopant element selected from the group consisting of. In one embodiment, the doped crystalline oxide, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide, is 0 to 15 atomic% of magnesium, calcium, strontium, titan ium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, mol ybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, ce rium, gadolinium, and europium, and contains at least one dopant element selected from the group consisting of. In one embodiment, the doped crystalline oxide is the doped crystalline oxide ribdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, se rium, gadolinium, and contains at least one dopant element selected from the group consisting of. In one embodiment, the doped crystalline oxide is the doped crystalline oxide When expressed as a percentage of all atoms excluding oxygen therein, 0 to 10 atomic % 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 contains at least one dopant element selected from the group consisting of. In one embodiment, the doped crystalline oxide, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide , contains 0 to 5 atomic % 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, and contains at least one dopant element selected from the group consisting of. In one embodiment, the doped crystalline oxide contains, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide , 0 to 2.5 atomic % 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, and contains at least one dopant element selected from the group consisting of. In one embodiment, the doped crystalline oxide contains, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide , 0 to 2 atomic % of magnesium, calcium , strontium, titanium, zirconium, vanadium Mu, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, a luminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and contains at least one dopant element selected from the group consisting of europium. One In an embodiment, the doped crystalline oxide, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide, is 0 to 1.5 atomic % of magnesium, calcium, strontium , titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, ni ckel, molybdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, la nthanum, cerium, gadolinium, and europium, and contains at least one dopant element selected from the group consisting of In one embodiment, the doped crystalline oxide, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide, is 0 to 1 atomic % of magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminum, and contains at least one dopant element selected from the group consisting of gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium. In one embodiment , the doped crystalline oxide, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide, is 0 to 0.5 atomic % of magnesium, calcium, strontium, titanium , zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, moly bdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, ceri um, gadolinium, and contains at least one dopant element selected from the group consisting of europium. In one embodiment , the doped crystalline oxide, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline oxide, is 0 to 0.5 atomic % of magnesium, calcium, strontium, titanium , zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, moly bdenum, zinc, boron, aluminum, gallium, tin, lead, bismuth, lanthanum, ceri um, gadolinium, and contains at least one dopant element selected from the group consisting of dopants It contains pant elements.

[0067] In one embodiment, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline lithium cobaltate, the doped crystalline lithium cobaltate component contains 45 to 55 atomic % of lithium, 4 0 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. A composition of the present invention containing the same is provided.

[0068] In one embodiment, when expressed as a percentage of all atoms excluding oxygen in the doped crystalline lithium cobaltate, the doped crystalline lithium cobaltate component contains 45 to 55 atomic % of lithium, 4 2.5 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. A composition of the present invention containing the same is provided.

[0069] In one embodiment, when expressed as a percentage of all atoms excluding oxygen in the crystalline oxide, the crystalline lithium cobaltate component consists of 45 to 55 atomic % of lithium and 45 to 55 atomic % of cobalt. A composition of the present invention containing the same is provided.

[0070] In one embodiment, when the amount is expressed as a percentage of all atoms excluding oxygen in the crystalline oxide, the crystalline cobalt lithium oxide component consists of 47.0 to 53.0 atomic% of lithium and 47.0 to 53.0 atomic% of cobalt, and the composition of the present invention is provided.

[0071] In one embodiment, when the amount is expressed as a percentage of all atoms excluding oxygen in the crystalline oxide, the crystalline cobalt lithium oxide component consists of 47.5 to 49.1 atomic% of lithium and 50.9 to 52.5 atomic% of cobalt, and the composition of the present invention is provided.

[0072] The crystalline composition of the embodiment of the present invention contains lithium, cobalt, and (optionally) oxygen that provides a negative ion source in the crystalline composition in addition to the dopant elements listed above. It can be understood that the composition also contains oxygen (as oxide ions O ) sufficient for the composition to be electrically neutral, and the exact amount of oxygen depends on the atomic percentages of the other elements present in the composition and the oxidation 2- state. state. It can be understood that the exact amount of oxygen is determined by the atomic percentages of the other elements present in the composition and the oxidation

[0073] A remarkable feature of the composition of the embodiment of the present invention is that the crystal structure of the composition includes a concentration localization of Co3O4. By introducing a concentration localization of Co3O4 into the crystal structure of the crystalline lithium cobalt oxide composition, the morphology of the composition can be controlled more precisely than in the prior art. The inventors have surprisingly found that this is possible. Without wishing to be bound by theory, it is believed that the concentration localization of Co3O4 may act as a seeding layer for the microcrystalline (crystallite) layer of LiCoO2. Also, without wishing to be bound by theory, the concentration localization of Co3O4 is present in the crystal structure of lithium cobalt oxide as described herein. The inventors have surprisingly found that the morphology of the composition can be controlled more precisely than in the prior art. Without wishing to be bound by theory, it is believed that the concentration localization of Co3O4 may act as a seeding layer for the microcrystalline (crystallite) layer of LiCoO2. Without wishing to be bound by theory, it is believed that the concentration localization of Co3O4 may act as a seeding layer for the microcrystalline (crystallite) layer of LiCoO2. layer. It is also believed that without wishing to be bound by theory, the concentration localization of Co3O4 may act as a seeding layer for the microcrystalline (crystallite) layer of LiCoO2. in the crystal structure of lithium cobalt oxide as described herein. Defects are generated to promote the preferred crystal orientation, and as a result, the coarse or irregular crystal morphology (such as those containing large plate-like grains) described herein is produced, which is considered to exhibit improved electrochemical properties compared to the lithium cobalt oxide compositions known in the art. When the composition is in the form of a film, the film typically exhibits large microcrystals with a size of 0.2 to 3.0 μm, preferably 0.3 to 2.5 μm. In one embodiment, the film exhibits large microcrystals with a size of 0.7 to 2.0 μm. In one embodiment, the film exhibits large microcrystals with a size of 0.5 to 1.0 μm. Typically, the size of the microcrystals is measured manually and / or using a scanning electron microscope (SEM) equipped with appropriate measuring devices and appropriate hardware and / or software.

[0074] Typically, the film contains microcrystals having a maximum dimension of at least 0.2 μm, preferably at least 0.3 μm, and in certain embodiments at least 0.4 μm, in the plane of the film. Typically, the film contains microcrystals having a maximum dimension of up to 3 μm, and in some cases up to 2 μm, in the plane of the film.

[0075] When the composition is in the form of a film, the average area of the large microcrystals of the film is typically 0.1 to 2 2 μm, preferably 0.2 to 1 μm. 2 In one embodiment, the average area of the large microcrystals of the film is 0. .8 μm. 2 In one embodiment, the average area of the large microcrystals of the film is 0.3 μm. 2 In one embodiment, the average area of the large microcrystals of the film is 0.3 μm. The average area of the large microcrystals is typically determined using appropriate measuring devices and appropriate It is measured using a scanning electron microscope (SEM) equipped with software.

[0076] 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 large microcrystals. In one embodiment, 70 to 90% of the surface area of the film, for example 75 to 85%, for example 79% is covered by large microcrystals. In one embodiment, 15 to 35% of the surface area of the film, for example 20 to 25%, for example 22% is covered by large microcrystals. In one embodiment, 1 to 10% of the surface area of the film, preferably 3 to 6%, for example 4.5 to 5.4 %, for example 5% is covered by large microcrystals. The proportion of the film covered by large microcrystals is typically measured using hardware and / or software from the area and number of large microcrystals in the imaging area by a scanning electron microscope (SEM).

[0077] As used herein, the term "crystallite" is used to denote a film region where the orientation of the crystal lattice is substantially constant. Thus, the boundaries of adjacent microcrystals are typically indicated by a change in lattice orientation. One microcrystal may contain secondary microcrystals, and all of the crystal lattices of the secondary microcrystals may be substantially in the same orientation. Typically, individual secondary microcrystals grow using adjacent secondary microcrystals as seeds, and as a result, the lattice orientations of these two secondary microcrystals are substantially oriented. In certain cases, the microcrystals as defined herein may be referred to as "grains" in the art.

[0078] Regarding the surface roughness, it can be measured using a method such as a stylus profilometry to obtain the average roughness R a and determined, and R ais the arithmetic mean value of the filtered roughness profile and is evaluated from the deviation with respect to the center line within the length of the object. When the composition is in the form of a film, the flat average surface roughness (R a ) is typically 10 - 200 nm, for example 20 - 150 nm, for example 40 - 120 nm. The average surface roughness (R a ) may be at least 10 nm, in some cases at least 30 nm, and in some cases at least 50 nm. In some cases , the average surface roughness (R a ) may be at most 250 nm. In contrast, for the smooth crystal surface where the (003) orientation which is generally not desirable for the purpose of the present invention is dominant, the average surface roughness R of the film is less than 10 nm, for example 4 nm. Typically, the average roughness is a measured using a stylus type profilometer, and the value R represents the average roughness (average deviation from the average). Typically, the average R a is calculated from the measured values at three different points spaced several millimeters apart, and each scan length is typically 2 mm. Typically, the average R a is calculated from the measured values at three different points spaced several millimeters apart, and each scan length is typically 2 mm. In an embodiment where the composition is in the form of a film, the concentration localization of Co3O4 may be present in an amount that promotes the desired structure of the resulting crystalline film.

[0079] In an embodiment where the composition is in the form of a film, the concentration localization of Co3O4 may be present in an amount that promotes the desired structure of the resulting crystalline film. In the composition of the embodiment of the present invention, 0.01% - 10% of the total mass of the composition is Co

[0080] 3O4. In one embodiment, 0.01% - 5% of the total mass of the composition is Co3O4 . In one embodiment, 5% - 7.5% of the total mass of the composition is Co3O4. In one embodiment . In one embodiment, 7.5% - 10% of the total mass of the composition is Co3O4. In one embodiment . 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, the composition has 0.1% to 0.5% of the total mass as Co3O4. In one embodiment, the composition has 0.5% to 1.0% of the total mass as Co3O4. In one embodiment, the composition has 1.0% to 1.5% of the total mass as Co3O4. In one embodiment, the composition has 1.5% to 2.0% of the total mass as Co3O4. In one embodiment, the composition has 2.0% to 3.0% of the total mass as Co3O4. In one embodiment, the composition has 3.0% to 4.0% of the total mass as Co3O4. In one embodiment, the composition has 4.0% to 5.0% of the total mass as Co3O4. The total mass represented includes all elements containing oxygen.

[0081] In one embodiment, the composition has a non-uniform distribution of Co3O4 in the composition.

[0082] Typically, the composition is formed in the form of a layer of a film, particularly a layer of a film on a substrate (as defined in detail below). In one embodiment, the composition has an upper surface and a bottom surface and is a thin film layer with a height of 1 to 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.

[0083] In one embodiment, the crystalline oxide thin film layer contains 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 from the bottom surface within 25% of the height. 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 includes the bottom surface of the thin film layer.

[0084] In one embodiment, the thickness of the seed layer is 0.1 - 100 nm. In one embodiment, the thickness of the seed layer is 0.1 - 50 nm. In one embodiment, the thickness of the seed layer is 0.1 - 25 nm. In one embodiment, the thickness of the seed layer is 0.1 - 10 nm In one embodiment, the thickness of the seed layer is 1 - 50 nm. In one embodiment, the thickness of the seed layer is 1 - 25 nm. In one embodiment, the thickness of the seed layer is 1 - 10 nm. In one embodiment, the thickness of the seed layer is 1 - 5 nm.

[0085] In one embodiment, the concentration localization of Co3O4 may be defined with respect to the thickness of the effective layer of Co3O4. As used herein, "effective layer" means the case where all Co3O4 present in the concentration localization is assumed to be uniformly dispersed throughout the bulk of the composition as a layer. The thickness of the effective layer with respect to the thickness of the crystalline oxide component of the composition can be used as an approximate value of the amount of Co3O 4 present in the concentration localization.

[0086] In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is 1 - 5 μm, and the thickness of the effective C o3O4 layer is 0.1 - 5 μm. In one embodiment, the crystalline lithium cobalt oxide ​The thickness of the composition is 2 to 20 μm, and the thickness of the effective Co3O4 layer is 0.2 to 500 nm. It is.

[0087] A further remarkable feature of the lithium cobalt oxide composition according to an embodiment of the present invention is its crystal structure. As described above, the crystalline lithium cobalt oxide composition having the morphology described herein is less homogeneous and coarser in nature than the crystalline lithium cobalt oxide used in solid-state batteries according to the prior art. In such solid-state batteries, in terms of both capacity and cycle life, compared with a film of the same composition having a flat and smooth crystal orientation, the inventors have unexpectedly found that it exhibits more favorable electrochemical behavior. The inventors have unexpectedly found that it exhibits more favorable electrochemical behavior. In one embodiment, the crystal structure of the lithium cobalt oxide composition or the doped lithium cobalt oxide composition can be defined by the Miller indices of the crystal lattice planes. As is known to those skilled in the art, the Miller indices define the notation of planes within a crystal (Bravais) lattice in crystallography. Specifically, the lattice plane group is determined by three integers h, k, l, called Miller indices. The Miller indices are described as (hkl) and represent a plane group orthogonal to hb1 + kb2 + lb3 (where b is the basis of the reciprocal lattice vector). These integers are typically written as irreducible fractions, that is, such that their greatest common divisor is 1. In one embodiment, at least a part of the crystal structure of the crystalline oxide, that is, the crystalline lithium cobalt oxide composition, the crystalline doped lithium cobalt oxide, is selected from the group consisting of (101), (104), (110), and (012), or any combination thereof.

[0088] In one embodiment, the crystal structure of the lithium cobalt oxide composition or the doped lithium cobalt oxide composition can be defined by the Miller indices of the crystal lattice planes. As is known to those skilled in the art, the Miller indices define the notation of planes within a crystal (Bravais) lattice in crystallography. Specifically, the lattice plane group is determined by three integers h, k, l, called Miller indices. The Miller indices are described as (hkl) and represent a plane group orthogonal to hb1 + kb2 + lb3 (where b is the basis of the reciprocal lattice vector). These integers are typically written as irreducible fractions, that is, such that their greatest common divisor is 1. i is the reciprocal lattice vector base). That is, they are described such that their greatest common divisor is 1.

[0089] In one embodiment, at least a part of the crystal structure of the crystalline oxide, that is, the crystalline lithium cobalt oxide composition, the crystalline doped lithium cobalt oxide, is selected from the group consisting of (101), (104), (110), and (012), or any combination thereof. 110), and (012), or any combination thereof. It has an orientation with Miller indices. In one embodiment, at least a part of the crystal structure of the crystalline oxide composition has an orientation with Miller indices selected from the group consisting of (101), (104), or both.

[0090] In the composition of an embodiment of the present invention, the crystal orientation of the crystal structure of the crystalline oxide may be defined with respect to a plane parallel to the bottom surface of the composition. Thus, in one embodiment, at least a part of the crystal structure of the crystalline oxide composition has a crystal orientation selected from the group consisting of (101), (1 04), (110), and (012), or any combination thereof, with respect to a plane parallel to the bottom surface of the composition. In one embodiment, at least a part of the crystal structure of the crystalline oxide composition has an orientation selected from the group consisting of (101), (104), or both, with respect to a plane parallel to the bottom surface of the composition.

[0091] Alternatively, in the composition of an embodiment of the present invention, the crystal orientation of the crystal structure of the crystalline oxide may be defined with respect 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.

[0092] Thus, in one embodiment, at least a part of the crystal structure of the crystalline oxide composition has a crystal orientation selected from the group consisting of (101), (104), (110), and (012), or any combination thereof, with respect to a plane parallel to the bottom surface of the composition. In one embodiment In a form, at least a part of the crystal structure of the crystalline oxide composition has a plane parallel to the bottom surface of the composition has an orientation selected from the group consisting of (101), (104), or both with respect to .

[0093] Alternatively, in the composition of an embodiment of the present invention, the crystal orientation of the crystal structure of the crystalline oxide may be defined with respect to a plane perpendicular to the crystal growth direction. In one embodiment, at least a part of the crystal structure of the crystalline oxide composition has a crystal orientation selected from the group consisting of (101), (10 4), (110), and (012), or any combination thereof, with respect to a plane perpendicular to the crystal growth direction of the crystalline oxide composition . In one embodiment, at least a part of the crystal structure of the crystalline oxide composition has an orientation selected from the group consisting of (101), (104), or both with respect to a plane perpendicular to the crystal growth direction of the crystalline oxide composition .

[0094] Alternatively, when the composition of an embodiment of the present invention is present in a lithium-ion battery, the crystal orientation of the crystal structure of the crystalline oxide may be defined with respect to a plane perpendicular to the direction of the lithium-ion path through the battery. Thus, in one embodiment, the composition of the present invention is 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 group consisting of (101), (104), (110), and (012), or any combination thereof, with respect to a plane perpendicular to the direction of the lithium-ion path through the battery . In one embodiment, at least a part of the crystal structure of the crystalline oxide composition has an orientation selected from the group consisting of (101), (104), or both with respect to a plane perpendicular to the direction of the lithium-ion path through the battery . In one embodiment, at least a part of the crystal structure of the crystalline oxide composition has an orientation selected from the group consisting of (101), (104), or both with respect to a plane perpendicular to the direction of the lithium-ion path through the battery .

[0095] ​​Alternatively, when the composition of the embodiment of the present invention is formed on a substrate, the crystal orientation of the crystal structure of the crystalline oxide may be defined with reference to a plane parallel to the substrate. Thus, in one embodiment at least a part of the crystal structure of the crystalline oxide composition has a crystal orientation selected from the group consisting of (10 1), (104), (110), and (012), or any combination thereof, with respect to a plane parallel to the substrate. In one embodiment at least a part of the crystal structure of the crystalline oxide composition has an orientation selected from the group consisting of (101), (104), or both with respect to a plane parallel to the substrate. In one embodiment, at least a part of the crystal structure of the crystalline oxide component of the composition has an orientation with a Miller index of (101) (the orientation is defined by optionally referring 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 (101) orientation. In one embodiment, at least 0.0 2% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 0.05% by mass

[0096] of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 0.1% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 0.2% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 0.5% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 1% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 2% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 5% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 1% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 2% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 5% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 5% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 5% by mass of the crystal structure of the crystalline oxide is in the (101) orientation. At least 10% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment is that at least 20% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment state, at least 30% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment state, at least 40% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment, at least 50% by mass of the crystal structure of the crystalline oxide is (101) oriented thereof. In one embodiment, at least 60% by mass of the crystal structure of the crystalline oxide is (101) oriented thereof. In one embodiment, at least 30% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment, at least 70% by mass of the crystal structure of the crystalline oxide is (10 1) oriented. In one embodiment, at least 30% by mass of the crystal structure of the crystalline oxide is ( 101) oriented. In one embodiment, at least 80% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment, at least 30% by mass of the crystalline oxide is (101) oriented. In one embodiment, at least 9 0% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment, at least 30% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment, at least 95% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment, at least 96% by mass of the crystal structure of the crystalline oxide composition is (101) oriented. In one embodiment, at least 97% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment, at least 98% by mass of the crystal structure of the crystalline oxide is (101) oriented. In one embodiment, cobalt At least 99% by mass of the crystal structure of the lithium tosylic acid composition is (101) oriented. In one embodiment, at least 99.5% by mass of the crystal structure of the crystalline oxide is (101) oriented . In one embodiment, at least 99.7% by mass of the crystal structure of the crystalline oxide composition is (10 1) oriented. In one embodiment, at least 99.9% by mass of the crystal structure of the crystalline oxide is (101) oriented. These percentages are expressed in mass relative to the total mass of the crystalline composition (i.e., , all crystal orientations present).

[0097] In one embodiment, at least a part of the crystal structure of the crystalline oxide has an orientation with a Miller index of (104 ), and the orientation is defined with reference to any of the above definitions, optionally ). In one embodiment, at least 0.01% by mass of the crystal structure of the crystalline oxide is (104) oriented. In one embodiment, at least 0.02% by mass of the crystal structure of the crystalline oxide is ([[]] 104) oriented. In one embodiment, at least 0.05% by mass of the crystal structure of the crystalline oxide is (104) oriented. In one embodiment, at least 0% by mass of the crystal structure of the crystalline oxide .1% is (104) oriented. In one embodiment, at least 0% by mass of the crystal structure of the crystalline oxide is at least 0.2% by mass and is (104) oriented. In one embodiment, the crystal structure of the crystalline oxide is at least 0.5% by mass and is (104) oriented. In one embodiment, the crystal of the crystalline oxide The structure is at least 1% by mass and is (104) oriented. In one embodiment, the crystal of the crystalline oxide The structure is at least 2% by mass and is (104) oriented. In one embodiment, the crystal structure of the crystalline oxide is at least 5% by mass and is (104) oriented. In one embodiment, the crystalline oxide At least 10% by mass of the crystal structure is (104)-oriented. In one embodiment, at least 20% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 30% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 40% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 50% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 60% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 70% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 80% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 90% by mass of the crystal structure of the crystalline oxide composition is (104)-oriented. In one embodiment, at least 95% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 96% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 97% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 98% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 99% by mass of the crystal structure of the crystalline composition is (104)-oriented. In one embodiment, at least 99.5% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 99.7% by mass of the crystal structure of the crystalline oxide composition is (104)-oriented. In one embodiment, at least 99.9% by mass of the crystal structure of the crystalline oxide composition is (104)-oriented. These percentages are based on the total mass of the crystalline oxide (i.e., all crystal orientations present). At least 20% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 30% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 40% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 50% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 60% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 70% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 80% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 90% by mass of the crystal structure of the crystalline oxide composition is (104 )-oriented. In one embodiment, at least 95% by mass of the crystal structure of the crystalline oxide is (1 04)-oriented. In one embodiment, at least 96% by mass of the crystal structure of the crystalline oxide is (104)-oriented. In one embodiment, at least 97% by mass of the crystal structure of the crystalline oxide is %. In one embodiment, at least 98% by mass of the crystal structure of the crystalline oxide is (104 -oriented. In one embodiment, at least 99% by mass of the crystal structure of the crystalline composition is oriented. In one embodiment, at least 99.5% by mass of the crystal structure of the crystalline oxide is oriented. In one embodiment, at least 99.7% by mass of the crystal structure of the crystalline oxide composition is oriented. In one embodiment, at least 99.9% by mass of the crystal structure of the crystalline oxide composition is (104)-oriented. These percentages are based on the total mass of the crystalline oxide (i.e., all crystal orientations present). In one embodiment, at least 99.9% by mass of the crystal structure of the crystalline oxide composition is (104)-oriented. These percentages are based on the total mass of the crystalline oxide (i.e., all crystal orientations present). These percentages are based on the total mass of the crystalline oxide (i.e., all crystal orientations present). It is represented by

[0098] In one embodiment, at least a part of the crystal structure of the crystalline oxide composition has an orientation with Miller indices of ( 110) (the orientation is defined, optionally, with 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 (1 10) orientation. In one embodiment, at least 0.02% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 0. 05% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 0.1% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 0.2% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 0.5% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 1% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 2% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 5% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 10% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 20% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment at least 30% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment at least 40% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment at least 50% by mass of the crystal structure of the crystalline oxide is in the (110) orientation. In one embodiment at least 60% by mass of the crystal structure of the crystalline oxide is in the (110) orientation In one embodiment, at least 70% by mass of the crystal structure of the crystalline oxide is (110) oriented. In one embodiment, at least 80% by mass of the crystal structure of the crystalline oxide is (110) oriented. In one embodiment, at least 90% by mass of the crystal structure of the crystalline oxide is (110) oriented. In one embodiment, at least 95% by mass of the crystal structure of the crystalline oxide is (110) oriented. In one embodiment, at least 96% by mass of the crystal structure of the crystalline oxide is (110) oriented. In one embodiment, at least 97% by mass of the crystal structure of the crystalline oxide is (110) oriented. In one embodiment, at least 98% by mass of the crystal structure of the crystalline oxide is (110) oriented. In one embodiment, at least... 99% by mass of the crystal structure of the crystalline oxide is (110) oriented. In one embodiment, at least 99.5% by mass of the crystal structure of the crystalline oxide is (110) oriented. In one embodiment, at least 99.7% by mass of the crystal structure of the crystalline oxide is (110) oriented. In one embodiment, at least 99.9% by mass of the crystal structure of the crystalline oxide is (110) oriented. These percentages are expressed in terms of mass relative to the total mass of the crystalline composition (i.e., all crystal orientations present).

[0099] In one embodiment, at least a part of the crystal structure of the lithium cobalt oxide composition has an orientation with a Miller index of (012) (the orientation is defined, optionally, with 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 (012) oriented. In one embodiment, at least 0.02% by mass of the crystal structure of the crystalline oxide is (012) oriented. In one embodiment, at least... 2% by mass of the crystal structure of the crystalline oxide is (012) oriented. Also, 0.05 mass% is (012) oriented. In one embodiment, the crystal structure of the crystalline oxide At least 0.1 mass% is (012) oriented. In one embodiment, the crystal structure of the crystalline oxide has at least 0.2 mass% that is (012) oriented. In one embodiment, the crystalline oxide has at least 0.5 mass% of its crystal structure that is (012) oriented. In one embodiment, the crystalline oxide has at least 1 mass% of its crystal structure that is (012) oriented. In one embodiment, the crystal line oxide has at least 2 mass% of its crystal structure that is (012) oriented. In one embodiment, the crystal line oxide has at least 5 mass% of its crystal structure that is (012) oriented. In one embodiment, the crystalline oxide has at least 10 mass% of its crystal structure that is (012) oriented. In one embodiment the crystalline oxide has at least 20 mass% of its crystal structure that is (012) oriented. In one embodiment the crystalline oxide has at least 30 mass% of its crystal structure that is (012) oriented. In one embodiment the crystalline oxide has at least 40 mass% of its crystal structure that is (012) oriented. In one embodiment, the crystalline oxide has at least 50 mass% of its crystal structure that is (012) oriented In one embodiment, the crystalline oxide has at least 60 mass% of its crystal structure that is (012) oriented In one embodiment, the crystalline oxide has at least 70 mass% of its crystal structure that is (012) oriented. In one embodiment, the crystalline oxide has at least 80 mass% of its crystal structure that is (01 2) oriented. In one embodiment, the crystalline oxide has at least 90 mass% of its crystal structure that is ( 012) oriented. In one embodiment, the crystalline oxide has at least 95 mass% of its crystal structure that is (012) oriented. In one embodiment, the crystalline oxide has at least 96 mass % of its crystal structure that is (012) oriented. In one embodiment, the crystal structure of the crystalline oxide composition has at least At least 97% by mass is (012)-oriented. In one embodiment, at least At least 98% by mass is (012)-oriented. In one embodiment, the crystal structure of the crystalline oxide At least 99% by mass is (012)-oriented. In one embodiment, the crystal At least 99.5% by mass of the structure is (012)-oriented. In one embodiment, the crystalline oxide At least 99.7% by mass of the crystal structure is (012)-oriented. In one embodiment, the At least 99.9% by mass of the crystal structure of the crystalline oxide is (012)-oriented. These percentages Are expressed as a mass relative to the total mass of the crystalline oxide (i.e., all crystal orientations present) Of.

[0100] In one embodiment, at least a part of the crystal structure of the crystalline oxide composition has a Miller index (0 03) and is oriented (the orientation is optionally defined with reference to any of the above definitions ). The presence of microcrystals having only (003) orientation results in crystals having no roughness of the above preferred orientation, and the preferred electrochemical Properties of lithium cobalt oxide having the above crystal orientation are not provided to the solid battery, which is undesirable for the purpose of the present invention. In one embodiment The maximum 99.9% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment The maximum 99.7% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment The maximum 99.5% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment The maximum 99% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment The maximum 97% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment The maximum 95% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment The maximum 95% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment Up to 90% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment up to 80% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment, up to 70% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment, the up to 60% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment, the up to 50% by mass of the crystal structure of the crystalline oxide is (003)-oriented. In one embodiment, the crystalline oxide has up to 40% by mass of its crystal structure (003)-oriented. In one embodiment, the crystalline oxide has up to 30% by mass of its crystal structure (003)-oriented. In one embodiment, the crystalline oxide has up to 20% by mass of its crystal structure (003)-oriented. In one embodiment, the crystalline oxide has up to 10% by mass of its crystal structure (003)-oriented. In one embodiment, the crystalline oxide has up to 5% by mass of its crystal structure (003)-oriented. In one embodiment, the crystalline oxide has up to 4% by mass of its crystal structure (003)-oriented. In one embodiment, the lithium cobalt oxide has up to 3% by mass of its crystal structure (003)-oriented. In one embodiment, the crystalline oxide has up to 2% by mass of its crystal structure (003)-oriented. In one embodiment, the crystalline oxide has up to 1% by mass of its crystal structure (003)-oriented. In one embodiment, the crystalline oxide composition has up to 0.5% by mass of its crystal structure (003)-oriented. In one embodiment, the crystalline oxide has up to 0.3% by mass of its crystal structure (003)-oriented. In one embodiment, the crystalline oxide has up to 0.1% by mass of its crystal structure (003)-oriented. These percentages are expressed in mass relative to the total mass of the crystalline composition (i.e., all crystal orientations present).

[0101] When the composition of the embodiment of the present invention includes a thin film layer (but not limited to, in particular, when the thin film layer includes a Co3O4 seed layer), in one embodiment, at least 2.5% of the upper surface of this thin film layer is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 4. 5% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 5% of the upper surface is a crystalline oxide having a crystal orientation selected from (1 01), (104), (110), or a combination thereof. In one embodiment, at least 7.5% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 10% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104) , (110), or a combination thereof. In one embodiment, at least 25% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110 ), or a combination thereof. In one embodiment, at least 50% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment , at least 75% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 80% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 9 % of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 10% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 25% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110 ), or a combination thereof. In one embodiment, at least 50% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment , at least 75% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 80% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 9% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 10% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 25% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110 ), or a combination thereof. In one embodiment, at least 50% of the upper surface is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, at least 0% is selected from (101), (104), (110), or a combination thereof is a crystalline oxide having a crystal orientation. In one embodiment, at least 95% of the upper surface is ( (101), (104), (110), or a crystalline oxide having a crystal orientation selected from a combination thereof is a crystalline oxide having a crystal orientation. In one embodiment, more than 95% of the upper surface is (101), (104 ), (110), or a crystalline oxide having a crystal orientation selected from a combination thereof is. In one embodiment, more than 97.5% of the upper surface is (101), (104), (110) , or a crystalline oxide having a crystal orientation selected from a combination thereof. In one embodiment , more than 99% of the upper surface is (101), (104), (110), or a combination of these is a crystalline oxide having a crystal orientation selected. In one embodiment, more than 9 9.5% is a crystalline oxide having a crystal orientation selected from (101), (104), (110), or a combination thereof .

[0102] In addition to or instead of the above, the crystal structure of the composition may be defined with respect to the bands in the Raman spectrum . As is known to those skilled in the art, in solid state physics, Raman spectroscopy is used for material property evaluation, temperature measurement, and determination of the crystallographic orientation of samples.

[0103] Typically, a Raman spectrometer uses a laser beam, typically a laser beam in the visible or near-infrared region of the electromagnetic spectrum (390 - 1000 nm), such as 450 - 900 nm, preferably 50 0 - 550 nm, more preferably 530 - 540 nm, and most preferably 532 nm . A Raman microscope typically has a magnification in the range of 5x to 500x, preferably 10x to 100x It is provided with an objective lens for the enclosure. The Raman spectrometer typically has a spatial resolution (defined as the sample surface spot area) of 0.5 to 2 μm 2 , preferably 1 μm 2 .

[0104] In a sample, the bands in the Raman spectrum may deviate from the indicated wavenumbers depending on the amount, crystal orientation, and purity of the substance having characteristic bands. In one embodiment , the wavenumbers of the bands in the Raman spectrum are indicated by ±25 cm . In one embodiment -1 , the wavenumbers of the bands in the Raman spectrum are indicated by ±20 cm . In one embodiment, the wavenumbers of the bands in the Raman -1 spectrum are indicated by ±15 cm . In one embodiment, the wavenumbers of the bands in the Raman spectrum are indicated by ±10 cm -1 . In one embodiment, the wavenumbers of the bands in the Raman spectrum are indicated by ±5 cm . In one embodiment, the wavenumbers of the bands in the Raman spectrum are indicated by ±2 cm -1 . In one embodiment, the wavenumbers of the bands in the Raman spectrum are indicated by ±1 cm . In one embodiment, the wavenumbers of the bands in the Raman spectrum are indicated by ±5 cm -1 . In one embodiment, the wavenumbers of the bands in the Raman spectrum are indicated by ±2 cm . In one embodiment, the wavenumbers of the bands in the Raman spectrum are indicated by ±1 cm -1 . In one embodiment, the composition exhibits a band at a wavenumber of 690 cm -1 in the Raman spectrum (with the tolerance shown above in either its broadest or most preferred aspect). This band is typically characteristic when the A

[0105] mode of Co3O4 in the composition is present . -1 . . 1g . .

[0106] In one embodiment, in the Raman spectrum (in either its broadest or most preferred aspect at a tolerance as shown above in either case) 526 cm -1 represents a band of frequencies. This band is typically characteristic when F of Co3O4 in the composition 2g is present.

[0107] In one embodiment, the composition shows a band of frequencies at (at a tolerance as shown above in either its broadest or most preferred embodiment) 625 cm -1 in the Raman spectrum. This band is typically characteristic when F of Co3O4 in the composition 2g is present.

[0108] In one embodiment, the composition shows a band of frequencies at (at a tolerance as shown above in either its broadest or most preferred embodiment) 484 cm -1 in the Raman spectrum.

[0109] In one embodiment, the composition shows a band of frequencies at (at a tolerance as shown above in either its broadest or most preferred embodiment) 539 cm -1 in the Raman spectrum.

[0110] In one embodiment, the (R-3m) crystal structure of the lithium cobalt oxide composition shows, in the Raman spectrum, respectively, A mode and E 1g mode, at (both at a tolerance as shown above in either its broadest or most preferred g embodiment) 484 cm and -1 593 cm -1 showing at least one band of frequencies selected from the group consisting of. These Raman bands of frequencies typically have a crystal structure of any of the preferred orientations described above It is characteristic when there is a high-temperature phase of lithium cobaltate.

[0111] In one embodiment, the composition has, in its Raman spectrum, (with the tolerance shown above in either its broadest or preferred embodiment) a band at a wavenumber of 690 cm and, -1 at least one other band at a wavenumber selected from the group consisting of (with the tolerance shown above in either its broadest or preferred embodiment) 484 cm -1 and 593 cm -1 . is shown.

[0112] In addition to or in place of the above, the crystal structure of the composition may be defined with respect to its powder X-ray diffraction pattern. As is known to those skilled in the art, X-ray crystallography is a technique used to determine the structure of atoms and molecules in a crystal, and the beam of incident X-rays is diffracted by the crystal atoms in a number of specific directions. In crystallography, by measuring the angles and intensities of this diffracted beam, a three-dimensional image of the electron density within the crystal can be created. From this electron density, in addition to the average positions of the atoms in the crystal, various information such as chemical bonds between atoms and atomic disorder can be obtained.

[0113] Typically, in X-ray diffraction, a Cu Kα X-ray source is used. Typically, measurements are made using the conditions of θ1 = 11°, θ2 = 21°, and scan time = 240 seconds. In one embodiment, the crystal structure of the crystalline oxide can be described by the measured values of 2 theta (2θ ) of the measured peaks in the X-ray powder diffraction pattern. These measured values are typically indicated as ±0.2°, preferably ±0.1°, more preferably ±0.05°.

[0114] ​​​​​In one embodiment, the crystal structure of the crystalline oxide has an X-ray powder diffraction peak where 2θ (±0.2°) is 37.4°, 39 .1°, 45.3°, and 66.4°, and is selected from the group consisting of at least one of them. The powder diffraction peak is shown.

[0115] In one embodiment, the crystal structure of the crystalline oxide has an X-ray powder diffraction peak where 2θ (±0.2°) is 37.4°. This peak is characteristic of LiCoO2 with a (101) crystal orientation. It is characteristic.

[0116] In one embodiment, the crystal structure of the crystalline oxide has an X-ray powder diffraction peak where 2θ (±0.2°) is 39.1°. This peak is characteristic of LiCoO2 with a (012) crystal orientation. It is characteristic.

[0117] In one embodiment, the crystal structure of the crystalline oxide has an X-ray powder diffraction peak where 2θ (±0.2°) is 45.3°. This peak is characteristic of LiCoO2 with a (104) crystal orientation. It is characteristic.

[0118] In one embodiment, the crystal structure of the crystalline oxide has an X-ray powder diffraction peak where 2θ (±0.2°) is 66.4°. This peak is characteristic of LiCoO2 with a (110) crystal orientation. It is characteristic.

[0119] In one embodiment, the crystal structure of the crystalline oxide can be described by the measured value of 2θ corresponding to the spacing value (d) between adjacent lattice planes (d-spacing value). This measured value is typically indicated by ±0.2 Å, preferably ±0.1 Å, more preferably ±0.05 Å. It is indicated by ±0.2 Å, preferably ±0.1 Å, more preferably ±0.05 Å.

[0120] In one embodiment, the crystal structure of the crystalline oxide corresponds to a d value (Å) of 2.339 (±0.1). It shows an X-ray powder diffraction peak where the corresponding 2θ is 37.4°. This peak is characteristic of LiCoO₂ with a crystal orientation of (101).

[0121] In one embodiment, the crystal structure of the crystalline oxide shows an X-ray powder diffraction peak where the corresponding 2θ is 39.1° for a d value (Å) of 2.301 (±0.1). This peak is characteristic of LiCoO₂ with a crystal orientation of (012). crystal orientation of (012).

[0122] In one embodiment, the crystal structure of the crystalline oxide shows an X-ray powder diffraction peak where the corresponding 2θ is 45.3° for a d value (Å) of 2.001 (±0.1). This peak is characteristic of LiCoO₂ with a crystal orientation of (104). crystal orientation of (104).

[0123] In one embodiment, the crystal structure of the crystalline oxide shows an X-ray powder diffraction peak where the corresponding 2θ is 66.4° for a d value (Å) of 1.406 (±0.1). This peak is characteristic of LiCoO₂ with a crystal orientation of (110). crystal orientation of (110).

[0124] In one embodiment, the crystalline oxide has a crystal structure showing X-ray powder diffraction where the 2θ corresponding to a d value (Å) (±0.1 Å) selected from 2.399 Å, 2.001 Å, or both 2.399 Å and 2.001 Å is selected from 3 7.4°, 45.3°, or both 37.4° and 45.3°. folds.

[0125] One skilled in the art will understand that the crystal structure of the lithium cobalt oxide composition may include microcrystals having two or more of the above orientations, and thus, two or more of the above peaks may be observed in the powder X-ray diffraction pattern of a sample of the composition. crystal orientation of (101). pattern of a sample of the composition.

[0126] In one embodiment, the crystal structure of the lithium cobalt oxide composition is 37.4°, 45.3°( each ±0.1 Å) or both of these, and / or the corresponding d-value (Å) is 2.39 9, 2.001 (each ±0.1 Å) or both of these, and exhibits at least one X-ray powder diffraction peak selected from the group consisting of

[0127] In one embodiment, a composition comprising a crystalline oxide of lithium and cobalt is provided, and in this composition, the atomic percentages of lithium and cobalt are as defined above in either its broadest or preferred aspect, and the crystal structure of the composition is characterized by a concentration localization of Co3O4 as defined above in either its broadest or preferred aspect, and the crystal structure is further characterized by the following parameters (a) to (c): (a) A crystal orientation selected from the group consisting of (101), (104), (110), and (012); (b) A band at a wavenumber of 690 cm -1 (±5 cm -1 ) in the Raman spectrum, and at least one other band at a wavenumber selected from the group consisting of -1 484 cm -1 and 593 cm -1 (each ±5 cm -1 ); (c) At least one X-ray powder diffraction peak selected from the group consisting of 37.4°, 39.1°, 45.3°, and 66.4° (each ±0.2 Å) and / or the corresponding d-value (Å) of 2.399, 2.301, 2.001 or 1.4 (each ±0.1°), characterized by at least one of these.

[0128]

[0128] In one embodiment, a composition comprising a crystalline oxide of lithium and cobalt is provided, and in this composition, In the product, the atomic percentages of lithium and cobalt are as defined above in either its broadest or preferred aspect, and in either case, the crystal structure of the composition is, in either its broadest or preferred aspect, characterized by the concentration localization of Co3O4 as defined above, and (101), (104), (110), and (012), preferably (101) or (1 04), by an orientation selected from the group consisting of.

[0129] In one embodiment, a composition comprising a crystalline oxide of lithium and cobalt is provided, and in this composition, the atomic percentages of lithium and cobalt are as defined above in either its broadest or preferred aspect, and in either case, the crystal structure of the composition is, in either its broadest or preferred aspect, characterized by the concentration localization of Co3O4 as defined above, and a band at a wavenumber of 690 cm -1 (±5 cm -1 ) and is characterized by by.

[0130] In one embodiment, a composition comprising a crystalline oxide of lithium and cobalt is provided, and in this composition, the atomic percentages of lithium and cobalt are as defined above in either its broadest or preferred aspect, and in either case, the crystal structure of the composition is, in either its broadest or preferred aspect, characterized by the concentration localization of Co3O4 as defined above, and 37.4°, 39.1°, 45.3°, and 66.4° (each ±0.2 Å), and / or the corresponding interplanar spacing value d(Å) is 2.399, 2.301, 2.001 or 1.40 6 (each ±0.1°), preferably the interplanar spacing value d(Å) 2.399 or 2.001 corresponding to characterized by at least one X-ray powder diffraction peak selected from the group consisting of 37.4° or 45.3° in response and is characterized by the following.

[0131] Typically, lithium cobaltate is formed in the form of a film, particularly a film on a substrate (defined in detail below). In one embodiment, the thickness of the crystalline lithium cobaltate composition is 1-30 μm. In one embodiment, the thickness of the crystalline lithium cobaltate composition is 2-20 μm In one embodiment, the thickness of the crystalline lithium cobaltate composition is 3-12 μm. In one embodiment, the thickness of the crystalline lithium cobaltate composition is 5-10 μm. In one embodiment the thickness of the crystalline lithium cobaltate composition is 6-7 μm. In one form, the thickness of the crystalline lithium cobaltate composition is 6-7 μm. Method

[0132] The present invention also provides a method for producing a composition containing Co3O4 and crystalline lithium cobaltate, although not limited to the composition according to the first aspect of the present invention. The method generally includes a step of providing a source for each component element of the compound, where the source includes a source of lithium, a source of oxygen, and a source of cobalt (and optionally a source of one or more dopant elements defined below), and a step of depositing these on a substrate, although not limited to but particularly a substrate heated to about 50°C to about 800°C. The component elements react on the substrate from the source to form a crystalline oxide of lithium and cobalt (doped with one or more elements defined below, optionally), and the component elements react on the substrate from the source of cobalt and the source of oxygen to form Co3O4. Including. The component elements react on the substrate from the source to form a crystalline oxide of lithium and cobalt (doped with one or more elements defined below, optionally), and the component elements react on the substrate from the source of cobalt and the source of oxygen to form Co3O4. Typically, the method involves crystalline lithium cobaltate (or crystalline doped lithium cobaltate

[0133] Typically, the method involves crystalline lithium cobaltate (or crystalline doped lithium cobaltate​ (Uhm) is formed in the form of a film, typically a film on a substrate. Suitable substrates are known to those skilled in the art and include metals (e.g., platinum, aluminum, titanium, chromium, iron, zinc, gold, silver, nickel, molybdenum, alloys thereof, and the alloys may contain non-metals such as carbon, and examples thereof include steels such as stainless steel), oxides such as aluminum oxide, particularly, conductive metal oxides such as indium tin oxide, silicon, silica, silicon oxide (including doped silicon oxide), aluminosilicate materials, glass, and ceramic materials, etc. are included.

[0134] In contrast to the methods described in the prior art, the method of the example of the present invention has the remarkable feature that one or more conditions of the method are changed such that a concentration localization of Co3O4 is formed that enables the crystal growth of a lithium cobaltate composition having the desired crystal structure (in either the broadest or most preferred embodiment as defined above).

[0135] In one embodiment, the method enables the crystal growth of a composition having the desired crystal structure, and furthermore, one or more conditions of the method are changed such that a concentration localization of Co3O4 is formed as a seed layer so that the roughness / asperity is greater than that of the prior art (as described above).

[0136] The method generally includes a step of providing a source for each component element of the compound, and the source includes a source of lithium, a source of oxygen, a source of cobalt, and optionally, a source of one or more of the dopant elements listed herein. This source of the element is not critical to the present invention as long as the necessary elements are contained. ​ 。

[0137] The reaction of the component elements to form the compound occurs not in the gas phase before deposition onto the substrate, but on the surface of the substrate. Without wishing to be bound by theory, each component element in the form of vapor impinges on and adheres to the heated substrate surface, and then the atoms of each element move on the surface, whereby they can react with each other to form an oxidation compound.

[0138] In one embodiment, the vapor source comprises an electron beam evaporator or a Knudsen cell (K-Cell), which are suitable for materials with low partial pressures. In either case, the material is placed in a crucible and heated to generate a flux of atoms. In a Knudsen cell, a series of heating filaments are used around the crucible, whereas in an electron beam evaporator, heating is effected by using a magnet to direct a high-energy electron beam towards the material.

[0139] Typically, lithium and cobalt can be deposited from a Knudsen cell source or an electron gun (E-gun).

[0140] In one embodiment, the source of oxygen is molecular oxygen. In one embodiment, the source of oxygen is atomic oxygen (typically produced by, but not limited to, an oxygen plasma source). In one embodiment, the source of oxygen is an ozone source.

[0141] The oxygen plasma source supplies a flux of plasma-phase oxygen, i.e., oxygen atoms, radicals, and ions. The source may be, for example, a radio frequency (RF) plasma source or an ozone source.

[0142] Optionally, a small amount of additional gas (typically, a noble gas such as helium, neon, argon, krypton, xenon; or nitrogen; preferably argon and / or nitrogen) may be added to the oxygen stream. When one or more additional gases are present, the amount of the additional gas present is up to 10% in total proportion, e.g., up to 5%, e.g., up to 3%, e.g., up to 2%, e.g., up to 1%. The total proportion is typically measured by a residual gas analyzer (RGA) and is defined as the mole percentage relative to 100 mole % of oxygen by dividing the partial pressure of one or more additional gases by the partial pressure of oxygen.

[0143] In addition to the sources of lithium, cobalt, and oxygen, sources of other dopant elements that form part of the crystal structure of the desired composition (as defined and exemplified above) may also be present. In one embodiment, the method further comprises one or more elements selected from the group consisting of 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, and provides a source of the one or more elements such that the one or more elements form part of a crystalline composition having the desired crystal structure.

[0144] Alternatively, an amorphous film can be deposited and then the method of the present invention can be used to anneal this amorphous form. However, this approach is not preferred because it does not exhibit the advantages of the present invention, such as being able to directly produce a stoichiometric compound at a low substrate temperature and eliminating the need for high-temperature annealing

[0145] One of the general methods used according to an embodiment of the present invention is physical vapor deposition (PVD). This method provides a vapor source for each component element of the compound, and the component elements are co-deposited from the vapor source onto a substrate, typically a heated substrate, so that a crystalline lithium cobalt oxide composition is formed from each component element of lithium, cobalt, and oxygen. Therefore, in this embodiment, a vapor source for each component element of the compound is provided, including a source of lithium, a source of oxygen, a source of cobalt, and optionally 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. A step of supplying a flux of lithium, a flux of cobalt, and optionally a flux of the at least one dopant element is performed. A step of heating the substrate to substantially 50 °C to 800 °C, and a step of depositing the component elements from the source onto the substrate to form a crystalline oxide of lithium and cobalt optionally containing one or more dopant elements are provided. During or before the co-deposition, one or more conditions of the physical vapor deposition method are changed such that a concentration localization of Co3O4 is formed to enable crystal growth of a composition having the desired crystal structure.

[0146] The physical vapor deposition (PVD) method according to one aspect of the present invention typically includes a step of co-depositing component elements from a vapor source onto a heated substrate. In one embodiment, the substrate is from about 150 to about

[0147] ​​​​​​​​​​​​​It is heated to 700 °C. In one embodiment, the substrate is heated to about 200 to about 700 °C. In one embodiment, the substrate is heated to about 300 to about 450 °C.

[0148] The physical vapor deposition (PVD) method according to one aspect of the present invention is typically 1×10 -7 ~1×1 0 -4 Torr, preferably 1×10 -6 ~5×10 -5 Torr, more preferably 5× 10 -6 ~2×10 -5 Torr and is carried out at a pressure of.

[0149] Typically, the method is carried out such that the deposition rate of the film is 0.1 to 10 μm / h . In one embodiment, the method is carried out such that the deposition rate of the film is 0.2 to 5 μm / h . In one embodiment, the method is carried out such that the deposition rate of the film is 0.3 to 1.6 μm / h . In one embodiment, the method is carried out such that the deposition rate of the film is 0.4 to 0.8 μm / h .

[0150] According to this aspect of the present invention, one or more conditions of the vapor deposition method are changed so as to enable crystal growth of a composition having a desired crystal structure so that a concentration localization of Co3O4 is formed. . In one embodiment, the change in one or more conditions includes supplying cobalt and lithium at a flux ratio different from the flux ratio supplied for depositing a crystalline oxide of lithium and cobalt . Without wishing to be bound by theory, supplying cobalt and lithium at a flux ratio different from the flux ratio supplied for depositing crystalline lithium cobaltate enables crystal growth of a lithium cobaltate composition having a desired crystal structure more than. Thus, a lithium cobaltate composition having a desired crystal structure is enabled to grow crystals Co3O4 is considered to be formable (typically as a seeding layer).

[0151] In one embodiment, the cobalt flux is 0.1 to 13 Å / sec. In one embodiment, the cobalt flux is 0.1 to 7 Å / sec. In one embodiment, the cobalt flux is 0.4 to 2 Å / sec. In one embodiment, the cobalt flux is 0.5 to 1 Å / sec. This flux is typically measured on the substrate surface. Typically, the cobalt flux is measured in the presence of oxygen (when measured in this way, the actually measured value is the flux of cobalt oxide).

[0152] In one embodiment, the lithium flux is 0.1 to 26 Å / sec. In one embodiment, the lithium flux is 0.5 to 13 Å / sec. In one embodiment, the lithium flux is 0.7 to 4 Å / sec. In one embodiment, the lithium flux is 0.8 to 2.2 Å / sec. This flux is typically measured on the substrate surface. Typically, the lithium flux is measured in the presence of oxygen (when measured in this way, the actually measured value is the flux of lithium oxide).

[0153] When one or more dopant elements are present, in one embodiment, the dopant element flux is 0.1 to 13 Å / sec. In one embodiment, the dopant element flux is 0.1 to 7 Å / sec . In one embodiment, the dopant element flux is 0.4 to 2 Å / sec. In one embodiment the dopant element flux is 0.5 to 1 Å / sec. This flux is typically measured on the substrate surface . Typically, the dopant element flux is measured in the presence of oxygen (in this way of measuring, the actually measured value is the flux of the oxide corresponding to the dopant element). ​​

[0154] During deposition, the velocity of each atomic flux can be measured and changed, enabling control of the composition of the entire film thickness, coping with changes in the conditions of the vapor source (e.g., deterioration or fluctuations of the source), and keeping the composition of lithium-cobalt constant throughout the film, or generating a film in which the composition of lithium-cobalt changes during deposition. The velocity of each atomic flux can be measured directly at the source during deposition and / or indirectly (by measuring the oxygen partial pressure during deposition). In one embodiment, the velocity of each atomic flux is measured by electron impact emission spectroscopy (EIES).

[0155] According to this aspect of the present invention, the controlled change in the composition during deposition can be effectively utilized to generate a seed layer in the film. For example, the addition of a Co3O4 seed layer into the film during deposition can be achieved by changing the individual atomic fluxes by the preferred methods described below.

[0156] In one embodiment, the change in one or more conditions includes increasing the cobalt flux relative to the lithium flux required for the deposition of the crystalline oxide of lithium and cobalt.

[0157] In one embodiment, the cobalt flux is increased relative to the level of the cobalt flux required for the deposition of the crystalline oxide of lithium and cobalt, and the lithium flux is maintained at the level of the lithium flux required for the deposition of the crystalline oxide of lithium and cobalt.

[0158] In one embodiment, the cobalt flux is maintained at the level of the cobalt flux required for the deposition of the crystalline oxide of lithium and cobalt, and the lithium flux required for the deposition of the crystalline oxide of lithium and cobalt ​​​​​​​​​​​​ Reduce the lithium flux below the level of the lithium flux.

[0159] In one embodiment, reduce the oxygen flux. In one embodiment, oxygen is supplied together with an (inert gas defined and exemplified above) to dilute the oxygen while maintaining the oxygen flux at the same level, thereby controlling by lowering the oxygen partial pressure. as described above). This is done by controlling the oxygen partial pressure.

[0160] The control of the atomic flux velocity is only one of the methods that can be used to control the morphology of lithium cobaltate in embodiments of physical vapor deposition methods. Other methods that can be used to provide a concentration localization (such as a seed layer) of Co3O4 include closing the shutter of lithium to stop the flux of lithium ions, and changing the oxygen partial pressure in the chamber (by changing the flow rate of oxygen or adding another gas such as argon). etc.) are mentioned. closing the shutter of lithium to stop the flux of lithium ions, or changing the oxygen partial pressure in the chamber (by changing the flow rate of oxygen or adding another gas such as argon). argon).

[0161] In one embodiment, in the vapor deposition method, the step of co-depositing component elements on a heated substrate includes directly co-depositing the component elements on the surface of the heated substrate. In one embodiment, in the vapor deposition method, the step of co-depositing component elements on a heated substrate includes co-depositing the component elements on one or more layers supported on the substrate.

[0162] According to an example of the present invention, the vapor deposition method outlined in Patent Document 1 is modified according to the essence of the present invention to form the required concentration localization of Co3O4.

[0163] The deposition method described in Patent Document 1 is carried out in a physical vapor deposition (PVD) system heated to 50 - 800°C. In one embodiment, on a bare substrate or (without including a heat-sensitive battery layer) ​ (i) When depositing the LCO film on the current collector layer, the temperature is preferably 300 to 450 °C, but a high substrate temperature of up to 800 °C can also be used.

[0164] In one embodiment, the method additionally has a step of 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 a lithium cobalt oxide film on the deposited battery layer to form a laminated battery, the annealing temperature of the substrate is preferably 300 to 450 °C.

[0165] Conventionally, by providing a vapor source for each of lithium, oxygen, and cobalt (and optionally a vapor source for one or more of the dopant elements), controlling the flux of each supply source to co-deposit on a substrate, and reacting these on the substrate to form a crystalline oxide, it is considered possible to prevent the formation of Co3O4 (as described above, conventionally, cobalt oxide (Co3O4) was considered an impurity in the LiCoO2 composition). Therefore, it seems at first glance disadvantageous to intentionally produce a composition containing Co3O4 and crystalline lithium cobalt oxide using this method.

[0166] Alternatively, the method according to the present invention may be carried out by sputtering. As is known to those skilled in the art, the sputter deposition method is a physical vapor deposition (PVD) method for depositing a thin film by sputtering. Sputtering releases material from one or more targets that are sources of the required elements and directs it towards the substrate, typically growing the required material as a film on the substrate. ​ It has a step of...

[0167] Therefore, in one embodiment, a method for preparing the composition of the embodiment of the present invention is provided, and the method is providing at least one sputtering target containing a source of lithium, at least one sputtering target containing a source of cobalt, and optionally one or more sputtering targets containing 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, scandium, lead, bismuth, lanthanum, cerium, gadolinium, and europium, the step of providing at least one sputtering target, wherein the sputtering targets may be the same or different, and sputtering the sputtering target to produce a composition containing Co3O4 and a crystalline oxide of lithium and cobalt, and optionally doped with at least one of the dopant elements, which is a sputtering deposition method having a step of... Typically, the sputtering target providing the source of the required element contains the oxide of that element such that the target provides the source of the element and at least a part of the source of oxygen. In one embodiment, the sputtering target that is the source of lithium contains lithium oxide (Li2O). In one embodiment, the sputtering target that is the source of cobalt contains cobalt(II) oxide (CoO). In one embodiment ... ... ... ... ... ... ...

[0168] ... ... ... ... ... , the sputtering target that is a source of cobalt is cobalt(III) oxide (Co2 O3). In one embodiment, the sputtering target that is a source of cobalt contains Co3O4.

[0169] In one embodiment, sputtering may be performed using one target that provides sources of both lithium and cobalt, preferably as oxides. In this embodiment, the sputtering target that provides sources of both lithium and cobalt contains Li CoO2. This target may optionally have lithium (e.g., Li2O) added to provide a composition with a high proportion of lithium. In this embodiment, the oxygen partial pressure may be varied during deposition of the composition to localize the concentration of Co3O4.

[0170] In one embodiment, sputtering is performed using one sputtering target that provides a source of lithium and part of a source of cobalt, preferably as an oxide, more preferably as LiCoO2 (optionally with Li2O added), and at least one other sputtering target that typically contains Co3O4 and provides part of a source of cobalt. The desired composition contains 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,

[0171] boron, aluminum, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium, and europium. In this case, the sputtering target typically contains an oxide of the element. The dope ring target containing an oxide of the doping element may be the same as or different from the sputtering target containing an oxide of lithium and / or cobalt.

[0172] If the sputtering targets are different, these targets may be sputtered simultaneously or sequentially.

[0173] In one embodiment, a method for preparing a composition of an embodiment of the present invention is provided, the method comprising: providing a first sputtering target containing cobalt oxide; (a) lithium cobaltate, or (b) at least one 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, and providing a second sputtering target containing a source of lithium cobaltate doped with at least one of the doping elements; sputtering the first sputtering target and the second sputtering target to produce a composition containing Co3O4 and a crystalline oxide of lithium and cobalt, and optionally doped with at least one of the doping elements, in a sputtering deposition method.

[0174] In one embodiment, a method for preparing a composition of an embodiment of the present invention is provided, the method comprising: sputtering the first target to produce a thin film layer of Co3O4, and then sputtering a second target to optionally produce a thin film crystalline oxide of lithium and cobalt doped with at least one of the dopant elements a step of forming a thin film crystalline oxide of lithium and cobalt doped with at least one of the dopant elements , which is a sputtering deposition method having

[0175] In one embodiment, there is provided a method for preparing a composition according to an embodiment of the present invention, the method comprising sputtering the first target to form a thin film layer of Co3O4 having an upper surface and a bottom surface a step of forming a layer; sputtering the second target to optionally form a thin film crystalline oxide of lithium and cobalt doped with at least one of the dopant elements on the upper surface of the thin film layer of Co3 O4, which is a sputtering deposition method having a step of forming on the upper surface of the thin film layer of O4

[0176] In one embodiment, there is provided a method for preparing a composition according to an embodiment of the present invention, the method comprising providing a first sputtering target containing Li2O and / or an oxide of lithium and cobalt, and a second sputtering target containing an oxide of cobalt (preferably Co3O4); a step of providing a second sputtering target containing an oxide of cobalt (preferably Co3O4); a step of sputtering the targets simultaneously to form a mixed thin film layer containing Co3O4 and a crystalline oxide of lithium and cobalt; which is a sputtering deposition method having a step of forming a mixed thin film layer containing Co3O4 and a crystalline oxide of lithium and cobalt a step of forming a mixed thin film layer containing Co3O4 and a crystalline oxide of lithium and cobalt

[0177] In one embodiment, there is provided a method for preparing a composition according to an embodiment of the present invention, the method comprising providing a first sputtering target containing Li2O or / and an oxide of lithium and cobalt, and a second sputtering target containing an oxide of cobalt (preferably Co3O4); a step of providing a second sputtering target containing an oxide of cobalt (preferably Co3O4); a step of providing a second sputtering target containing an oxide of cobalt (preferably Co3O4); Sputter the second target to form a thin film layer of Co3O4, and then sputter the first target to form a thin film crystalline oxide of lithium and cobalt on the thin film layer of Co3O4. The sputtering deposition method has such a process.

[0178] Typically, the high-energy particles are gaseous ions. In one embodiment, the gaseous ions are argon ions.

[0179] Examples of types of sputtering deposition methods include RF sputtering, DC sputtering , pulsed DC sputtering, ion beam sputtering, reactive sputtering, target high utilization sputtering (HiTUS), high power impulse magnetron sputtering (HiPiMS), and gas flow sputtering.

[0180] The sputtering method according to this example of the present invention is typically at a pressure of 1×10 -4 ~1×10 -2 Torr, preferably 5×10 -4 ~5×10 -2 Torr, more preferably 1×10 - 3 ~2×10 -3 Torr.

[0181] Alternatively, the method according to the present invention may be implemented by a chemical vapor deposition method. As is known to those skilled in the art, the chemical vapor deposition method includes a step of providing a vapor source of each component element of a desired substance containing one or more precursor compounds containing the required elements, and a step of depositing the volatilized elements on a heated substrate, typically by spraying. The component elements react on the substrate from the supply source to form the desired substance.

[0182] Accordingly, a method for preparing a crystalline lithium cobaltate composition (not limited thereto, particularly the composition of an embodiment of the present invention) is further provided, and the method includes: providing a source of each component element of the compound, wherein the source contains at least one precursor compound containing lithium, at least one precursor compound containing cobalt, and at least one precursor compound containing oxygen, and contains at least one precursor compound; heating a substrate to about 200°C to about 1000°C; spraying the precursor compound onto the heated substrate, which is a vapor deposition method, wherein component elements react on the substrate from the source to form a crystalline oxide of lithium and cobalt, and one or more conditions of the method are changed so that a concentration localization of Co3O4 is formed to enable crystal growth of a composition having a desired crystal structure. In one embodiment, the substrate is heated to 250 to 950°C. In one embodiment, the substrate is heated to 300 to 600°C. 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. In one embodiment, the precursor compounds are mixed to form a sol before being sprayed onto the heated substrate. The precursor compounds are not particularly limited as long as at least one precursor compound contains lithium and at least one precursor compound contains cobalt. In one embodiment, lithium is provided by a lithium compound such as lithium acetate, lithium carbonate, lithium hydroxide, or lithium oxide. Cobalt is provided by a cobalt compound such as cobalt acetate, cobalt carbonate, cobalt hydroxide, or cobalt oxide. Oxygen is provided by an oxygen-containing compound such as water vapor, oxygen gas, or air. In one embodiment, the precursor compounds are mixed to form a sol before being sprayed onto the heated substrate. The precursor compounds are not particularly limited as long as at least one precursor compound contains lithium and at least one precursor compound contains cobalt. In one embodiment, lithium

[0183] is provided by a lithium compound such as lithium acetate, lithium carbonate, lithium hydroxide, or lithium oxide. Cobalt is provided by a cobalt compound such as cobalt acetate, cobalt carbonate, cobalt hydroxide, or cobalt oxide. Oxygen is provided by an oxygen-containing compound such as water vapor, oxygen gas, or air. is provided by a lithium compound such as lithium acetate, lithium carbonate, lithium hydroxide, or lithium oxide. Cobalt is provided by a cobalt compound such as cobalt acetate, cobalt carbonate, cobalt hydroxide, or cobalt oxide. Oxygen is provided by an oxygen-containing compound such as water vapor, oxygen gas, or air.

[0184] 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. is provided by a lithium compound such as lithium acetate, lithium carbonate, lithium hydroxide, or lithium oxide. Cobalt is provided by a cobalt compound such as cobalt acetate, cobalt carbonate, cobalt hydroxide, or cobalt oxide. Oxygen is provided by an oxygen-containing compound such as water vapor, oxygen gas, or air.

[0185] In one embodiment, the precursor compounds are mixed to form a sol before being sprayed onto the heated substrate. is provided by a lithium compound such as lithium acetate, lithium carbonate, lithium hydroxide, or lithium oxide. Cobalt is provided by a cobalt compound such as cobalt acetate, cobalt carbonate, cobalt hydroxide, or cobalt oxide. Oxygen is provided by an oxygen-containing compound such as water vapor, oxygen gas, or air.

[0186] The precursor compounds are not particularly limited as long as at least one precursor compound contains lithium and at least one precursor compound contains cobalt. In one embodiment, lithium is provided by a lithium compound such as lithium acetate, lithium carbonate, lithium hydroxide, or lithium oxide. Cobalt is provided by a cobalt compound such as cobalt acetate, cobalt carbonate, cobalt hydroxide, or cobalt oxide. Oxygen is provided by an oxygen-containing compound such as water vapor, oxygen gas, or air. The precursor compound containing mu contains a lithium salt and / or a precursor containing cobalt. The compound contains a cobalt salt.

[0187] [Electrode] The crystalline lithium cobaltate composition of an embodiment of the present invention is typically particularly useful for forming an electrode used in a cell such as an electrochemical cell and a fuel cell.

[0188] Therefore, according to a further aspect, the present invention provides, in either its broadest or preferred aspect ( as defined above), an electrode comprising the crystalline lithium cobaltate composition of an embodiment of the present invention.

[0189] Typically, in the electrode of an embodiment of the present invention, the crystalline lithium cobaltate composition is supported on a support. In one embodiment, the crystalline lithium cobaltate composition forms a layer on the support.

[0190] Typically, the support is a substrate on which a current collector is supported. In one embodiment, the current collector is a metal or a conductive metal oxide. In one embodiment, the current collector is selected from the group consisting of platinum, aluminum, titanium, chromium, iron, zinc, gold, silver, nickel, molybdenum, tin oxide, indium tin oxide, and stainless steel.

[0191] Typically, the substrate is an inert substrate. In one embodiment, the substrate is selected from the group consisting of silicon, silicon oxide, aluminum oxide, aluminosilicate material, doped silicon oxide, glass, metal, and ceramic material.

[0192] In one embodiment, the substrate is a silicon substrate. In one embodiment, the silicon substrate has one layer It is covered by the above passivation layer. In one embodiment, at least one layer of passi vation layer contains silicon dioxide. In one embodiment, at least one additional pa ssivation layer contains silicon nitride.

[0193] In one embodiment, an adhesive layer is present between the current collector and the substrate. In one embodiment, the adhesive layer is selected from metals and metal oxides. In certain embodiments, the adhesive layer is selected from the group consisting of titanium oxide , titanium, zirconium, and chromium.

[0194] [Electrochemical cell] The crystalline lithium cobalt oxide composition of embodiments of the present invention can be usefully used in cells, particularly electrochemical cells.

[0195] Therefore, in a further aspect of the present invention, an electrolyte, an anode, a cathode, and is provided with an electrochemical cell in which the anode and / or the cathode includes an electrode according to the third aspect of the present invention is provided.

[0196] The lithium cobalt oxide composition of embodiments of the present invention has been found to be particularly suitable for use as a cathode in such cells. Therefore, as defined above, the present invention further provides an electrochemical cell in which the cathode includes an electrode according to the present invention.

[0197] The cell may be a solid cell (also called a solid-state battery).

[0198] Typically, the cell is a lithium-ion battery. As defined above, in a lithium-ion battery, lithium ions (Li +) moves from the negative electrode to the positive electrode during discharge and in the reverse direction during charging. Therefore, as defined above, the present invention further provides a lithium-ion battery comprising a cathode of the electrode according to the present invention.

[0199] The electrolyte may be any electrolyte commonly used in an electrochemical cell. However, it is particularly preferred that the electrolyte is a solid electrolyte. By applying the cobalt lithium oxide composition of the embodiment of the present invention to a battery using a solid electrolyte, characteristics (particularly, cycle life, capacity, adhesion to the lower layer, and stress control) are improved, and such utilization is not disclosed in the art.

[0200] Examples of solid electrolytes include the following. - Lithium phosphonitride oxide (LiPON) - Lithium borosilicate (such as those described in WO2017 / 216532, WO2015 / 104540, and WO2015 / 104538) - Sulfide-based glasses and glass-ceramic electrolytes, e.g., LPS (xLi2S - y P2S5), Li2 - SiS2 - Garnet-type solid electrolytes, e.g., Li5La3M2O 12 or LLZO (Li7La3 Zr2O 12 ) - Argyrodite-type solid electrolytes, e.g., Li6PS5X (X is a halogen such as Cl, Br, I, etc.) - Oxide-based perovskite-type solid electrolytes, e.g., LLTO (Li 0.5 La 0.5 TiO3) - LISICON-type, e.g., Li 10 GeP2S 12 ; NASICON-type, e.g., Li 1. 4[Al0.4 Ge 1.6 (PO4)3], LATP (Li 1+x Al x Ti 2-x (P O4)3) - Solid polymer electrolyte, e.g., polyethylene oxide (PEO)

[0201] In one embodiment, the electrolyte contains lithium oxynitride phosphate (LiPON).

[0202] Also provided is a method for manufacturing a solid cell, which uses the method according to the present invention to deposit an electrode of the cell as a layer of the crystalline lithium cobalt oxide composition according to an embodiment of the present invention and has a step of depositing. After the deposition of the lithium cobalt oxide composition, a further layer of the solid battery is deposited using a physical vapor deposition method or a vapor deposition method such as sputtering to form a multilayer structure. The production of a solid battery by PVD alone is described in International Publication No. WO 2015 / 104538. Preferred layers of the solid battery and methods for manufacturing the same are shown below. However, as is known to those skilled in the art

[0203] the layers and manufacturing methods of solid batteries are not limited to those described below. In one embodiment, the electrochemical cell is a fuel cell. As is known to those skilled in the art, a fuel cell is an electrochemical cell that converts the chemical energy of a fuel into electricity by an electrochemical reaction between a fuel (typically hydrogen, or a simple organic compound such as methanol or formic acid) and oxygen or another oxidizing agent. In a battery, the chemical energy is derived from chemical substances present in the battery, whereas in a fuel cell, the chemical energy is derived from a fuel and an oxidizing agent present outside the battery.

[0204]

Table 1

[0205] In one embodiment, the electrochemical cell is a fuel cell. As is known to those skilled in the art, a fuel cell is an electrochemical cell that converts the chemical energy of a fuel (typically hydrogen, or a simple organic compound such as methanol or formic acid) and oxygen or another oxidizing agent into electricity by an electrochemical reaction. In a battery, the chemical energy is derived from chemical substances present in the battery, whereas in a fuel cell, the chemical energy is derived from a fuel and an oxidizing agent present outside the battery. A fuel cell differs from a battery in that it requires a continuous supply of fuel and oxygen (typically air ) to sustain the chemical reaction. A fuel cell can generate electricity continuously as long as the supply of fuel and oxygen continues.

[0206] Thus, in a further aspect of the present invention, there is provided a fuel cell comprising an anode, a cathode, and an electrolyte, wherein the anode and / or the cathode comprises a crystalline oxide material of an embodiment of the present invention.

[0207] Also, a fuel cell typically comprises a fuel supply source or is connected to a fuel supply source. In one embodiment, the fuel is hydrogen. In one embodiment, the fuel is an organic compound, examples of which include methane, methanol, ethanol, formic acid, and acetic acid.

[0208] Also, a fuel cell typically comprises an oxidant supply source or is connected to an oxidant supply source. In one embodiment, the oxidant is molecular oxygen. In one embodiment, the oxidant is an oxidizing agent, examples of which are known to those skilled in the art.

[0209] Also provided is an electronic device comprising an electrochemical cell (particularly a lithium-ion battery) according to the present invention. Examples of such electronic devices are known to those skilled in the art and include portable electronic devices such as mobile phones.

Examples

[0210] FIG. 1 shows a schematic view of an apparatus 10 that is suitable for implementing an embodiment of the physical vapor deposition method of the method of the present invention. Deposition is carried out in a vacuum system 12, which may be an ultra-high vacuum system. A substrate 14 of a desired material (determined according to the intended purpose of the thin film layer to be deposited) is placed in the vacuum system. (depending on the intended purpose of the thin film layer to be deposited) within the vacuum system. It is placed in 12 and heated to a temperature exceeding room temperature using the heater 16. Vacuum system There are also a plurality of vapor sources in it, and one vapor source is provided for each component element of 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 lithium vapor source. The third vapor source 22 includes a cobalt vapor source.

[0211] During the deposition process, a controlled flux of each component element is emitted from each vapor source onto the heated substrate 14, and various elements are co-deposited on the substrate. These elements react on the substrate 14 to form a thin film layer 29 of crystalline lithium cobaltate.

[0212] A remarkable advantage of the described physical vapor deposition method is that the composition and structure of the compound can be directly controlled by the deposition rate of the component elements by directly depositing the components of the compound from the elements. That is, the flux of each element can be independently controlled by appropriately operating each vapor source, whereby the chemical composition of the compound to be deposited can be adjusted according to strict requirements as needed.

[0213] During deposition, the fluxes of lithium and cobalt are monitored, and appropriate adjustments are made to each vapor source as needed. The deposition rates of both the lithium flux and the cobalt flux can be measured, for example, using a quartz crystal microbalance method (QCM) or an electron impact emission spectroscopy (EIES ). Also, the cobalt flux can be monitored by monitoring the stability of the oxygen pressure in the deposition chamber using a residual gas analyzer (RGA ) or an ion gauge. ​​​​​​​​can be monitored indirectly. Due to the reactivity of the cobalt flux with respect to oxygen, an inverse change in the oxygen pressure is observed when the cobalt flux changes. Using a residual gas analyzer (RGA) and the total pressure measured using an ion gauge, the gases present in the vacuum system, namely oxygen, nitrogen, argon, carbon dioxide (trace amounts), and carbon monoxide (trace amounts), can be monitored. The pressure of the gas introduced into the system can be changed by altering the flux of the gas introduced into the chamber. In addition, for example, ellipsometry or other optical techniques can be used to monitor the growth of the film during deposition. The formation / addition of a film / seed layer with a non-uniform composition can, for example, cause defects, and these defects can function as nucleation sites for crystal growth, enabling control of the film structure and morphology, which can be advantageous. Controlling the film composition in this way also affects film properties such as adhesion to the surrounding layer and is useful for balancing the stress within the film. The method of the present invention can precisely control the film composition in this way and adjust it during deposition to control the final film properties, making it more advantageous than other techniques such as pulsed laser deposition (PLD), where light elements such as lithium are more prone to loss and it is more difficult to control the final film composition. According to this method, a LiCoO₂ film with a thickness of 1 to 30 μm for use in a solid-state battery can be deposited. When depositing LiCoO₂ for use in a solid-state battery, a thin test LiCoO₂ layer less than 1 μm (typically about 250 nm) is deposited in the same way, and Raman spectroscopy and laser can be monitored.

[0214] The change in the pressure of the gas introduced into the system can be achieved by changing the flux of the gas introduced into the chamber. In addition, for example, ellipsometry or other optical techniques can be used to monitor the growth of the film during deposition. The formation / addition of a film / seed layer with a non-uniform composition can, for example, cause defects, and these defects can function as nucleation sites for crystal growth, enabling control of the film structure and morphology, which can be advantageous. Controlling the film composition in this way also affects film properties such as adhesion to the surrounding layer and is useful for balancing the stress within the film. The method of the present invention can precisely control the film composition in this way and adjust it during deposition to control the final film properties, making it more advantageous than other techniques such as pulsed laser deposition (PLD), where light elements such as lithium are more prone to loss and it is more difficult to control the final film composition. According to this method, a LiCoO₂ film with a thickness of 1 to 30 μm for use in a solid-state battery can be deposited. When depositing LiCoO₂ for use in a solid-state battery, a thin test LiCoO₂ layer less than 1 μm (typically about 250 nm) is deposited in the same way, and Raman spectroscopy and laser

[0215] The formation / addition of a film / seed layer with a non-uniform composition can, for example, cause defects, and these defects can function as nucleation sites for crystal growth, enabling control of the film structure and morphology, which can be advantageous. Controlling the film composition in this way also affects film properties such as adhesion to the surrounding layer and is useful for balancing the stress within the film. The method of the present invention can precisely control the film composition in this way and adjust it during deposition to control the final film properties, making it more advantageous than other techniques such as pulsed laser deposition (PLD), where light elements such as lithium are more prone to loss and it is more difficult to control the final film composition. The formation / addition of a film / seed layer with a non-uniform composition can, for example, cause defects, and these defects can function as nucleation sites for crystal growth, enabling control of the film structure and morphology, which can be advantageous. Controlling the film composition in this way also affects film properties such as adhesion to the surrounding layer and is useful for balancing the stress within the film. The method of the present invention can precisely control the film composition in this way and adjust it during deposition to control the final film properties, making it more advantageous than other techniques such as pulsed laser deposition (PLD), where light elements such as lithium are more prone to loss and it is more difficult to control the final film composition. The formation / addition of a film / seed layer with a non-uniform composition can, for example, cause defects, and these defects can function as nucleation sites for crystal growth, enabling control of the film structure and morphology, which can be advantageous. Controlling the film composition in this way also affects film properties such as adhesion to the surrounding layer and is useful for balancing the stress within the film. The method of the present invention can precisely control the film composition in this way and adjust it during deposition to control the final film properties, making it more advantageous than other techniques such as pulsed laser deposition (PLD), where light elements such as lithium are more prone to loss and it is more difficult to control the final film composition. The formation / addition of a film / seed layer with a non-uniform composition can, for example, cause defects, and these defects can function as nucleation sites for crystal growth, enabling control of the film structure and morphology, which can be advantageous. Controlling the film composition in this way also affects film properties such as adhesion to the surrounding layer and is useful for balancing the stress within the film. The method of the present invention can precisely control the film composition in this way and adjust it during deposition to control the final film properties, making it more advantageous than other techniques such as pulsed laser deposition (PLD), where light elements such as lithium are more prone to loss and it is more difficult to control the final film composition. The formation / addition of a film / seed layer with a non-uniform composition can, for example, cause defects, and these defects can function as nucleation sites for crystal growth, enabling control of the film structure and morphology, which can be advantageous. Controlling the film composition in this way also affects film properties such as adhesion to the surrounding layer and is useful for balancing the stress within the film. The method of the present invention can precisely control the film composition in this way and adjust it during deposition to control the final film properties, making it more advantageous than other techniques such as pulsed laser deposition (PLD), where light elements such as lithium are more prone to loss and it is more difficult to control the final film composition. The formation / addition of a film / seed layer with a non-uniform composition can, for example, cause defects, and these defects can function as nucleation sites for crystal growth, enabling control of the film structure and morphology, which can be advantageous. Controlling the film composition in this way also affects film properties such as adhesion to the surrounding layer and is useful for balancing the stress within the film. The method of the present invention can precisely control the film composition in this way and adjust it during deposition to control the final film properties, making it more advantageous than other techniques such as pulsed laser deposition (PLD), where light elements such as lithium are more prone to loss and it is more difficult to control the final film composition. The formation / addition of a film / seed layer with a non-uniform composition can, for example, cause defects, and these defects can function as nucleation sites for crystal growth, enabling control of the film structure and morphology, which can be advantageous. Controlling the film composition in this way also affects film properties such as adhesion to the surrounding layer and is useful for balancing the stress within the film. The method of the present invention can precisely control the film composition in this way and adjust it during deposition to control the final film properties, making it more advantageous than other techniques such as pulsed laser deposition (PLD), where light elements such as lithium are more prone to loss and it is more difficult to control the final film composition.

[0216] According to this method, a LiCoO₂ film with a thickness of 1 to 30 μm for use in a solid-state battery can be deposited. When depositing LiCoO₂ for use in a solid-state battery, a thin test LiCoO₂ layer less than 1 μm (typically about 250 nm) is deposited in the same way, and Raman spectroscopy and laser is used. The structure of this test layer was determined using ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). and analyze the composition.

[0217] If a suitable test sample is obtained, the conditions are repeated with increased deposition time to obtain a solid-state Obtain a thick LiCoO2 film for use in the pond.

[0218] Raman spectroscopy is useful for determining the structure of Li as different crystal structures give Raman fingerprints. This is a very useful technique for the microstructural analysis of CoO2. ) and four bands at low temperature (Fd3m) (LT-LCO) were observed. In addition, since Co3O4 has a high scattering intensity, it is expected that the secondary generated Co 3O4 can be detected by Raman spectroscopy even at trace / impurity levels. Molecular spectroscopy is a particularly useful method for studying these materials.

[0219] The Raman spectrometer used in the examples had a 532 nm (green) laser and 10x, 50x, and a 100x microscope objective lens. The 532 nm laser and NA0.90 / 100x objective lens achieve a spatial resolution of 3. However, the optical process of Raman microscopy is expected to be It is much more complicated than observing with a standard optical microscope. Resolution is limited by a variety of factors. For this reason, the typical Raman spatial resolution is generally considered to be 1 μm (although (The value of may be improved under ideal conditions.)

[0220] The Raman spectroscopy measurements are performed according to the acquisition parameters shown in Table 2. Use a magnification of 50, a slit width of 50, a hole of 100, and a filter of 2%. For cross-section measurement, Use the same settings as above, but set the objective lens magnification to 100 and use lines with a pitch of 1 μm The integration times are 2, and the number of points covers the entire sample.

[0221]

Table 2

[0222] The ratio of lithium to cobalt present in the film is determined using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). In a preferred embodiment, the lithium cobalt oxide film may be formed with a composition slightly deficient in lithium, for example, a lithium:cobalt ratio of (when expressed as the ratio of all metal atoms excluding oxygen) 47.5 to 49.1% lithium to 52.5 to 50.9% cobalt.

[0223] However, the properties and performance of the formed film vary, and it is suggested that the composition is not the only important factor that affects the film's properties. Figure 2 shows the cycle life of many films, indicating that for a Li:Co composition in the range of 47.5 to 49.1 atomic % Li, even for films with the same Li:Co composition, the cycle life can be either long or short (under the same cycle conditions). The same is true for the utilization number (capacity normalized by area and thickness), and Figure 3 shows that the utilization number is widely distributed within the target composition range.

[0224] The crystalline nature of the deposited LiCoO2 film is shown by Raman spectroscopy and X-ray diffraction. Raman spectroscopy shows that the deposited film is the HT-LiCoO2 phase (R-3m) (Figure 4) , this high-temperature phase is typically formed at a substrate temperature lower than that of the film described in Patent Document 1 Due to the nature of this synthesis method that allows for the deposition of a crystalline lithium-containing material, it was formed at a relatively low substrate temperature of 400 °C The hexagonal R-3m phase consists of a regular lamellar structure composed of alternately stacked lithium layers and cobalt layers (as described, for example, in Porthault et al. Vibrational Spec 62 (2012) 152-158).

[0225] The X-ray diffraction (XRD) pattern of the deposited film (Figure 5) shows that the film is mainly (001)-oriented with the (003) peak at 18.9° being the strongest, and in some examples peaks at 37.4° (101), 38.4° (006), 39.1° (012), and 45. 3° (104) are also observed, indicating the presence of microcrystals with other orientations. When cross-sectional Raman spectroscopy was performed on these films , changes in the film due to slight changes during deposition were shown, and such changes may be related to the morphology of the film.

[0226] Figure 6 shows a film (Film 4) with deposition conditions kept constant over the deposition time (not made according to the present invention). The Raman spectrum is constant throughout the film, indicating that the same phase and composition exist throughout the entire thickness of the film.

[0227] The fabricated film is smooth and flat, containing only small microcrystals (Figure 7), and X-ray diffraction (XR D) shows that the film is preferentially oriented in the (003) direction, with only peaks at 18.9° and 38.4° corresponding to the (003) orientation and (006) orientation respectively being observed ( Figure 5). The (001) orientation of LiCoO2 is formed parallel to the substrate surface with an R-3m structure The existence of a two-dimensional lithium diffusion surface parallel to the substrate allows lithium to migrate along a long path. This limits the rate at which lithium intercalation occurs. The orientation of the ZnO is not ideal for the electrochemical intercalation of lithium, and thus It has been shown that the capacity is lower than the capacity (Non-Patent Document 5). A strong (003) orientation was observed in film 4 (not a film grown on the same cycle conditions as the other films described). When cycled at 25°C under these conditions, the theoretical capacity (13μ Ah cm -1 -2μm -1 ) was only 20% of the total.

[0228] The morphology of this film is close-packed and dense, with Width 100~300(±50)nm and length 0.1~7μm (maximum value is total film thickness (6700n The film is composed of thin columnar microcrystals of 0.1 mm thick, uniform in nature, and has a smooth surface when viewed from the top. In the SEM top view, only small crystallites with sizes less than 350 nm are observed (Fig. 7) In some cases, the film is prone to cracks that can have detrimental effects on solid-state batteries. It is known that...

[0229] FIG. 8 shows three example films according to embodiments of the invention where deposition conditions are varied during deposition. The film produced had only the two Raman bands associated with the LiCoO2 phase of R-3m. In order to achieve this, deposition was started with the Co flux and the Li flux being equal. The amount of Co in the film was increased slightly by varying the Li flux relative to the Co flux. In the Raman spectrum, the cobalt oxide phase Co3O4A 1g Mode related It can be seen that an additional band at 690 cm -1 appears. The timing and magnitude of this change affect the morphology of the final film and enable morphology adjustment. The amount of additional cobalt added to the film is small, and the average composition of the entire LCO film present in this region has lithium at 47 - 49.5%.

[0230] As can be seen from FIG. 8, by slightly changing the deposition conditions during film deposition, the morphology of the deposited film changes. For example, large plate - shaped microcrystals with sizes in the range of 0.4 - 2 μm in length (typically greater than 0.3 μm) are observed in the film, and these microcrystals cover more than 4 % of the surface area of the film and may even cover 80% of the surface area in top - view (Table 3), while the rest of the film consists of the small microcrystals described above (typically less than 0.3 μm).

[0231] Table 3 shows a comparison of the microcrystal sizes of the LiCoO2 films described in this specification shown in FIG. 12 (films 1 - 3 are films according to embodiments of the present invention, and film 4 is not according to the present invention). Since film 4 is very smooth, microcrystals are not generally observed. Note that for the sample of film 3, there are a large number of large microparticles on it, making it difficult to calculate the average roughness.

[0232]

Table 3

[0233] In the XRD patterns of these films, peaks at 3 7.4° and 45.3° appear due to the appearance of (101) and (104) orientations, indicating that the film is no longer preferentially (003) - oriented, and the intensities of these peaks increase as the surface area of the large microcrystals in the film increases. ​​​​ as shown in FIG. 5. Such morphological changes are due to Co3O4 added as a small amount of seeds functioning as a seed layer for growing microcrystals with orientations ((101) and (104)) different from those of the majority (bulk) of the (003) film and were thus observed.

[0234] By adding microcrystals with different orientations, a Li diffusion path through the film rather than parallel to the substrate is formed This is beneficial for use in lithium ion batteries as it results in improved capacity (utilization) and a material with high rate performance. Also, by producing a film with low homogeneity, the film stress is reduced and the film adhesion is improved. In the cross-sectional image of the film, it has the same structure as that observed in film 4 (described above), and a film consisting of densely packed microcrystals with a width of 100 - 300 (±50) nm arranged perpendicular to the surface of the substrate is observed near the substrate. When the film deposition conditions are changed such that a small amount of Co3O4 that can function as a seeding layer is formed

[0235] this structure deviates from that of regular and small microcrystals and crystals with a size in the range of 300 - 2500 nm and low regularity are formed ( FIG. 9). FIG. 9 shows a cross-sectional image of film 1, and a change in the morphology within the film is observed when the film thickness reaches 3000 nm. This change corresponds to a change in the Raman cross-section and may be related to a change in the deposition conditions that vary the ratio of the Co flux to the Li flux. Another example (according to an embodiment of the present invention) shown in FIG. 10 is film 5. Film 5 is rich in Co in the center of the film as shown by the peak at 690 cm which is known to be related to and crystals with large sizes and low regularity in the range of 300 - 2500 nm are formed ( FIG. 9). FIG. 9 shows a cross-sectional image of film 1, and a change in the morphology within the film is observed when the film thickness reaches 3000 nm. This change corresponds to a change in the Raman cross-section and may be related to a change in the deposition conditions that vary the ratio of the Co flux to the Li flux. as shown by the peak at 690 cm which is known to be related to Co3O4 and is shown at the center of the film

[0236] Another example (according to an embodiment of the present invention) shown in FIG. 10 is film 5. Film 5 is rich in Co in the center of the film as shown by the peak at 690 cm which is known to be related to -1 as shown by the peak at 690 cm which is known to be related to Co3O4 and is shown at the center of the film It has regions and is growing. The Co-rich regions have a small proportion in the overall film thickness. From the SEM image, it can be confirmed that the film morphology consists of large microcrystals covering most of the film surface. It is shown that Co3O4 acts as a seeding layer and the subsequently formed lithium cobaltate is formed as large plate-like microcrystals. This film contains 47 atomic% lithium (when expressed as the percentage of all atoms excluding oxygen in the crystalline oxide).

[0237] The above example shows that the film morphology can be controlled by changing the relative ratio of Co and Li during the deposition of lithium cobaltate, and that, for example, only a small amount of Co3O4 is required to act as a seeding layer. Co3O4 is not a cathode material, and since the presence of Co3O4 reduces the capacity of the lithium cobaltate film, only a small amount of the necessary Co3O4 is required.

[0238] As other methods that can be used to obtain a similar effect, depositing a seeding layer at the start of the deposition of lithium cobaltate, i.e., instead of dispersing Co3O4 as a small amount of species in the lithium cobaltate film, forming a thin layer of Co3O4 by stopping the Li flux for a short time during deposition (an example where film 5 is more extreme), interrupting the deposition of lithium cobaltate from a short time to a maximum of several days, changing the substrate temperature during deposition, generating a seeding layer using an additional element either at the start or during deposition, etc. can be mentioned.

[0239] Similar irregularities provided in the pulsed laser deposition (PLD) film were measured using a liquid electrolyte. In some cases, improving the rate of lithium intercalation and the capacity of the film has been reported in the prior art (Non-Patent Document 5). However, when using a liquid electrolyte, the high intercalation rate and capacity of a film with a large surface area are often attributed to a rough surface. That is, when the surface area is large, the contact area with the liquid electrolyte increases, which is advantageous for Li intercalation and deintercalation (Jung et al. Thin Solid Films 546 ( 2013) 414 - 417).

[0240] The measurements described herein were performed on a solid cell without a liquid electrolyte. Therefore, when using a solid electrolyte that does not wet the surface of the electrode like a liquid electrolyte, the same tendency is not considered to be obtained. The liquid electrolyte enters the voids between microcrystals, and because the electrode surface is rough, an electrode with a large surface area can be fully utilized. However, since the solid electrolyte is deposited as a film on the electrode, (as described in International Publication No. 2015 / 104538), a smooth film was considered preferable in a solid cell. Therefore, although this morphology of LiCoO2 promotes Li intercalation and improves the performance of LiCoO2, this does not directly lead to an increase in the capacity of the solid cell. Furthermore, the irregular LiCoO2 film was previously considered unsuitable for research due to its non-uniformity (Non-Patent Document 5 etc.).

[0241] Here, as shown in the figure, a solid composed of a platinum current collector arranged in the form of Pt / LiCoO2 / LiPON / Si / Pt, a LiCoO2 cathode, a LiPON electrolyte, and a Si anode ​A sealing agent (not shown) was provided to the solid cell (Fig. 11), and tests on the LiCoO2 film were conducted.

[0242] Due to the presence of large microcrystals (over 0.3 μm) in the LiCoO2 film, the utilization number (capacity) of the solid cell is improved compared to the case where only small microcrystals (less than 0.3 μm) are present. However, unexpectedly, within the tested range, even if the size or surface coverage rate of the microcrystals is further increased, the obtained utilization number did not change much.

[0243] When the solid electrolyte covers the surface of LiCoO2, it has been reported that the capacity degradation associated with cycling is suppressed compared to LiCoO2 tested using a liquid electrolyte. Although not wishing to be bound by theory, this capacity degradation is thought to be related to the degradation of the liquid electrolyte (Tintignac et al. Electrochimica Acta 60 (2012) 121-129).

[0244] Unexpectedly, in the films (films 1 to 3) according to the embodiments of the present invention containing irregular microcrystals, the cycle life is significantly extended compared to the films (film 4) according to the present invention containing only small and homogeneous microcrystals. As shown in Tables 3 and 4, this effect is also shown in the films with a small number (4.5% of the surface area) of large microcrystals (0.4 to 0.9 μm).

[0245] Table 4 shows the number of cycles until the discharge capacity of the 5th cycle reaches 80% at a temperature of 25 °C and a depth of 100% for the solid cells equipped with the LiCoO2 films having the above-mentioned morphology.

[0246]

Table 4

[0247] In fact, for the films with 820 cycles and 190 cycles shown in Table 4, although the Li :Co composition was measured to be the same (Li 48.25 atomic %), the film morphologies were different, and this result indicates the importance of the desired morphology.

[0248] There have been few reports on the effect of the morphology of LiCoO2 on the cycle life. Although the capacity of the (003)-oriented LiCoO2 thin film is small, it shows more stable cycles with less capacity degradation than other (101 )-oriented or (104)-oriented films, as reported in the literature (Kim et al. J. Electrochem. Soc. 151 (2004) A1062 / Jung et al . Thin Solid Films 546 (2013) 414-417). Therefore, in contrast to the results of the present invention, it has been considered that the cycle life is longer in a smooth film of small microcrystals with a high degree of (003) orientation.

[0249] [Additional surface roughness measurement] For the films according to Examples (Examples A to D) and Comparative Example E (not according to the present invention) of the present invention, further surface roughness measurements were carried out. The measurement results are shown by the root mean square surface roughness, that is, the root mean square of the deviation of the surface of the profile height from the mean line. The results are shown in Table 5.

[0250]

Table 5

[0251] All documents described in this specification are incorporated herein by reference. For those skilled in the art Without departing from the scope and spirit of the present invention, various modifications and variations of the described methods and systems of the present invention will be apparent. Although the present invention has been described with respect to specific preferred embodiments, it should be understood that the present invention as claimed should not be unduly limited to such specific embodiments. In fact, various modifications that are obvious to those skilled in the art of chemistry and materials science or related fields with respect to the manner of practicing the described invention are intended to be included within the scope of the following claims. ​

Claims

1. A method for producing a composition, wherein the composition is (a) a main phase provided by a layered mixed metal oxide having a rock salt structure belonging to the R-3m space group, and when the layered mixed metal oxide is expressed in atomic % with respect to all atoms excluding oxygen in the layered mixed metal oxide, 45 to 55 atomic % of lithium, 20 to 55 atomic % of one or more transition metals selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof, 0 to 25 atomic % of one or more additional 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, and a main phase containing (b) a secondary phase provided by a metal oxide having no crystal structure of the layered mixed metal oxide and containing one or more of the transition metals selected from the group consisting of chromium, manganese, iron, nickel, and cobalt contained in the layered mixed metal oxide, a composition in which the main phase provides 90% to 99.5% of the total mass of the composition and the secondary phase provides 0.5% to 10% of the total mass of the composition, the method comprising - a source of lithium, - a source of a transition metal selected from the group consisting of chromium, manganese, iron, nickel, and cobalt, - a source of oxygen, - optionally, a source of at least one dopant element 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, providing a vapor source for each component element of the composition, at least including heating a substrate at about 30 °C to about 900 °C, a step of supplying a flux of each of the component elements onto the substrate, wherein the component elements react on the substrate to form a first phase provided by a layered mixed metal oxide having a rock salt structure belonging to the R-3m space group A step of supplying fluxes of the transition metal and the oxygen, which are selected from the group consisting of at least chromium, manganese, iron, nickel, and cobalt, onto the substrate, wherein the transition metal and the oxygen react on the substrate to form a second phase provided by a metal oxide having no crystal structure of the first phase.

2. The method comprises: a step of depositing the second phase as a seed layer on the substrate; a step of depositing a film of the first phase on the seed layer. The method according to claim 1.

3. The method comprises: a step of depositing a first film of the first phase on the substrate; a step of depositing the second phase as a seed layer on the first film; a step of depositing a second film of the first phase on the seed layer. The method according to claim 1.

4. The method according to claim 1, comprising a step of depositing the second phase simultaneously with the first phase on the substrate to form a mixture layer containing the first phase and the second phase.

5. The method according to claim 4, wherein the mixture layer is deposited on the substrate.

6. The method according to claim 4, wherein the mixture layer is deposited on an existing film of the first phase.

7. The method according to any one of claims 4 to 6, further comprising a step of depositing a film of the first phase on the mixture layer.

8. The method according to any one of claims 1 to 6, wherein the substrate is heated to about 150 °C to about 700 °C, preferably about 200 °C to 700 °C.

9. The method according to claim 8, wherein the substrate is heated to about 200 °C to about 500 °C, preferably about 300 °C to 500 °C.

10. The method according to any one of claims 1 to 9, comprising a step of changing the flux of one or more of the component elements to increase the formation amount of the second phase.

11. The method according to claim 10, comprising a step of reducing or eliminating the flux of lithium.

12. The method according to claim 10 or claim 11, comprising a step of increasing the flux of the at least one transition metal element selected from the group consisting of chromium, manganese, iron, nickel, and cobalt.

13. The method according to any one of claims 10 to 12, comprising a step of reducing the flux of oxygen.

14. The method according to any one of claims 10 to 13, having a step of supplying oxygen together with an inert gas such as nitrogen or a noble gas.

15. A method for producing a composition, comprising: The composition is: (a) A main phase provided by a layered mixed metal oxide having a rock salt structure belonging to the R-3m space group, wherein when the layered mixed metal oxide is expressed in atomic % with respect to all atoms excluding oxygen in the layered mixed metal oxide, 45 to 55 atomic % of lithium, 20 to 55 atomic % of one or more transition metals selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof, 0 to 25 atomic % of one or more additional 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, and a main phase containing the same, (b) A secondary phase provided by a metal oxide having no crystal structure of the layered mixed metal oxide and containing one or more of the transition metals selected from the group consisting of chromium, manganese, iron, nickel, and cobalt contained in the layered mixed metal oxide, The main phase provides 90% to 99.5% of the total mass of the composition, and the secondary phase provides 0.5% to 10% of the total mass of the composition. The method includes: Providing a sputtering target containing a mixed metal oxide containing lithium and 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; Providing a further sputtering target containing a metal oxide phase containing one or more of the transition metals selected from the group consisting of chromium, manganese, iron, nickel, and cobalt contained in the sputtering target. A sputtering deposition method comprising a step of sputtering the sputtering target and the further sputtering target to produce a composition, wherein the composition is provided by a layered mixed metal oxide of lithium, which is optionally doped with at least one of the dopant elements, and one or more of the transition metals selected from the group consisting of chromium, manganese, iron, nickel, and cobalt, and having a rock salt structure belonging to the R-3m space group; and a first phase A method comprising a second phase provided by a metal oxide having no crystal structure of the first phase and containing one or more of the transition metals selected from the group consisting of chromium, manganese, iron, nickel, and cobalt contained in the layered mixed metal oxide.

16. The method according to claim 15, further comprising a step of sputtering the sputtering target to form a film of the first phase, wherein, prior to this step, a step of sputtering the further sputtering target to form a film of the second phase is performed.

17. The method according to claim 15 or 16, further comprising a step of annealing the composition.

18. The method according to any one of claims 15 to 17, wherein the secondary phase contains less than 1 atomic % of lithium.

19. The method according to claim 18, wherein the secondary phase substantially does not contain lithium.

20. The layered mixed metal oxide is 45 to 55 atomic % of lithium, 40 to 55 atomic % of one or more transition metals selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof, and 0 to 5 atomic % of one or more additional 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. The method according to any one of claims 1 to 19.

21. The layered mixed metal oxide is 45 to 55 atomic % of lithium, 45 to 55 atomic % of one or more transition metals selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof. The method according to claim 20.

22. The method according to any one of claims 1 to 21, wherein the secondary phase provides 1% to 10% of the total mass of the composition.

23. The method according to claim 22, wherein the secondary phase provides 2.5% to 10% of the total mass of the composition.

24. The method according to any one of claims 1 to 23, wherein the composition is a thin film layer having a top surface and a bottom surface, and the height between the top surface and the bottom surface is 1 to 50 μm.

25. wherein the layered mixed metal oxide has the general formula Li １ Co １－２y Mn ｙ Ni ｙ O ２ and the secondary phase contains at least one transition metal selected from the group consisting of cobalt, manganese, and nickel, the method according to any one of claims 1 to 24.

26. wherein the layered mixed metal oxide has the general formula Li ｘ Mn １－y M ｙ O ２ and M is a transition metal selected from the group consisting of chromium, nickel, iron and cobalt, the method according to any one of claims 1 to 24.

27. A method for manufacturing a solid electrochemical cell, the method comprising a step of depositing an electrode of the cell using the method according to any one of claims 1 to 26.

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