WO2019193324A1 - Composition, methods for its production, and its use - Google Patents

Composition, methods for its production, and its use Download PDF

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Publication number
WO2019193324A1
WO2019193324A1 PCT/GB2019/050946 GB2019050946W WO2019193324A1 WO 2019193324 A1 WO2019193324 A1 WO 2019193324A1 GB 2019050946 W GB2019050946 W GB 2019050946W WO 2019193324 A1 WO2019193324 A1 WO 2019193324A1
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WIPO (PCT)
Prior art keywords
composition
lithium
cobalt
oxide
crystalline
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/GB2019/050946
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English (en)
French (fr)
Inventor
Laura PERKINS
William Richardson
Louise TURNER
Thomas RISBRIDGER
Samuel Guerin
Brian Hayden
Owain CLARK
Robert Noble
Jean-Philippe SOULIÉ
Patrick Casey
Kyriakos GIAGLOGLOU
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Ilika Technologies Ltd
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Ilika Technologies Ltd
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Application filed by Ilika Technologies Ltd filed Critical Ilika Technologies Ltd
Priority to JP2020554303A priority Critical patent/JP7384420B2/ja
Priority to KR1020207031489A priority patent/KR102853845B1/ko
Priority to US17/041,276 priority patent/US12202738B2/en
Priority to CN201980024389.4A priority patent/CN112204774B/zh
Priority to EP19717553.2A priority patent/EP3776700A1/en
Publication of WO2019193324A1 publication Critical patent/WO2019193324A1/en
Anticipated expiration legal-status Critical
Priority to JP2023187413A priority patent/JP7705668B2/ja
Priority to US18/987,389 priority patent/US20250122092A1/en
Priority to US19/021,332 priority patent/US20250154024A1/en
Ceased legal-status Critical Current

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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Definitions

  • composition methods for its production, and its use
  • This invention relates to a composition containing a first phase provided by a layered mixed metal oxide having a rocksalt structure and a second phase provided by a metal oxide that does not have the crystal structure of the layered mixed metal oxide.
  • the composition may contain C03O4 and a crystalline oxide of lithium and cobalt, optionally containing one or more dopant elements as described herein.
  • the invention also relates to methods for the production of the composition and its use, particularly as an electrode and in electrochemical cells, particularly lithium-ion batteries
  • a lithium-ion battery is a type of rechargeable battery in which lithium ions (Li + ) move from the negative electrode to the positive electrode during discharge and back when charging.
  • Lithium-ion batteries use a lithium intercalating compound as one electrode material, compared to the metallic lithium used in a non-rechargeable lithium-ion battery.
  • the electrolyte, which allows for ionic movement, and the two electrodes are the constituent components of a lithium-ion battery.
  • lithium-ion batteries are composed of at least three components. Two active electrodes (the anode and the cathode) are separated by an electrolyte. Each of these components is formed as a thin film, deposited in sequence on a supporting substrate. Additional components such as current collectors, interface modifiers and encapsulations may also be provided. In manufacture, the components may be deposited in the order of cathode current collector, cathode, electrolyte, anode, anode current collector and encapsulation, for example. In the lithium-ion example, the anode and the cathode are capable of reversibly storing lithium.
  • anode and cathode materials are high gravimetric and volumetric storage capacities which can be achieved from a low mass and volume of material, while the number of lithium ions stored per unit should be as high as possible.
  • the materials should also exhibit acceptable electronic and ionic conduction so that ions and electrons can move through the electrodes during the battery charge and discharge process.
  • lithium-ion batteries based on layered mixed metal oxides having a rocksalt structure belonging to the R-3m space group.
  • These layered mixed metal oxides are of the formula type Li x M’ y 0 2 , wherein M’ is a transition metal selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof.
  • alternate layers of lithium ions and ions of the transition metal occupy the octahedral sites of a cubic close packed lattice of oxide ions. Diffusion of lithium ions occurs preferentially along the lithium planes.
  • Examples of such mixed metal oxides include Li x Mni- y M y 0 2 (wherein M is a transition metal selected from the group consisting of chromium, iron, nickel, cobalt, and combinations thereof) and lithium cobalt oxide (UC0O2).
  • UC0O2 has a hexagonal layered crystal structure, with Li + ions in octahedral sites between O-Co-O sheets. Li + diffusion occurs via vacancy hopping within the lithium planes.
  • the (101) and (104) orientations have the lithium planes at slight angles compared to the (1 10) orientation still allowing for easy Li + removal and insertion into the structure.
  • the (003) orientation consists of Li + planes aligned parallel to the substrate: this orientation is less favourable as the lithium ions are less accessible being effectively trapped in the structure.
  • WO 2015/104539 describes a vapor deposition method for preparing crystalline lithium-containing compounds, including lithium cobalt oxides.
  • a lithium cobalt oxide film is formed on a substrate when the component elements react on the substrate to form a crystalline material. The depositions described in
  • WO 2015/104539 were carried out in a physical vapor deposition (PVD) system which has been previously described in the literature (Guerin, S. and Hayden, B. E., Journal of Combinatorial Chemistry 2006, 8, 66-73).
  • PVD physical vapor deposition
  • X-ray amorphous films are obtained which are crystallised by annealing.
  • C02O3, C03O4, Lii 47C03O4 and Pt3C>4 are observed in the X-ray diffraction patterns of some films, but no further mention of these is made: it can be understood that these are a by-product of the annealing process as the films are stated to be X-ray amorphous before heating.
  • Bates et al. also discusses the influence of substrate temperature. Deposition at high temperature leads to larger grains and increased void fraction (i.e. a greater fraction of empty spaces in the material, as a fraction of the volume of voids over the total volume). Bates et al. does not describe any attempt to introduce C03O4 into the films or use it as a seeding layer, and provides no analysis of film composition.
  • Ceder et al. J Alloys and Compounds 2006, 417, 304-310 describes substrate effects on the orientation of lithium cobalt oxide films between 0.3 - 0.5 pm thick grown by pulsed laser deposition (PLD).
  • Ceder et al. describes that stainless steel (SS) substrates give films with rough surfaces and random orientation, while silica / silicon (SiCVSi; SOS) substrates give relatively smooth surfaces with preferred (003) orientation.
  • the electrochemistry described therein shows that the rough films deposited on SS have higher utilization of the film whereas the smooth films deposited on SOS have better capacity retention and structural stability.
  • the reference indicates that all non-substrate peaks in the X-ray diffraction pattern are attributed to UC0O2 thin film and no impurity peaks such as C03O4 can be seen from the XRD diffractogram.
  • Yoon et al. J. Power Sources 2013, 226, 186-190 - use substrate temperature and/or a LhO buffer layer to control the orientation of sputtered lithium cobalt oxide layers.
  • substrate temperature and/or a LhO buffer layer to control the orientation of sputtered lithium cobalt oxide layers.
  • At 400°C films with (1 10) or (101) preferred orientation are obtained.
  • the U 2 0 buffer layer suppresses the formation of the (003) orientation and promotes the (110) orientation.
  • the films are annealed at 600°C either in situ or ex situ.
  • RF sputtering or pulsed laser deposition (PLD) from a stoichiometric UC0O2 target
  • the films are annealed at 600°C either in situ or ex situ.
  • evaporation of volatile U 2 0 results in C03O4 formation (estimated ⁇ 5 % C03O4).
  • the method of prolonged high temperature treatment taught in this document does not provide any control over the morphology of the lithium cobalt oxide film. Specifically, it is taught that when UC0O2 is deposited by means of PLD on an annealed RF seed layer, the existing (110) orientation is not continued, but overgrown with a preferential (00/) alignment. However, the film structure differs from that grown on a blank silicon substrate as not all (001) reflections are observed.
  • the document describes that, to examine the consistency of the preferred lattice orientation towards each other of the films produced by PLD and by RF sputtering, a PLD film was grown on an RF-sputtered seed layer of 0.1 mm UC0O2 and annealed at 600°C for 30 minutes.
  • PLD was simultaneously performed on a blank silicon substrate.
  • This reference sample revealed the typical PLD film diffraction pattern, indicating (00/) lattice plane orientation.
  • the PLD film deposited on the seed layer which exhibited only the (110) reflection before PLD, showed distinct (006) and (0012) reflections, but the (003) and (009) reflections were completely absent. This result indicates that the film structure is not entirely determined by the deposition technique.
  • US 2014/0272560 A1 describes production of lithium cobalt oxides, altering the orientation of sputtered films by altering the substrate surface, addition of a seed layer of UC0O2 on the substrate surface and/or depositing a multilayer structure by sputtering lithium cobalt oxide under different conditions (changing the gases).
  • lithium cobalt oxide concentration would enable the production of lithium cobalt oxide with a crystal orientation with advantageous properties in lithium-ion batteries, such as capacity and cycle life.
  • any of the prior art teach methods of producing a crystalline lithium cobalt oxide composition so as to form, in a controlled manner, localised concentrations of C03O4 to enable the crystalline orientation of lithium cobalt oxide to be controlled.
  • composition comprising: (a) C03O4, and
  • crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide comprising the following component elements:
  • At least one additional dopant element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, zinc, molybdenum, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium; wherein said atomic% is expressed as a % of total atoms of said crystalline oxide, excluding oxygen;
  • composition has a bottom surface and a top surface
  • said crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide has a crystalline structure characterized by at least one of the following parameters (a) to (c):
  • each component element comprises cobalt, lithium, oxygen, and, optionally, 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium; heating a substrate to between about 30°C and about 900°C; co-depositing each component element onto the substrate, wherein the component elements react on the substrate to form crystalline oxide comprising lithium, cobalt and optionally one or more of the dopant elements; and
  • an electrode comprising the composition of the first or seventh aspects of the invention.
  • the electrode may be a positive electrode or a negative electrode.
  • the electrode is a positive electrode.
  • an electrochemical cell comprising: an electrolyte; an anode; and a cathode; wherein the anode and/or the cathode comprises an electrode according to the third aspect of the invention.
  • the cathode comprises an electrode according to the third aspect of the invention.
  • a method of making a solid-state electrochemical cell comprising depositing an electrode of the cell as a layer of the crystalline composition according to the first aspect of the invention using a method according to the second aspect of the invention.
  • an electronic device comprising an electrochemical cell according to the fourth aspect of the invention.
  • composition comprising:
  • transition metals selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof;
  • one or more additional dopant elements selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, copper, ruthenium, zinc, molybdenum, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium;
  • atomic% is expressed as a % of total atoms of said layered oxide, excluding oxygen
  • 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 one or more of the transition metals contained in the layered mixed metal oxide, the transition metals being selected from the group consisting of chromium, manganese, iron, nickel, and cobalt;
  • the principal phase provides 90% to 99.5% of the total mass of the composition
  • the minor phase provides 0.5% to 10% of the total mass of the composition
  • the minor phase may be considered to disrupt the crystal structure of the layered mixed metal oxide.
  • the minor phase may be amorphous.
  • the minor phase may be crystalline, but have a crystal structure that is different to that of the layered mixed metal oxide, for example, belonging to a different space group.
  • the minor phase may have a crystal structure belonging to the Fd-3m space group (this is the case when the minor phase is provided by, for example, C0 3 O4).
  • the present invention may provide a method of preparing a composition according to the seventh aspect of the invention, the method comprising the steps of:
  • vapour sources comprise at least:
  • a source of a transition metal selected from the group consisting of chromium, manganese, iron, nickel, and cobalt,
  • 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium;
  • transition metal and the oxygen react on the substrate to form a second phase that is provided by a metal oxide that does not have the crystal structure of the first phase.
  • the present invention may provide a method of preparing a composition according to the seventh aspect of the invention, wherein the method is a sputtering deposition method comprising:
  • a sputtering target comprising a mixed metal oxide comprising lithium
  • 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium;
  • a further sputtering target comprising a metal oxide phase comprising one or more of the transition metals contained in the first sputtering target, the transition metals being selected from the group consisting of chromium, manganese, iron, nickel, and cobalt;
  • a first phase that 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 said dopant elements, and having a rocksalt structure belonging to the R-3m space group; and and a second phase that is provided by a metal oxide that does not have the crystal structure of the first phase, the second phase comprising one or more of the transition metals contained in the layered mixed metal oxide, the transition metals being selected from the group consisting of chromium, manganese, iron, nickel, and cobalt.
  • a method of making a solid-state electrochemical cell comprising depositing an electrode of the cell as a layer of the composition according to the seventh aspect of the invention using a method according to the eighth or ninth aspect of the invention.
  • Figure 1 is a schematic representation of an example apparatus suitable for implementing a method according to embodiments of the invention.
  • Figure 2 shows the number of cycles to 80 % of (5th cycle) discharge capacity when cycled at 100% depth of discharge (DoD) at a rate of 1C at a temperature of 25°C versus lithium percentage in lithium cobalt oxides as measured by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).
  • Figure 3 shows Utilisation number (capacity normalised to area and thickness) at a temperature of 25°C versus lithium percentage in lithium cobalt oxides when measuring the Li:Co ratio by LA-ICP-MS.
  • Figure 4 shows a Raman spectrum taken on the top of a film (film 1 as described in the Examples) containing a composition according to an aspect of the invention.
  • Figure 5 shows X-ray diffractogram for films 1-3 containing a composition according to an aspect of the invention and film 4 (not according to the invention).
  • Figure 6 shows cross-sectional Raman spectra for film 4 (not according to the invention).
  • Figure 7 shows a scanning electron microscopy (SEM) cross section and top view of the LCO layer for film 4 (not according to the invention).
  • Figure 8 shows a top view SEM, cross-sectional Raman spectra and average percentage of lithium relative to cobalt in films 1-3 according to an aspect of the invention.
  • Figure 9 shows a SEM cross section and top view of the LCO layer for film 1 according to an aspect of the invention.
  • Figure 10 shows SEM top view and cross-sectional Raman spectra for film 5 (according to an aspect of the invention) containing a layer of C03O4 in the middle of the film.
  • Figure 11 shows a cross section of a solid-state battery containing UC0O2 (film 1) according to an aspect of the invention.
  • Figure 12 shows SEMs of the films 1 to 3 (according to an aspect of the invention) and 4 (not according to the invention) for which data are provided in Tables 2 and 3.
  • a crystalline lithium cobalt oxide is grown by various methods as disclosed herein, particularly although not exclusively physical vapor deposition (PVD).
  • the lithium cobalt oxide films may be used in electrodes, for example, as a film on an inert substrate, and combined with an electrolyte, such as a lithium phosphorus oxynitride (LiPON) solid electrolyte, for use in an electrochemical cell, particularly a solid-state battery.
  • an electrolyte such as a lithium phosphorus oxynitride (LiPON) solid electrolyte
  • layered mixed metal oxides 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 rocksalt structure belonging to the R-3m space group may be grown e.g. through PVD.
  • the resulting films may be used in electrodes, for example, as a film on an inert substrate, and optionally combined with an electrolyte, such as a lithium phosphorus oxynitride (LiPON) solid electrolyte, for use in an electrochemical cell, particularly a solid-state battery.
  • an electrolyte such as a lithium phosphorus oxynitride (LiPON) solid electrolyte
  • Such layered mixed metal oxides include, for example, Li x Mni- y M y 0 2 (wherein M is a transition metal selected from the group consisting of chromium, iron, nickel, cobalt, and combinations thereof), in addition to lithium cobalt oxide.
  • electrode active material such as lithium cobalt oxide or U x Mni- y M y 02
  • cobalt oxide (C03O4) is electrochemically inactive and considered an impurity in UC0O2 compositions. See, e.g., Jo et al. 2009 J. Electrochem. Soc.
  • the capacity of a battery with an UC0O2 cathode is defined by the amount of the UC0O2 material.
  • the addition of C03O4 to the UC0O2 material will therefore be at the expense of the overall battery capacity.
  • energy density e.g. gravimetric energy density which defines capacity in weight (Wh/kg) any inclusion of C03O4 is contributing to the weight but not providing any additional capacity.
  • the method of production of the crystalline lithium cobalt oxide composition is a physical vapor deposition (PVD) method
  • PVD physical vapor deposition
  • localised concentrations of C03O4 can be introduced into the crystal structure of the composition (for example, by changing the cobalt flux relative to the lithium flux, varying the partial pressure of the gases supplied, or shutting off the lithium supply during the deposition) enabling controlling the morphology of the crystalline lithium cobalt oxide composition.
  • the control of one atomic flux relative to another during deposition, and the advantages it confers as regards the morphology of the composition has not been previously disclosed in the art.
  • crystalline lithium cobalt oxide compositions having the crystal orientations described herein which are typically less uniform and rougher in nature, exhibit better electrochemical behaviour in solid-state batteries with respect to both capacity and cycle life (particularly although not exclusively when cycled with 100% depth of discharge and/or when cycled at a temperature of 25°C) compared with films of the same composition which have crystal orientations that are flat and smooth.
  • ranges of values set forth herein as“X to Y” or“between X and Y” are inclusive of the end values X and Y.
  • the term“battery” is taken to be synonymous with the term“cell”, and is a device capable of either generating electrical energy from chemical reactions or facilitating chemical reactions through the introduction of electrical energy.
  • crystalline means a solid that has a regular internal arrangement of atoms, ions or molecules characteristic of crystals, i.e. that has a long range order in its lattice.
  • layered oxide refers generally to a layered mixed metal oxide having a rocksalt structure belonging to the R-3m space group, the oxide comprising lithium and one or more transition metals selected from the group consisting of chromium, manganese, iron, nickel, cobalt, and combinations thereof.
  • the term“crystalline oxide” means the crystalline lithium cobalt oxide or crystalline doped lithium cobalt oxide component of the composition described herein in relation to certain embodiments of the invention (as opposed to the whole composition which also includes C0 3 O 4 ).
  • the term“crystalline oxide” means a crystalline lithium cobalt oxide, i.e. it contains only lithium, cobalt and oxygen.
  • the term“crystalline oxide” means a doped crystalline doped lithium cobalt oxide, i.e. which also contains at least one dopant element (selected from those listed herein) in addition to lithium, cobalt and oxygen.
  • the invention provides a composition comprising C0 3 O 4 and a crystalline oxide of lithium and cobalt (as defined herein) or crystalline doped lithium cobalt oxide (as defined herein). In one embodiment, the invention provides a composition consisting essentially of C0 3 O 4 and a crystalline oxide of lithium and cobalt). In one embodiment, the invention provides a composition consisting of C0 3 O 4 and a crystalline oxide of lithium and cobalt.
  • the composition in one embodiment has a solid- state structure that includes both C0 3 O 4 and the crystalline oxide.
  • both C0 3 O 4 and the crystalline oxide are incorporated into the solid-state structure of the composition.
  • C0 3 O 4 is present on a surface of the solid-state structure of the composition.
  • C0 3 O 4 is incorporated into the solid-state structure of the composition as a layer 1-50 nm thick.
  • C03O4 is incorporated into the solid-state structure of the composition as a seed layer.
  • composition of certain embodiments of the invention comprises a crystalline oxide of lithium and cobalt (as defined herein) or crystalline doped lithium cobalt oxide (as defined herein).
  • at least 90% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline.
  • at least 95% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline.
  • at least 97% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline.
  • At least 98% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 99% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 99.5% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 99.7% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline.
  • At least 99.8% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 99.9% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, at least 99.95% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline. In one embodiment, 100% by mass of the total mass of the lithium cobalt oxide or doped lithium cobalt oxide is crystalline.
  • crystalline lithium cobalt oxide may comprise a high temperature phase, a low temperature phase, or a mixture thereof.
  • the high temperature phase of UC0O2 that is synthesised at a higher temperature typically 700°C or above, preferably 800 to 1000°C, more preferably about 900°C
  • the low temperature phase of UC0O2 that is synthesised at a lower temperature has approximately 6% cobalt within the lithium layers.
  • the crystalline lithium cobalt oxide contains at least 40% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains at least 50% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains at least 60% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains at least 70% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains at least 80% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains at least 85% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains at least 90% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains at least 95% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains at least 97% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains at least 98% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains at least 99% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains at least 99.5% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains at least 99.7% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains at least 99.9% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains 100% of the high temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 60% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 50% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 40% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains up to 30% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 20% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 15% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 10% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 5% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 3% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 2% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 1 % of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 0.5% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 0.3% of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains up to 0.1 % of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the crystalline lithium cobalt oxide contains 45 to 90 % of the high temperature phase and 10 % to 55 % of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide. In one embodiment, the crystalline lithium cobalt oxide contains 60 to 95 % of the high temperature phase and 5 % to 40 % of the low temperature phase, by mass of the total mass of crystalline lithium cobalt oxide.
  • the relative amounts of low temperature and high temperature phase of crystalline lithium cobalt oxide can be estimated using a Raman fitting technique similar to that described by Tintignac Electrochi mica Acta, 2012, 60, 121-129.
  • the majority of the cobalt present in the composition is in an oxidation state of +3, such that the stoichiometry of the lithium cobalt oxide is generally expressed as UC0O2.
  • the lithium cobalt oxide is deficient in lithium, such that the stoichiometry of the lithium cobalt oxide is Li x CoC where 0 ⁇ x ⁇ 1.
  • the lithium cobalt oxide contains a greater proportion of lithium and/or at least some of the cobalt present in the composition is in an oxidation state of +2, such that that the stoichiometry of the lithium cobalt oxide is U x Co0 2 where 1 ⁇ x£2.
  • the crystalline oxide according to certain embodiments of the invention comprises 45 to 55 atomic% lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 46 to
  • the crystalline oxide comprises 47 to 53 atomic % lithium, expressed as a percentage of the total atoms in the composition excluding oxygen. In one embodiment, the crystalline oxide comprises 47.0 to 53.0 atomic % lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.1 to 52.0 atomic % lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.2 to 51.0 atomic % lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.
  • the crystalline oxide comprises 47.3 to 50.0 atomic % lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.4 to 49.5 atomic % lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.5 to 49.1 atomic % lithium, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.
  • the crystalline oxide according to certain embodiments of the invention comprises 20 to 55 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 22.5 to
  • the crystalline oxide comprises 25 to 55 atomic% cobalt, expressed as a percentage of the total atoms in the composition excluding oxygen. In one embodiment, the crystalline oxide comprises 27.5 to 55 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the composition comprises 30 to 55 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the composition comprises 32.5 to 55 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.
  • the composition comprises 35 to 55 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.
  • the crystalline oxide comprises 37.5 to 55 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.
  • the crystalline oxide comprises 40 to 55 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.
  • the composition comprises 42.5 to 55 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.
  • the crystalline oxide comprises 45 to 55 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 46 to 54 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 46.5 to 53.5 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 47.0 to 53 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.
  • the crystalline oxide comprises 49.0 to 52.8 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 50.0 to 52.7 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 50.5 to 52.6 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 50.5 to 52.5 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen. In one embodiment, the crystalline oxide comprises 50.9 to 52.5 atomic% cobalt, expressed as a percentage of the total atoms in the crystalline oxide excluding oxygen.
  • the crystalline oxide may also include dopant elements, in addition to lithium and cobalt.
  • dopant elements in addition to lithium and cobalt.
  • the term“doped crystalline oxide” means a crystalline oxide of lithium and cobalt in which other elements (hereinafter“dopant elements”) may substitute for lithium, cobalt or oxygen in the crystalline structure.
  • dopant elements substitute for lithium.
  • such elements substitute for cobalt.
  • dopant elements substitute for lithium and cobalt.
  • dopant elements substitute for oxygen.
  • dopant elements which may substitute for lithium include sodium and potassium.
  • dopant elements which may substitute for oxygen include sulphur and selenium.
  • the dopant element which substitutes for cobalt is divalent (in other words, in a +2 oxidation state). In one embodiment, the dopant element which substitutes for cobalt is trivalent (in other words, in a +3 oxidation state). In one embodiment, the dopant element which substitutes for cobalt is tetravalent (in other words, in a +4 oxidation state).
  • dopant elements which may substitute for cobalt include alkaline earth metals (such as magnesium, calcium and strontium), transition metals (such as titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum and zinc), p-block elements (such as boron, aluminium, gallium, tin, lead and bismuth) and lanthanides (such as lanthanum, cerium, gadolinium and europium).
  • alkaline earth metals such as magnesium, calcium and strontium
  • transition metals such as titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum and zinc
  • p-block elements such as boron, aluminium, gallium, tin, lead and bismuth
  • lanthanides such as lanthanum, cerium, gadolinium and europium.
  • the dopant element which substitutes for cobalt, where present may be present in an amount of up to 25%, such as up to 20%, such as up to 15%, such as up to 12.5%, such as up to 10%, such as up to 7.5%, such as up to 5%, such as up to 4%, such as up to 3%, such as up to 2%, such as up to 1.5%, such as up to 1%, such as up to 0.9%, such as up to 0.8%, such as up to 0.7%, such as up to 0.6%, such as up to 0.5%, such as up to 0.4%, such as up to 0.3%, such as up to 0.2%, such as up to 0.15%, such as up to 0.1%, such as up to 0.09%, such as up to 0.08%, such as up to 0.07%, such as up to 0.06%, such as up to 0.05%, such as up to 0.04%, such as up to 0.03%, such as up to 0.02%, such as up to 0.01 %, such as up to 0.009%
  • the doped crystalline oxide comprises 0 to 25 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.
  • dopant element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped
  • the doped crystalline oxide comprises 0 to 20 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.
  • dopant element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped
  • the doped crystalline oxide comprises 0 to 15 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.
  • dopant element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped
  • the doped crystalline oxide comprises 0 to 10 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.
  • dopant element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped
  • the doped crystalline oxide comprises 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.
  • dopant element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped
  • the doped crystalline oxide comprises 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.
  • dopant element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped
  • the doped crystalline oxide comprises 0 to 2 atomic% of at least one element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.
  • the doped crystalline oxide comprises 0 to 1.5 atomic% of at least one element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.
  • the doped crystalline oxide comprises 0 to 1 atomic% of at least one element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.
  • the doped crystalline oxide comprises 0 to 0.5 atomic% of at least one element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen.
  • element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the amount expressed as a percentage of the total atoms in the doped crystalline oxide excluding oxygen
  • the doped crystalline lithium cobalt oxide component having: 45 to 55 atomic% lithium; 40 to 55 atomic% 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium,; the amounts expressed as % of the total atoms in the doped crystalline lithium cobalt oxide excluding oxygen.
  • dopant element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, ce
  • the doped crystalline lithium cobalt oxide component having: 45 to 55 atomic% lithium; 42.5 to 55 atomic% 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium; the amounts expressed as % of the total atoms in the doped crystalline lithium cobalt oxide excluding oxygen.
  • dopant element selected from the group consisting of: magnesium, calcium, strontium, titanium, zirconium, vanadium, chromium, manganese, iron, copper, ruthenium, nickel, molybdenum, zinc, boron, aluminium, gallium, tin, lead, bismuth, lanthanum, ce
  • composition of the invention consisting of: 45 to 55 atomic% lithium and 45 to 55 atomic% cobalt; the amounts expressed as % of the total atoms in the crystalline oxide excluding oxygen.
  • composition of the invention consisting of: 47.0 to 53.0 atomic % lithium and 47.0 to 53.0 atomic % cobalt; the amounts expressed as % of the total atoms in the crystalline oxide excluding oxygen.
  • composition of the invention consisting of: 47.5 to 49.1 atomic % lithium and 50.9 to 52.5 atomic % cobalt; the amounts expressed as % of the total atoms in the crystalline oxide excluding oxygen.
  • the crystalline composition of an embodiment of the present invention also includes oxygen which provides the source of negative ions in the crystalline composition. It can be understood that the composition comprises sufficient oxygen (as oxide ions O 2 ) to ensure it is electrically neutral, the precise amount of oxygen depending on the atomic percentage and oxidation state of the other elements present in the composition.
  • a distinguishing feature of the composition of an embodiment of the present invention is that the crystalline structure of the composition includes a localized concentration of C03O4.
  • the inventors have found that introducing localized concentrations of C03O4 into the crystal structure of a crystalline lithium cobalt oxide composition allows the morphology of the composition to be controlled in a more precise manner than was previously possible in the art. Without wishing to be bound by theory, it is thought that the localized concentration of C03O4 may act as a seeding layer for UC0O2 crystallites.
  • the localized concentration of C03O4 creates defects in the crystal structure of lithium cobalt oxides which promote the preferred crystal orientations described herein, resulting in the rough or irregular morphology of the crystal as described herein (comprising, for example, large plate-like grains), and which exhibit improved electrochemical properties compared with lithium cobalt oxide compositions as known in the art.
  • the composition is in the form of a film
  • the film typically exhibits a large crystallite size of between 0.2 and 3.0 pm, preferably 0.3 to 2.5 pm. In one embodiment the film exhibits a large crystallite size of between 0.7 and 2.0 pm. In one embodiment the film exhibits a large crystallite size of between 0.5 and 1.0 pm.
  • the film exhibits a large crystallite size of between 0.4 and 0.9 pm.
  • the crystallite sizes are measured by hand and/or using a scanning electron microscope (SEM) having an appropriate measurement tool and appropriate hardware and/or software.
  • the film comprises crystallites having a maximum dimension, in the plane of the film, that is at least 0.2pm, preferably at least 0.3 pm, in certain embodiments at least 0.4 pm.
  • the film comprises crystallites having a maximum dimension, in the plane of the film, of up to 3 pm, in certain cases up to 2 pm.
  • the film When the composition is in the form of a film, the film typically exhibits an average area of larger crystallites of between 0.1 and 2 pm 2 , preferably between 0.2 and 1 pm 2 . In one embodiment, the film exhibits an average area of larger crystallites of 0.8 pm 2 . In one embodiment, the film exhibits an average area of larger crystallites of 0.3 pm 2 . Typically, the average area of larger crystallites are measured using a scanning electron microscope (SEM) having an appropriate measurement tool and appropriate hardware and/or software.
  • SEM scanning electron microscope
  • composition 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 larger crystallites. In one embodiment 70 to 90%, such as 75 to 85 %, such as 79%, of the surface area of the film is covered by larger crystallites. In one embodiment 15 to 35 %, such as 20 to 25 %, such as 22%, of the surface area of the film is covered by larger crystallites.
  • 1 to 10 %, preferably 3 to 6%, such as 4.5 to 5.4%, such as 5% of the surface area of the film is covered by larger crystallites.
  • the proportion of the film covered by larger crystallites is measured using a scanning electron microscope (SEM) using the area and the number of larger crystallites within the image area using appropriate hardware and/or software.
  • crystallite is used herein to denote a region of the film within which the orientation of the crystal lattice remains substantially constant. Thus, the boundary between adjacent crystallites is typically indicated by a change in lattice orientation.
  • a single crystallite may include multiple sub-crystallites, all having crystal lattices of substantially the same orientation.
  • an individual sub-crystallite grows through seeding on an adjacent sub-crystallite, such that the lattice orientations of the two sub-crystallites are substantially aligned.
  • a crystallite, as defined herein may be referred to in the art as a“grain”.
  • the roughness of the surface may be measured using a technique such as stylus profilometry to determine the average roughness R a , which is the arithmetic average value of filtered roughness profile determined from deviations about the centre line within the evaluation length.
  • the average surface roughness (R a ) of the film is between 10 and 200 nm, such as 20 to 150 nm, such as 40 to 120 nm.
  • the average surface roughness (R a ) of the film may be at least 10nm, in certain cases at least 30nm, in certain cases at least 50nm. In certain cases, the average surface roughness (R a ) of the film may be up to 250 nm.
  • films having the smooth surfaces of the crystal having predominantly (003) orientation which is generally undesirable for the purpose of the present invention, have an average surface roughness R a of less than 10 nm, such as 4 nm.
  • the average roughness is measured using a stylus profilometer, the figure R a denoting the average roughness (average deviation from the mean).
  • the average R a is calculated from three different measurements a few millimetres apart, each scan typically being 2mm long.
  • the localised concentration of C0 3 O 4 may be present in an amount to facilitate the desired structure of the resulting crystalline film.
  • 0.01% to 10% of the total mass of said composition is C0 3 O 4 .
  • 0.01 % to 5% total mass of said composition is C0 3 O 4 .
  • 5% to 7.5% total mass of said composition is C0 3 O 4 .
  • 7.5% to 10% total mass of said composition is C0 3 O 4 .
  • 0.01 % to 0.05% total mass of said composition is C0 3 O 4 .
  • 0.05% to 0.1 % total mass of said composition is C0 3 O 4 .
  • 0.1 % to 0.5% total mass of said composition is C0 3 O 4 . In one embodiment, 0.5% to 1.0% total mass of said composition is C0 3 O 4 . In one embodiment, 1.0% to 1.5% total mass of said composition is C0 3 O 4 . In one embodiment, 1.5% to 2.0% total mass of said composition is C0 3 O 4 . In one embodiment, 2.0% to 3.0% total mass of said composition is C0 3 O 4 . In one embodiment, 3.0% to 4.0% total mass of said composition is C03O4. In one embodiment, 4.0% to 5.0% total mass of said composition is C03O4. The total mass expressed includes all elements including oxygen.
  • the composition is non-homogeneous with regard to the distribution of C03O4 within the composition.
  • the composition is formed in the form of a film layer, especially a film layer on a substrate (as defined in more detail below).
  • said composition is a thin-film layer comprising a top surface, a bottom surface, and a height of 1-50 pm.
  • the height of the layer is from 1 to 30 pm.
  • the height of the layer is from 2 to 20 pm.
  • the height of the layer is from 3 to 12 pm.
  • the height of the layer is from 5 to 10 pm.
  • the height of the layer is from 6 to 7 pm.
  • the crystalline oxide thin-film layer comprises a seed layer of C03O4. In one embodiment, said seed layer is within 75% of the height from the bottom surface. In one embodiment, said seed layer is within 50% of the height from the bottom surface. In one embodiment, said seed layer is within 25% of the height from the bottom surface. In one embodiment, said seed layer is within 10% of the height from the bottom surface. In one embodiment, said seed layer is within 5% of the height from the bottom surface. In one embodiment, said seed layer is within 2.5% of the height from the bottom surface. In one embodiment, said seed layer comprises the bottom surface of the thin-film layer.
  • said seed layer is 0.1-100 nm thick. In one embodiment, said seed layer is 0.1-50 nm thick. In one embodiment, said seed layer is 0.1-25 nm thick. In one embodiment, said seed layer is 0.1-10 nm thick. In one embodiment, said seed layer is 1-50 nm thick. In one embodiment, said seed layer is 1-25 nm thick. In one embodiment, said seed layer is 1-10 nm thick. In one embodiment, said seed layer is 1-5 nm thick.
  • the localized concentration of C03O4 may be defined in terms of the thickness of an effective layer of C03O4.
  • by“effective layer” is meant that if all of the C03O4 present in the localized concentration were, hypothetically, to be distributed evenly throughout the bulk of the composition as a layer.
  • the thickness of the effective layer compared with the thickness of the crystalline oxide component of the composition, can be used as an estimation of the amount of the C0 3 O 4 present in the localized concentration.
  • the thickness of the crystalline lithium cobalt oxide composition is from 1 to 50 pm and the thickness of the effective C03O4 layer is from 0.1 to 5 pm. In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is from 2 to 20 pm and the thickness of the effective C03O4 layer is from 0.2 to 500 nm.
  • a further distinguishing feature of the lithium cobalt oxide composition of an embodiment of the present invention is its crystalline structure.
  • the present inventors have surprisingly found that crystalline lithium cobalt oxide compositions having the morphology described herein are typically less uniform and rougher in nature than the crystalline lithium cobalt oxides used in solid-state batteries according to the prior art, and exhibit more favourable electrochemical behaviour in such solid-state batteries with respect to both capacity and cycle life compared with films of the same composition which have crystal orientations that are flat and smooth.
  • the crystalline structure of the lithium cobalt oxide composition or doped lithium cobalt oxide composition may be defined in terms of the Miller indices of the crystal lattice planes.
  • the Miller indices form a notation system in crystallography for planes in crystal (Bravais) lattices.
  • a family of lattice planes is determined by three integers h, k, and t, the Miller indices. They are written (hkt), and denote the family of planes orthogonal to hbi + kb 2 + L> 3 , where bi are the basis of the reciprocal lattice vectors.
  • the integers are usually written in lowest terms, i.e. their greatest common divisor should be 1.
  • At least a portion of the crystalline structure of the crystalline oxide i.e. the crystalline lithium cobalt oxide composition, crystalline doped lithium cobalt oxide, has an orientation having a Miller index selected from the group consisting of: (101), (104), (110) and (012), or a mixture of any thereof.
  • at least a portion of the crystalline structure of the crystalline oxide composition has an orientation having a Miller index selected from the group consisting of: (101), (104) or both.
  • the crystal orientation of the crystalline structure of the crystalline oxide may be defined by reference to a plane parallel to the bottom surface of the composition.
  • At least a portion of the crystalline structure of the crystalline oxide has a crystal orientation, relative to a plane parallel to the bottom surface, selected from the group consisting of: (101), (104), (110) and (012), or a mixture of any thereof.
  • at least a portion of the crystalline structure of the crystalline oxide composition has an orientation, relative to a plane parallel to the bottom surface, selected from the group consisting of: (101), (104) or both.
  • the crystal orientation of the crystalline structure of the crystalline oxide may be defined by reference to at least one lattice plane parallel to the bottom surface of the composition.
  • the lattice plane defined by the Miller index h is parallel to the bottom surface of the composition.
  • the lattice plane defined by the Miller index k is parallel to the bottom surface of the
  • the lattice plane defined by the Miller index t is parallel to the bottom surface of the composition.
  • At least a portion of the crystalline structure of the crystalline oxide has a crystal orientation, relative to a plane parallel to the bottom surface, selected from the group consisting of: (101), (104), (1 10) and (012), or a mixture of any thereof.
  • at least a portion of the crystalline structure of the crystalline oxide composition has an orientation, relative to a plane parallel to the bottom surface, selected from the group consisting of: (101), (104) or both.
  • the crystal orientation of the crystalline structure of the crystalline oxide may be defined by reference to a plane perpendicular to the direction of growth of the crystal.
  • At least a portion of the crystalline structure of the crystalline oxide has a crystal orientation, relative to a plane perpendicular to the direction of growth of the crystal, selected from the group consisting of: (101), (104), (110) and (012), or a mixture of any thereof.
  • at least a portion of the crystalline structure of the crystalline oxide composition has an orientation, relative to a plane perpendicular to the direction of growth of the crystal, selected from the group consisting of: (101), (104) or both.
  • the crystal orientation of the crystalline structure of the crystalline oxide may be defined by reference to a plane perpendicular to the direction of the lithium-ion pathway through the battery. Therefore, in one embodiment, the composition of the present invention is present in a lithium-ion battery and at least a portion of the crystalline structure of the crystalline oxide has a crystal orientation, relative to a plane perpendicular to the direction of the lithium-ion pathway through the battery, selected from the group consisting of: (101), (104),
  • the crystalline structure of the crystalline oxide composition has an orientation, relative to a plane perpendicular to the direction of the lithium-ion pathway through the battery, selected from the group consisting of: (101), (104) or both.
  • the crystal orientation of the crystalline structure of the crystalline oxide may be defined by reference to a plane parallel to the substrate. Therefore, in one embodiment, at least a portion of the crystalline structure of the crystalline oxide has a crystal orientation, relative to a plane parallel to the substrate, selected from the group consisting of: (101), (104), (110) and (012), or a mixture of any thereof. In one embodiment, at least a portion of the crystalline structure of the crystalline oxide composition has an orientation, relative to a plane parallel to the substrate, selected from the group consisting of: (101), (104) or both.
  • At least a portion of the crystalline structure of the crystalline oxide component of the composition has an orientation having the Miller index (101) (the orientations optionally being defined by reference to any of the definitions above).
  • at least 0.01 % by mass of the crystalline structure of the crystalline oxide is in the (101) orientation.
  • at least 0.02% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation.
  • at least 0.05% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation.
  • at least 0.1% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation.
  • at least 0.2% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation.
  • At least 0.5% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 1% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 2% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 5% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 10% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 20% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation.
  • At least 40% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 50% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 60% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 70% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 80% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation.
  • At least 30% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 90% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 95% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 96% by mass of the crystalline structure of the crystalline oxide composition is in the (101) orientation. In one embodiment, at least 97% by mass of the crystalline structure of crystalline oxide is in the (101) orientation. In one embodiment, at least 98% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation.
  • At least 99% by mass of the crystalline structure of the lithium cobalt oxide composition is in the (101) orientation. In one embodiment, at least 99.5% by mass of the crystalline structure of the crystalline oxide is in the (101) orientation. In one embodiment, at least 99.7% by mass of the crystalline structure of the crystalline oxide composition is in the (101) orientation. In one embodiment, at least 99.9% by mass of the crystalline structure of the crystalline oxide composition is in the (101) orientation. These percentages are expressed by mass of the total mass of the crystalline composition (i.e. in all crystal orientations present).
  • At least a portion of the crystalline structure of the crystalline oxide has an orientation having the Miller index (104) (the orientations optionally being defined by reference to any of the definitions above).
  • at least 0.01 % by mass of the crystalline structure of the crystalline oxide is in the (104) orientation.
  • at least 0.02% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation.
  • at least 0.05% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation.
  • at least 0.1% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation.
  • at least 0.2% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation.
  • At least 0.5% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 1 % by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 2% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 5% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 10% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 20% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation.
  • At least 40% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 50% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 60% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 70% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 80% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 90% by mass of the crystalline structure of the crystalline oxide composition is in the (104) orientation. In one embodiment, at least 95% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation.
  • At least 96% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 97% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 98% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 99% by mass of the crystalline structure of the crystalline composition is in the (104) orientation. In one embodiment, at least 99.5% by mass of the crystalline structure of the crystalline oxide is in the (104) orientation. In one embodiment, at least 99.7% by mass of the crystalline structure of the crystalline oxide composition is in the (104) orientation. In one embodiment, at least 99.9% by mass of the crystalline structure of the crystalline oxide composition is in the (104) orientation. These percentages are expressed by mass of the total mass of the crystalline oxide (i.e. in all crystal orientations present).
  • At least a portion of the crystalline structure of the crystalline oxide composition has an orientation having the Miller index (110) (the orientations optionally being defined by reference to any of the definitions above).
  • at least 0.01 % by mass of the crystalline structure of the crystalline oxide is in the (1 10) orientation.
  • at least 0.02% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation.
  • at least 0.05% by mass of the crystalline structure of the crystalline oxide is in the (1 10) orientation.
  • at least 0.1% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation.
  • at least 0.2% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation.
  • At least 0.5% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 1% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 2% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 5% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 10% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 20% by mass of the crystalline structure of the crystalline oxide is in the (1 10) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (1 10) orientation.
  • At least 40% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 50% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 60% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 70% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 80% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 90% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 95% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation.
  • At least 96% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 97% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 98% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 99% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 99.5% by mass of the crystalline structure of the crystalline oxide is in the (1 10) orientation. In one embodiment, at least 99.7% by mass of the crystalline structure of the crystalline oxide is in the (110) orientation. In one embodiment, at least 99.9% by mass of the crystalline structure of the crystalline oxide is in the (1 10) orientation. These percentages are expressed by mass of the total mass of the crystalline composition (i.e. in all crystal orientations present).
  • At least a portion of the crystalline structure of the lithium cobalt oxide composition has an orientation having the Miller index (012) (the orientations optionally being defined by reference to any of the definitions above).
  • at least 0.01% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation.
  • at least 0.02% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation.
  • at least 0.05% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation.
  • at least 0.1% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation.
  • At least 0.2% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 0.5% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 1 % by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 2% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 5% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 10% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation.
  • At least 20% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 30% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 40% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 50% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 60% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 70% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 80% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation.
  • At least 90% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 95% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 96% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 97% by mass of the crystalline structure of the crystalline oxide composition is in the (012) orientation. In one embodiment, at least 98% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 99% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation.
  • At least 99.5% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 99.7% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. In one embodiment, at least 99.9% by mass of the crystalline structure of the crystalline oxide is in the (012) orientation. These percentages are expressed by mass of the total mass of the crystalline oxide (i.e. in all crystal orientations present).
  • At least a portion of the crystalline structure of the crystalline oxide composition is in an orientation having the Miller index (003) (the orientations optionally being defined by reference to any of the definitions above).
  • the presence of crystallites solely in the (003) orientation is undesirable from the purpose of the present invention as crystals having that orientation lack the roughness of the crystals having the preferred orientations above and solid-state batteries lack the favourable electrochemical properties of the lithium cobalt oxides having those crystal orientations.
  • at most 99.9% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation.
  • at most 99.7% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation.
  • At most 99.5% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 99% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 97% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 95% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 90% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 80% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation.
  • At most 70% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 60% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 50% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 40% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 30% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 20% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 10% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation.
  • At most 5% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 4% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 3% by mass of the crystalline structure of the crystalline lithium cobalt oxide is in the (003) orientation. In one embodiment, at most 2% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 1 % by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 0.5% by mass of the crystalline structure of the crystalline oxide composition is in the (003) orientation.
  • At most 0.3% by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. In one embodiment, at most 0.1 % by mass of the crystalline structure of the crystalline oxide is in the (003) orientation. These percentages are expressed by mass of the total mass of the crystalline composition (i.e. in all crystal orientations present).
  • composition of an embodiment of the present invention comprises a thin film layer (particularly although not exclusively wherein the thin-film layer comprises a seed layer of C03O4), in one embodiment, at least 2.5% of the top surface of the thin film layer is crystalline oxide comprises a crystal orientation selected from (101),
  • the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • at least 4.5% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • at least 5% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • at least 7.5% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • at least 10% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • At least 25% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • at least 50% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • at least 75% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • at least 80% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • at least 90% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, greater than 95% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, greater than 97.5% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, greater than 99% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof. In one embodiment, greater than 99.5% of the top surface is crystalline oxide comprising a crystal orientation selected from (101), (104), (110), or a combination thereof.
  • the crystalline structure of the composition may be defined in terms of bands in the Raman spectrum.
  • Raman spectroscopy is used to characterize materials, measure temperature, and determine the crystallographic orientation of a sample.
  • the Raman spectrometer uses laser light, typically laser light in the visible or near infra-red portion of the electromagnetic spectrum (390 to 1000 nm), such as 450 to 900 nm, preferably 500 to 550 nm, more preferably 530 to 540 nm, and most preferably 532 nm.
  • the Raman microscope has objectives ranging from 5X to 500X, preferably 10X to 100X.
  • the Raman spectrometer has a spatial resolution (defined as sample surface spot area) of 0.5 to 2 pm 2 , preferably 1 pm 2 .
  • the bands in the Raman spectra may vary from the quoted wavenumber depending on the amount, crystal orientation and purity of the substance having that characteristic band.
  • the wavenumbers of the bands in the Raman spectrum are quoted to ⁇ 25 cm -1 .
  • the wavenumbers of the bands in the Raman spectrum are quoted to ⁇ 20 cm -1 .
  • the wavenumbers of the bands in the Raman spectrum are quoted to ⁇ 15 cm -1 .
  • the wavenumbers of the bands in the Raman spectrum are quoted to ⁇ 10 cm -1 .
  • the wavenumbers of the bands in the Raman spectrum are quoted to ⁇ 5 cm 1 .
  • the wavenumbers of the bands in the Raman spectrum are quoted to ⁇ 2 cm 1 .
  • the wavenumbers of the bands in the Raman spectrum are quoted to ⁇ 1 cm 1 .
  • the composition exhibits a band in the Raman spectrum at a wavenumber of 690 cm 1 (to the tolerances quoted above, either in its broadest aspect or a preferred aspect). This band is typically characteristic of the presence of Ai g mode of C03O4 in the composition.
  • the composition exhibits a band in the Raman spectrum at a wavenumber of 526 cm 1 (to the tolerances quoted above, either in its broadest aspect or a preferred aspect). This band is typically characteristic of the presence of F 2g of C03O4 in the composition.
  • the composition exhibits a band in the Raman spectrum at a wavenumber of 625 cm 1 (to the tolerances quoted above, either in its broadest aspect or a preferred aspect). This band is typically characteristic of the presence of F 2g of C03O4 in the composition.
  • the composition exhibits a band in the Raman spectrum at a wavenumber of 484 cm 1 (to the tolerances quoted above, either in its broadest aspect or a preferred aspect).
  • the composition exhibits a band in the Raman spectrum at a wavenumber of 593 cm 1 (to the tolerances quoted above, either in its broadest aspect or a preferred aspect).
  • the ( R-3m ) crystalline structure of the lithium cobalt oxide composition exhibits at least one band in the Raman spectrum at a wavenumber selected from the group consisting of: 484 and 593 cm 1 (both to the tolerances quoted above, either in its broadest aspect or a preferred aspect) attributed to the Ai g and E g modes respectively.
  • Raman bands at these wavenumbers are typically characteristic of the presence of the high temperature phase of lithium cobalt oxide having a crystal structure in one of the preferred orientations set out above.
  • the composition exhibits a band in the Raman spectrum at a wavenumber of 690 cm -1 (to the tolerances quoted above, either in its broadest aspect or a preferred aspect) and at least one other band at a wavenumber selected from the group consisting of: 484 and 593 cm 1 (to the tolerances quoted above, either in its broadest aspect or a preferred aspect).
  • the crystalline structure of the composition may be defined in terms of its powder X-ray diffraction pattern.
  • X-ray crystallography is a technique used for determining the atomic and molecular structure of a crystal, in which the crystalline atoms cause a beam of incident X-rays to diffract into many specific directions. By measuring the angles and intensities of these diffracted beams, a crystallographer can produce a three- dimensional picture of the density of electrons within the crystal. From this electron density, the mean positions of the atoms in the crystal can be determined, as well as their chemical bonds, their disorder, and various other information.
  • the X-ray diffraction uses a Cu Ka X-ray source.
  • the crystalline structure of the crystalline oxide can be described in terms of the measured two-theta (2Q) measurements of the peaks in the X-ray powder diffraction pattern. Typically, these measurements are quoted to ⁇ 0.2°, preferably ⁇ 0.1 ° and more preferably ⁇ 0.05°.
  • the crystalline structure of the crystalline oxide exhibits at least one X-ray powder diffraction peak selected from the group consisting of: 2Q ( ⁇ 0.2°) 37.4°, 39.1 °, 45.3° and 66.4°. In one embodiment, the crystalline structure of the crystalline oxide exhibits an X-ray powder diffraction peak at 2Q ( ⁇ 0.2°) 37.4°. This peak is characteristic of UC0O2 in the (101) crystal orientation.
  • the crystalline structure of the crystalline oxide exhibits an X-ray powder diffraction peak at 2Q ( ⁇ 0.2°) 39.1 °. This peak is characteristic of UC0O2 in the (012) crystal orientation.
  • the crystalline structure of the crystalline oxide exhibits an X-ray powder diffraction peak at 2Q ( ⁇ 0.2°) 45.3°. This peak is characteristic of UC0O2 in the (104) crystal orientation.
  • the crystalline structure of the crystalline oxide exhibits an X-ray powder diffraction peak at 2Q ( ⁇ 0.2°) 66.4°. This peak is characteristic of UC0O2 in the (1 10) crystal orientation.
  • the crystalline structure of the crystalline oxide can be described in terms of the 2Q measurement which corresponds to the distance (d) between adjacent lattice planes (d-spacing). Typically, these measurements are quoted to ⁇ 0.2A, preferably ⁇ 0.1 A and more preferably ⁇ 0.05A.
  • the crystalline structure of the crystalline oxide exhibits an X-ray powder diffraction peak at 2Q 37.4° corresponding to d (A) 2.399 ( ⁇ 0.1). This peak is characteristic of UC0O2 in the (101) crystal orientation.
  • the crystalline structure of the crystalline oxide exhibits an X-ray powder diffraction peak at 2Q 39.1 0 corresponding to d (A) 2.301 ( ⁇ 0.1). This peak is characteristic of UC0O2 in the (012) crystal orientation.
  • the crystalline structure of the crystalline oxide exhibits an X-ray powder diffraction peak at 2Q 45.3° corresponding to d (A) 2.001 ( ⁇ 0.1). This peak is characteristic of UC0O2 in the (104) crystal orientation.
  • the crystalline structure of the crystalline oxide exhibits an X-ray powder diffraction peak at 2Q 66.4° corresponding to d (A) 1.406 ( ⁇ 0.1). This peak is characteristic of UC0O2 in the (1 10) crystal orientation.
  • said crystalline oxide has a crystalline structure exhibiting an X- ray powder diffraction comprising peaks at 2Q selected from 37.4°, 45.3° or both 37.4°and 45.3°, corresponding to d(A) ( ⁇ 0.1 A) selected from 2.399 A, 2.001 A or both 2.399 A and 2.001 A.
  • the crystalline structure of the lithium cobalt oxide composition may comprise crystallites having more than one of the above orientations, and therefore more than one of the above peaks may be observed in the powder X-ray diffraction pattern of a given sample of the
  • the crystalline structure of the lithium cobalt oxide composition exhibits at least one X-ray powder diffraction peak at 2Q selected from the group consisting 37.4°, 45.3° (each ⁇ 0.1 °) or both, and/or of corresponding to d(A) 2.399 , 2.001 each ( ⁇ 0.1 A) or both.
  • a composition comprising a crystalline oxide of lithium and cobalt, wherein the lithium and cobalt atomic% are as defined above, either in its broadest aspect or a preferred aspect, the crystalline structure of the composition being characterized by a localized concentration of C03O4, as defined above, either in its broadest aspect or a preferred aspect, the crystalline structure being further characterized by at least one of the following parameters (a) to (c):
  • a composition comprising a crystalline oxide of lithium and cobalt, wherein the lithium and cobalt atomic% are as defined above, either in its broadest aspect or a preferred aspect, the crystalline structure of the composition being characterized by a localized concentration of C03O4, as defined above, either in its broadest aspect or a preferred aspect, and an orientation selected from the group consisting of: (101), (104), (1 10) and (012), preferably (101) or (104).
  • a composition comprising a crystalline oxide of lithium and cobalt, wherein the lithium and cobalt atomic% are as defined above, either in its broadest aspect or a preferred aspect, the crystalline structure of the composition being characterized by a localized concentration of C03O4, as defined above, either in its broadest aspect or a preferred aspect, and by a band in the Raman spectrum at a wavenumber of 690 cm -1 ( ⁇ 5 cm -1 ).
  • a composition comprising a crystalline oxide of lithium and cobalt, wherein the lithium and cobalt atomic% are as defined above, either in its broadest aspect or a preferred aspect, the crystalline structure of the composition being characterized by a localized concentration of C03O4, as defined above, either in its broadest aspect or a preferred aspect, and by at least one X-ray powder diffraction peak at selected from the group consisting of: 37.4°, 39.1 °, 45.3° and 66.4° (each ⁇ 0.2°), and/or corresponding to spacing d(A) 2.399, 2.301 , 2.001 or 1.406, preferably ( ⁇ 0.1 °) 37.4° or 45.3° corresponding to spacing d(A) 2.399 or 2.001.
  • the lithium cobalt oxide is formed in the form of a film, especially a film on a substrate (as defined in more detail below).
  • the thickness of the crystalline lithium cobalt oxide composition is from 1 to 30 pm. In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is from 2 to 20 pm. In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is from 3 to 12 pm. In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is from 5 to 10 pm. In one embodiment, the thickness of the crystalline lithium cobalt oxide composition is from 6 to 7 pm.
  • the invention may also provide a method of preparing a composition comprising C03O4 and crystalline lithium cobalt oxide, particularly although not exclusively the composition according to the first aspect of the invention.
  • the method generally comprises providing a source of each component element of the compound, wherein the sources comprise a source of lithium, a source of oxygen and a source of cobalt (and optionally a source of one or more dopant elements as defined below); and depositing these onto a substrate, particularly although not exclusively a substrate heated to between about 50°C and about 800°C.
  • the component elements from the sources react on the substrate to form a crystalline oxide of lithium and cobalt (optionally doped with one or more of the elements defined below) and the component elements from the sources of cobalt and oxygen react on the substrate to form C03O 4 .
  • the method involves forming the crystalline lithium cobalt oxide (or crystalline doped lithium cobalt oxide) in the form of a film, typically on a substrate.
  • Suitable substrates are well known to the person skilled in the art, and include metals (such as platinum, aluminium, titanium, chromium, iron, zinc, gold, silver, nickel, molybdenum, including alloys thereof, which may include non-metals such as carbon, examples of which include steels such as stainless steel), metal oxides, such as aluminium oxide, particularly conducting metal oxides such as indium tin oxide), silicon, silica, silicon oxide (including doped silicon oxide), aluminosilicate materials, glasses, and ceramic material.
  • metals such as platinum, aluminium, titanium, chromium, iron, zinc, gold, silver, nickel, molybdenum, including alloys thereof, which may include non-metals such as carbon, examples of which include steels such as stainless steel
  • metal oxides such as aluminium oxide, particularly conducting metal oxides such as indium t
  • the method of an example of the invention has the distinguishing feature that one or more conditions of the method are varied such that a localized concentration of C03O4 (as defined above, either in its broadest aspect or a preferred aspect) formed so as to enable crystal growth of a lithium cobalt oxide composition having the desired crystalline structure (as defined above, either in its broadest aspect or a preferred aspect).
  • the method is characterized in that one or more conditions of the method are varied such that a localized concentration of C03O4 is formed as a seed layer so as to enable crystal growth of a composition having the required crystalline structure, and greater roughness / irregularity (as described above) than those of the prior art.
  • the method generally comprises providing a source of each component element of the compound, wherein the sources comprise a source of lithium, a source of oxygen and a source of cobalt, and optionally a source of one or more of the dopant elements listed herein.
  • the sources comprise a source of lithium, a source of oxygen and a source of cobalt, and optionally a source of one or more of the dopant elements listed herein.
  • the precise nature of the sources of such elements is not critical to the present invention provided that it contains the required element.
  • each component element in the vapor form collides with and adheres to the surface of the heated substrate, where the atoms of each element are then mobile on the surface and so are able to react with each other to form the oxide compound.
  • the vapor source comprises an electron beam evaporator or a Knudsen cell (K-Cell); these are well-suited for materials with low partial pressures.
  • K-Cell Knudsen cell
  • a Knudsen cell uses a series of heating filaments around the crucible, whereas in an electron beam evaporator the heating is achieved by using magnets to direct a beam of high energy electrons onto the material.
  • lithium and cobalt can be deposited from a Knudsen cell source or an electron gun (E-gun).
  • the source of oxygen is molecular oxygen. In one embodiment, the source of oxygen is atomic oxygen (typically although not exclusively produced by means of an oxygen plasma source). In one embodiment, the source of oxygen is an ozone source.
  • An oxygen plasma source delivers plasma-phase oxygen, i.e. a flux of oxygen atoms, radicals and ions.
  • the source may be a radio frequency (RF) plasma source or ozone source for example.
  • RF radio frequency
  • Further gases may be added to the oxygen flow in small quantities if desired.
  • the one or more further gases is present in a total proportion of up to 10 %, such as up to 5 %, such as up to 3 %, such as up to 2 %, such as up to 1 %. This is typically measured by a Residual Gas Analyser (RGA) and is defined as molar % relative to 100 mol% oxygen, by dividing the partial pressure of the one or more further gases by the oxygen partial pressure.
  • RAA Residual Gas Analyser
  • the method additionally comprises providing a source of 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium such that the one or more elements form part of the crystalline composition having the required crystal structure.
  • an amorphous film could be deposited, and then the method of the invention could be used to anneal the amorphous form.
  • this is not preferred as such a method does not exhibit the advantages of the invention, such as the direct formation of stoichiometric compounds at low substrate temperature and avoiding the requirement for higher temperature post deposition annealing.
  • One general method used in accordance with one embodiment of the invention is a physical vapor deposition (PVD) method.
  • PVD physical vapor deposition
  • the crystalline lithium cobalt oxide composition is formed from the component elements lithium, cobalt and oxygen, by providing a vapor source of each component element of the compound and co-depositing the component elements from the vapor sources onto a substrate, typically a heated substrate.
  • a vapor deposition method comprising: providing a vapor source of each component element of the compound, wherein the vapor sources comprise a source of lithium, a source of oxygen and 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, to deliver a flux of lithium, a flux of oxygen, a flux of cobalt and optionally a flux of the said at least one dopant elements; heating a substrate to between substantially 50°C and 800°C; depositing the component elements from the sources onto the heated substrate, wherein the component elements react on the substrate to form a crystalline oxide of lithium and cobalt
  • the physical vapor deposition (PVD) method typically involves co-depositing the component elements from the vapor sources onto a heated substrate.
  • the substrate is heated to about 150 to about 700°C.
  • the substrate is heated to about 200 to about 700°C.
  • the substrate is heated to about 300 to about 450°C.
  • the physical vapor deposition (PVD) method is typically carried out at a pressure of 1 x 10 7 to 1 x 10 4 Torr, preferably 1 x 10 ® to 5 x 10 5 Torr, and more preferably 5 x 10 ® to 2 x 10 5 Torr.
  • the method is carried out such that the deposition rate of the film is between 0.1 and 10 pm/hour. In one embodiment, the method is carried out such that the deposition rate is between 0.2 and 5 pm/hour. In one embodiment, the method is carried out such that the deposition rate is between 0.3 and 1.6 pm/hour.
  • the method is carried out such that the deposition rate is between 0.4 and 0.8 pm/hour.
  • one or more conditions of the vapor deposition method are varied such that a localized concentration of C03O4 is formed so as to enable crystal growth of a composition having the required crystalline structure.
  • the varying one or more conditions comprises delivering the cobalt and the lithium at a ratio of fluxes different from the ratio of fluxes delivered to deposit a crystalline oxide of lithium and cobalt.
  • delivering the cobalt and the lithium at a ratio of fluxes different from the ratio of fluxes delivered to deposit crystalline lithium cobalt oxide may allow C03O4 to be formed (typically as a seeding layer) so as to enable crystal growth of a lithium cobalt oxide composition having the required crystalline structure.
  • the flux of cobalt is between 0.1 and 13 A/s. In one embodiment, the flux of cobalt is between 0.1 and 7 A/s. In one embodiment, the flux of cobalt is between 0.4 and 2 A/s. In one embodiment, the flux of cobalt is between 0.5 and 1 A/s. This flux is typically measured at the substrate surface. Typically, the flux of cobalt is measured in the presence of oxygen (such that, when it is measured in this way, what is actually measured is the flux of cobalt oxide).
  • the flux of lithium is between 0.1 and 26 A/s. In one
  • the flux of lithium is between 0.5 and 13 A/s. In one embodiment, the flux of lithium is between 0.7 and 4 A/s In one embodiment, the flux of lithium is between 0.8 and 2.2 A/s. This flux is typically measured at the substrate surface. Typically, the flux of lithium is measured in the presence of oxygen (such that, when it is measured in this way, what is actually measured is the flux of lithium oxide).
  • the flux of the dopant element(s) is between 0.1 and 13 A/s. In one embodiment, the flux of the dopant element(s) is between 0.1 and 7 A/s. In one embodiment, the flux of the dopant element(s) is between 0.4 and 2 A/s. In one embodiment, the flux of the dopant element(s) is between 0.5 and 1 A/s. This flux is typically measured at the substrate surface. Typically, the flux of the dopant element(s) is measured in the presence of (such that, when it is measured in this way, what is actually measured is the flux of its corresponding oxide).
  • the ability to measure the rates of the individual atomic fluxes and make changes during the deposition allows for control of the composition through the film thickness and can be used to either account for any changes in the vapor source conditions (e.g. aging or drift of the source) to maintain a constant lithium-cobalt composition through the film or to produce films with a change in lithium-cobalt composition during the deposition.
  • the rate of the individual atomic fluxes can be measured either directly at the source during the deposition, and / or indirectly (by measuring the oxygen partial pressure during the deposition). In one embodiment, the rate of the individual atomic fluxes is measured by electron-impact emission spectroscopy (EIES).
  • producing a controlled change in the composition during the deposition can be effectively used to produce a seed layer within the film.
  • the inclusion of a seed layer of C03O4 within the film during deposition may be achieved by altering the individual atomic fluxes by the preferred methods set out below.
  • the varying one or more conditions comprises the flux of cobalt exceeding the flux of lithium required to deposit a crystalline oxide of lithium and cobalt.
  • the flux of cobalt is increased relative to a cobalt flux level required to deposit a crystalline oxide of lithium and cobalt, and the flux of lithium is maintained at a lithium flux level required to deposit a crystalline oxide of lithium and cobalt. In one embodiment, the flux of cobalt is maintained at a cobalt flux level required to deposit a crystalline oxide of lithium and cobalt, and the flux of lithium is decreased relative to a lithium flux level required to deposit a crystalline oxide of lithium and cobalt.
  • the flux of oxygen is decreased. In one embodiment, wherein the oxygen is delivered together with an inert gas (as defined and exemplified above), the flux of oxygen is maintained at the same level, the control conferred by the dilution of the oxygen and consequent reduction in its partial pressure .
  • Controlling the rates of the atomic fluxes is only one method which may be used to control the morphology of the lithium cobalt oxide in the physical vapor deposition embodiment.
  • Other methods which may be used in order to provide a localized concentration (such as a seed layer) of C03O4, may include stopping the flux of lithium by closing of the lithium shutter, and variation of the oxygen partial pressure in the chamber (by varying oxygen flow rate or addition of further gases, for example argon).
  • the vapor deposition method comprises co-depositing the component elements onto the heated substrate comprises co-depositing the component elements directly onto a surface of the heated substrate. In one embodiment, the vapor deposition method comprises co-depositing the component elements onto the heated substrate comprises co-depositing the component elements onto one or more layers supported on the substrate.
  • the vapor deposition method is that generally described in WO 2015/104539, varied according to this aspect of the invention to produce the required localized concentration of C03O4.
  • the depositions described in WO 2015/104539 were carried out in a physical vapor deposition (PVD) system heated to between 50-800°C; for LCO films being deposited on to a bare substrate or a current collector layer (not containing heat sensitive battery layers) the temperature is preferably 300-450°C, however higher substrate temperatures up to 800°C can be used.
  • the method additionally comprises annealing the deposited lithium cobalt oxide film after the deposition. This additional step is particularly useful when the deposition is carried out at temperatures below 400°C.
  • the annealing temperature of the substrate is preferably heated to 300-450°C.
  • the method according to the invention may be carried out by sputtering.
  • sputter deposition is a physical vapor deposition (PVD) method of thin film deposition by sputtering.
  • Sputtering involves ejecting material from one or more targets that is a source of the required element(s) and directing it onto a substrate to enable growth of the required material, typically as a film on the substrate.
  • a sputtering deposition method comprising:
  • At least one sputtering target at least one sputtering target comprising a source of lithium, at least one sputtering target comprising a source of cobalt, and optionally one or more sputtering targets comprising 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium, the sputtering targets being the same or different; and
  • the sputtering target that provides a source of the required element comprises the oxide of that element, such that the target provides both the source of the element and at least part of the source of the oxygen.
  • the sputtering target that is a source of lithium comprises lithium oxide (LhO).
  • the sputtering target that is a source of cobalt comprises cobalt (II) oxide (CoO).
  • the sputtering target that is a source of cobalt is cobalt (III) oxide (C02O 3 ).
  • the sputtering target that is a source of cobalt comprises C0 3 O4.
  • the sputtering may be carried out using a single target which provides the sources of both lithium and cobalt, preferably as an oxide.
  • the sputtering target which provides the sources of both lithium and cobalt comprises UC0O2.
  • This target may optionally have additional lithium added (e.g. U 2 0) thereto to provide a composition having a greater proportion of lithium.
  • the oxygen partial pressure may be varied during deposition of the composition in order to achieve localised concentrations of C03O4.
  • the sputtering may be carried out using one sputtering target which provides the source of lithium and part of the source of cobalt, preferably as an oxide, more preferably UC0O2 (to which U 2 0 is optionally added) and at least one different sputtering target which provides part of the source of cobalt, typically comprising C03O4.
  • the sputtering target typically comprises the oxide of that element.
  • the sputtering target containing the oxide of the dopant element(s) may be the same or different to the sputtering target(s) containing the oxide of lithium and/or the oxide of cobalt.
  • the targets may be sputtered at the same time or sequentially.
  • a method of producing a composition of an embodiment of the invention wherein the method is a sputtering deposition method comprising:
  • a second sputtering target comprising a source of (a) lithium cobalt oxide or (b) lithium cobalt oxide comprising 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, aluminium, gallium, tin, lead, bismuth, lanthanum, cerium, gadolinium and europium;
  • a method of producing a composition of an embodiment of the invention wherein the method is a sputtering deposition method comprising:
  • a method of producing a composition of an embodiment of the invention wherein the method is a sputtering deposition method comprising:
  • a method of producing a composition of an embodiment of the invention wherein the method is a sputtering deposition method comprising:
  • first sputtering target comprising U 2 O and/ or an oxide of lithium and cobalt and a second sputtering target comprising an oxide of cobalt (preferably C03O 4 ); and sputtering said targets coincidentally to produce a mixed thin-film layer comprising C0 3 O 4 and a crystalline oxide of lithium and cobalt.
  • a method of producing a composition of an embodiment of the invention wherein the method is a sputtering deposition method comprising:
  • first sputtering target comprising LhO and / or an oxide of lithium and cobalt
  • second sputtering target comprising an oxide of cobalt, preferably C03O4
  • the high energy particles are gas ions.
  • the gas ions are argon ions.
  • Examples of types of sputter deposition include RF sputtering, DC sputtering, pulsed- DC sputtering, ion-beam sputtering, reactive sputtering, high-target utilization sputtering (HiTUS), high-power impulse magnetron sputtering (HiPiMS) and gas flow sputtering.
  • the sputtering method according to this example of the invention is typically carried out at a pressure of 1 x 10 4 to 1 x 10 2 Torr, preferably 5 x 10 4 to 5 x 10 2 Torr, and more preferably 1 x 10 3 to 2 x 10 3 Torr.
  • the method according to the invention may be carried out by chemical vapor deposition.
  • chemical vapor deposition comprises providing a vapor source of each component element of the desired substance, wherein the sources comprise one or more precursor compounds containing the required element, and depositing the vaporised elements onto a heated substrate, typically by spraying. The component elements from the sources react on the substrate to form the desired material.
  • a method of producing a crystalline lithium cobalt oxide composition (particularly although not exclusively the composition of an embodiment of the invention) wherein the method is a vapor deposition method comprising: providing a source of each component element of the compound, wherein the sources comprise one or more precursor compounds, at least one precursor compound containing lithium, at least one precursor compound containing cobalt, and at least one precursor compound containing oxygen;
  • component elements from the sources react on the substrate to form a crystalline oxide of lithium and cobalt
  • one or more conditions of the method are varied such that a localized concentration of C03O4 is formed so as to enable crystal growth of a composition having the required crystalline structure.
  • the substrate is heated to between 250 and 950°C. In one embodiment, the substrate is heated to between 300 and 600°C.
  • the CVD method according to this example of the invention is typically carried out at a pressure of 0.1 to 500 Torr, preferably 1 to 100 Torr.
  • the precursor compounds are mixed to form a sol prior to spraying on the heated substrate.
  • the precursor compounds are not particularly limited provided that at least one precursor compound includes lithium and at least one precursor compound contains cobalt.
  • the precursor compound containing lithium comprises a lithium salt and/or the precursor compound containing cobalt comprises a cobalt salt.
  • the crystalline lithium cobalt oxide composition of an embodiment of the present invention is particularly useful for the formation of electrodes, typically for use in cells such as electrochemical cells and fuel cells.
  • the invention further provides an electrode comprising the crystalline lithium cobalt oxide composition of an embodiment of the invention (as defined above, either in its broadest aspect or a preferred aspect).
  • the crystalline lithium cobalt oxide composition is supported on a support.
  • the crystalline lithium cobalt oxide composition forms a layer on the support.
  • the support is a substrate on which a current collecting material is supported.
  • the current collecting material is a metal or a conducting metal oxide.
  • the current collecting material is selected from the group consisting of: platinum, aluminium, titanium, chromium, iron, zinc, gold, silver, nickel, molybdenum, tin oxide, indium tin oxide and stainless steel.
  • the substrate is an inert substrate.
  • the substrate is selected from the group consisting of: silicon, silicon oxide, aluminium oxide, an aluminosilicate material, doped silicon oxide, a glass, a metal, and a ceramic material.
  • the substrate is a silicon substrate.
  • the silicon substrate is covered by one or more passivation layers.
  • at least one passivation layer comprises silicon dioxide.
  • at least one further passivation layer comprises silicon nitride.
  • an adhesion layer is present between the current collector and substrate.
  • the adhesion layer is selected from a metal and a metal oxide.
  • the adhesion layer is selected from the group consisting of: titanium oxide, titanium, zirconium and chromium.
  • the crystalline lithium cobalt oxide composition of an embodiment of the present invention may usefully be used in a cell, particularly an electrochemical cell.
  • an electrochemical cell comprising: an electrolyte; an anode; and a cathode; wherein the anode and/or the cathode comprises an electrode according to the present invention.
  • the lithium cobalt oxide composition of an embodiment of the present invention is particularly suitable for use at the cathode of such a cell. Accordingly, the invention further provides an electrochemical cell, as defined above, wherein the cathode comprises an electrode according to the present invention.
  • the cell may be a solid-state cell (also referred to as a solid-state battery).
  • the cell is a lithium-ion battery.
  • lithium ions Li +
  • the cathode comprises an electrode according to the present invention.
  • the electrolyte may be any electrolyte typically used in electrochemical cells.
  • the electrolyte is a solid electrolyte.
  • solid-state electrolytes examples include the following:
  • Lithium borosilicate (as described in WO2017/216532, WO2015/104540 and WO2015/104538)
  • Sulfide based glassy and glass-ceramic electrolytes e.g. LPS (xLi2S-yP2Ss), Lb-SiS2
  • Garnet-type solid electrolytes e.g. LisLasIVhO ⁇ or LLZO (Li 7 La 3 Zr 2 0i 2 )
  • Oxide based perovskite-type solid electrolytes e.g.LLTO (Lio . sLao . sTiCb)
  • LISICON-type e.g. LiioGeP 2 Si2
  • NASICON-type e.g. Li1.4[AI 0.4 Gei . s(PO 4 ) 3 ], LATP (Lii +x Al x Ti 2 -x(P0 4 ) 3
  • Solid polymer electrolytes e.g. polyethylene oxide (PEO)
  • the electrolyte comprises lithium phosphorus oxynitride (UPON).
  • UPON lithium phosphorus oxynitride
  • a method of making a solid-state cell comprising depositing an electrode of the cell as a layer of a crystalline lithium cobalt oxide composition according to an embodiment of the present invention using a method according to the invention.
  • the further layers of the solid- state battery are deposited using a vapor deposition technique such as physical vapor deposition or sputtering to create a multi-layered structure.
  • a vapor deposition technique such as physical vapor deposition or sputtering
  • the electrochemical cell is a fuel cell.
  • a fuel cell is an electrochemical cell that converts the chemical energy from a fuel into electricity through an electrochemical reaction of a fuel (typically hydrogen or a simple organic compound, e.g. methanol or formic acid) with oxygen or another oxidising agent.
  • a fuel typically hydrogen or a simple organic compound, e.g. methanol or formic acid
  • oxygen or another oxidising agent typically hydrogen or a simple organic compound, e.g. methanol or formic acid
  • Fuel cells are different from batteries in requiring a continuous source of fuel and oxygen (usually from air) to sustain the chemical reaction, whereas in a battery the chemical energy comes from chemicals already present in the battery. Fuel cells can produce electricity continuously for as long as fuel and oxygen are supplied.
  • a fuel cell comprising: an anode; a cathode; and an electrolyte; wherein the anode and/or the cathode comprises the crystalline oxide material of an embodiment of the invention.
  • the fuel cell also typically comprises, or is connected to, a fuel supply.
  • the fuel is hydrogen.
  • the fuel is an organic compound, typical examples of which include methane, methanol, ethanol, formic acid and acetic acid.
  • the fuel cell also typically comprises, or is connected to, a supply of oxidant.
  • the oxidant is molecular oxygen.
  • the oxidant is an oxidising agent, examples of which are known to those skilled in the art.
  • an electronic device comprising an electrochemical cell (especially a lithium ion battery) according to the invention.
  • electrochemical cell especially a lithium ion battery
  • Examples of such electronic devices are well known to those skilled in the art, and include hand held electronic devices such as mobile telephones.
  • FIG. 1 shows a schematic representation of an example apparatus 10 suitable for implementing the physical vapor deposition embodiment of the method of the present invention.
  • the deposition is carried out within a vacuum system 12, which may be an ultrahigh vacuum system.
  • a substrate 14 of a desired material (depending on the intended purpose of the deposited material) is mounted within the vacuum system 12, and heated above room temperature using a heater 16.
  • Also within the vacuum system is a plurality of vapor sources, one source for each of the component elements in the desired thin film compound.
  • a first vapor source 18 comprises a source of atomic oxygen, such as an oxygen plasma source.
  • a second vapor source 20 comprises a source of lithium vapor.
  • a third vapor source 22 comprises a source of cobalt vapor.
  • each component element is released from its respective vapor source onto the heated substrate 14, whereupon the various elements are co-deposited.
  • the elements react on the substrate 14 to form a thin film layer 29 of the crystalline lithium cobalt oxide.
  • a significant advantage of the physical deposition method described is that deposition of the constituents of the compound directly from the elements allows for direct control of the compound composition and structure via the rates of deposition of the component elements.
  • the flux of each element can be independently controlled by appropriate operation of its respective vapor source so that the chemical composition of the deposited compound can be tailored according to exacting requirements if desired.
  • the rates of the fluxes of lithium and cobalt are monitored, and appropriate adjustments made to the respective vapor sources, if desired.
  • the deposition rates of both the lithium and cobalt fluxes can be measured for example using quartz crystal microbalance (QCM) or electron-impact emission spectroscopy (EIES).
  • the cobalt flux can also be monitored indirectly by monitoring the stability of the oxygen pressure within the deposition chamber using a Residual Gas Analyser (RGA) or an ion gauge; the reactivity of the cobalt flux towards oxygen means that an inverse change in oxygen pressure is observed when the cobalt flux changes.
  • RAA Residual Gas Analyser
  • the gases present in the vacuum system namely oxygen, nitrogen, argon, carbon dioxide (trace), and carbon monoxide (trace) can be monitored using a Residual Gas Analyser (RGA) and the total pressure measured using an ion gauge.
  • RAA Residual Gas Analyser
  • Changes to pressures of gases being introduced into the system can be made by altering the flow of gases into the chamber. Further to this the film growth can be monitored during the deposition for example by ellipsometry and other optical techniques.
  • Producing a film with a non-constant composition / inclusion of a seed layer can be advantageous as it can allow for control of the structure and morphology of the film, for example by introducing defects which can act as nucleation sites for crystal growth. Controlling the composition of the film in this way can also influence properties of the film such as the adhesion to the surrounding layers and help to balance stress within the film.
  • Such precise control of the film composition and the ability to adjust during the deposition, thus controlling the properties of the final film confers an advantage of the method of the present invention with other techniques such as pulsed laser deposition (PLD) which can suffer from preferential loss of lighter elements such as lithium, making control of the composition in the final film more difficult.
  • PLD pulsed laser deposition
  • UC0O2 films of thicknesses 1-30 pm may be deposited for use in solid-state batteries.
  • ⁇ 1 pm typically ⁇ 250 nm
  • test UC0O2 layers are deposited using the same method, the structure and composition of these test layers are analysed by Raman spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA- ICP-MS). When a suitable test sample is obtained the conditions are repeated during a longer deposition to obtain the thicker UC0O2 films for use in solid-state batteries.
  • Raman Spectroscopy is a powerful technique for the microstructural analysis of UC0O 2 due to the different crystal structures providing a Raman fingerprint.
  • Raman spectroscopy is able to detect the secondary product C0 3 O 4 even at trace/impurity level, due to the strong scattering intensity of this oxide.
  • Raman spectroscopy is a particularly effective method to study these materials.
  • the Raman spectrometer used in these Examples is a Horiba XploRA Plus equipped with a 532 nm (green) laser and 10X, 50X and 100X microscope objectives. For a 532 nm laser with a 0.90N A/100X objective this would predict a spatial resolution of 361 nm. However, the optical processes occurring during Raman microscopy are much more complex than for standard light microscopy. A number of factors can reduce this resolution. Thus, typical Raman spatial resolution is usually quoted as 1 pm (although this can be improved under ideal conditions).
  • Raman spectroscopy measurements are taken following acquisition parameters shown in Table 1. Top down measurements use objective 50X, slit 50, hole 100, filter 2%. Cross section measurements use same settings as above although objective 100X and accumulation is 2 using a line with pitch 1 pm, number of points to cover whole sample.
  • lithium cobalt oxide films may be formed which are slightly lithium-deficient in composition, for example with lithium: cobalt ratios of 47.5-49.1 % lithium and 52.5- 50.9 % cobalt (expressed as a percentage of the total metal atoms excluding oxygen).
  • the crystalline nature of the deposited UC0O2 films is demonstrated by both Raman spectroscopy and X-ray diffraction.
  • Raman spectroscopy shows that the deposited films are of the HT-UC0O2 phase ( R-3m ) ( Figure 4), this high temperature phase being obtained at a relatively low substrate temperature of 400°C due to the nature of this synthesis method which allows crystalline lithium containing materials to be deposited using lower substrate temperatures than those typically described in WO 2015/104539.
  • the hexagonal R-3m phase consists of an ordered lamellar structure consisting of cobalt layers alternating with lithium layers (for example, as described in Porthault et al. Vibrational Spec 62 (2012) 152-158).
  • X-ray diffraction (XRD) patterns of the deposited films show the films to be primarily of the (00/) orientation, with the (003) peak at 18.9° being the strongest peak, in addition peaks at 37.4° (101), 38.4° (006), 39.1 ° (012) and 45.3° (104) are observed for some examples indicating the presence of crystallites with other orientations.
  • Cross-sectional Raman spectroscopy has been carried out on these films to demonstrate the changes in the film produced by small changes during the deposition: these changes can be related to the morphology of the films.
  • Figure 6 shows an example of a film (not produced according to the invention) where the deposition conditions remained constant for the whole deposition time (film 4): the Raman spectra can be seen to be constant through the film showing that the same phase and composition is present for the whole film thickness.
  • the film produced is smooth and flat, containing only small crystallites ( Figure 7) and X-ray Diffraction (XRD) shows that the film is preferentially orientated in the (003) direction with only peaks at 18.9 and 38.4° corresponding to the (003) and (006) orientation being observed ( Figure 5).
  • the (00/) orientation of UC0O2 has the layers of the R-3m structure formed parallel to the surface of the substrate.
  • the two- dimensional lithium diffusion planes being parallel to the substrate makes this orientation non-ideal for electrochemical intercalation of lithium due to the long pathways the lithium is required to travel, thus limiting the rates at which the intercalation of lithium can occur and it has also been shown to yield lower than theoretical capacities (Bouwman et al. Solid-state Ionics 152 (2002) 181-188).
  • film 4 (not according to the invention) which is observed to be strongly (003) orientated provides only 20 % of its theoretical capacity (13 pAh cnr 1 -2 pm -1 ) by the 5th cycle discharge when cycled under the same cycling conditions as for the other films discussed, at 25°C.
  • the closely packed, dense morphology of these films consists of narrow columnar crystallites arranged perpendicular to the substrate surface with widths between 100 - 300 ( ⁇ 50) nm and lengths of 0.1 - 7 pm (up to the full film thickness (6700 nm)) and is homogeneous in nature producing a smooth surface to the film, the SEM image of the top surface only shows small crystallites of sizes less than 350 nm when viewed from above ( Figure 7). In some instances, these films have been shown to be susceptible to cracking which can be detrimental to a solid-state battery.
  • Figure 8 shows three examples of films according to embodiments of the invention where the deposition conditions change during the film deposition.
  • the deposition starts with the Co and Li fluxes balanced to produce a film which has only the two Raman bands relating to the R-3m UC0O2 phase.
  • the Li flux changes relative to the Co flux to slightly increase the quantity of Co in the film: this is seen in the Raman by the appearance of an extra band at 690 cnr 1 which is known to relate to the cobalt oxide phase CosCLAi g mode.
  • the timing and magnitude of this change can influence the morphology of the final film and allows for the morphology to be tuned.
  • the quantity of extra cobalt added to the film is small with the average composition of the whole LCO film remaining in the region 47- 49.5 % lithium.
  • small variations in the deposition conditions during the film deposition results in deviations in the morphology of the deposited films.
  • larger plate-like crystallites of sizes typically > 0.3 pm
  • ranging from 0.4 to 2 pm in length are observed within the films: these crystallites cover more than 4 % of the surface area of the film, but can cover as much as 80 % of the surface area when viewed from above (Table 2), with the rest of the film consisting of the small crystallites (typically ⁇ 0.3 pm) described above.
  • Table 2 provides a comparison of crystallite sizes in the UC0O2 films described herein and shown in Figure 12 (Films 1 to 3 being according to embodiments of the invention) Film 4 not according to the invention.) No crystallites are generally observed in Film 4 as it is very smooth. It was noted that the sample of Film 3 had lots of large particulates on it, making it difficult to calculate the average roughness. Table 2
  • the XRD patterns for these films show that the films become less preferentially orientated in the (003) orientation with peaks at 37.4 and 45.3°due to the (101) and (104) orientations appearing, the intensity of these peaks becoming larger as the films have a higher surface area of larger crystallites ( Figure 5).
  • the changes in morphology observed are believed to be because the addition of C03O4 as a minority species acts as a seeding layer to seed growth of crystallites with different orientations ((101) and (104)) to that of the bulk of the film (003).
  • Figure 9 shows the cross- sectional image for film 1 and shows that once the film reaches a thickness of 3000 nm the film the morphology within the film changes, this change corresponds to the change seen in the Raman cross section and can be related to a change in the deposition conditions where the ratio of the Co to Li flux changed.
  • FIG. 10 shows film 5; film 5 was grown with a Co-rich region in the centre of the film as shown by the peak at 690 cm -1 which is known to relate to C03O4, although the Corich region is small relative to the overall film thickness the SEM image shows that the film morphology consists of large crystallites covering the vast majority (of the film surface, therefore showing that the C03O4 has acted as a seeding layer with the lithium cobalt oxide deposited afterwards forming large plate-like crystallites.
  • the film contains 47 % at. % lithium (expressed as a proportion of the total atoms in the crystalline oxide, excluding oxygen).
  • a seeding layer at the beginning of the lithium cobalt oxide deposition include: briefly stopping the Li flux during the deposition to produce a thin layer of C03O4 rather than having the C03O4 as a minor species interspersed within the lithium cobalt oxide film (a more extreme version of film 5); interrupting the lithium cobalt oxide deposition either briefly or for up to several days changing the substrate temperature during the deposition; use of an extra element either at the beginning or during the deposition to produce a seeding layer.
  • PLD pulsed laser deposition
  • Solid-state Ionics 152 (2002) 181-188.
  • higher intercalation rates and capacities for films with higher surface areas is often assigned to the rougher surface meaning that a bigger surface area being in contact with the liquid electrolyte which is favourable for Li intercalation and deintercalation (Jung et al. Thin Solid Films 546 (2013) 414-417).
  • the UC0O2 films are tested in solid-state cells consisting of platinum current collectors, the UC0O2 cathode, a UPON electrolyte and a Si anode arranged in the form Pt/LiCo0 2 /LiPON/Si/Pt as shown in the figure, along with an encapsulation which is not shown in the figure ( Figure 11).
  • Table 3 shows the number of cycles achieved to 80 % of the 5th cycle discharge capacity for solid-state cells containing UC0O2 films with the morphologies displayed when cycled with 100% depth of discharge at a temperature of 25°C.
  • Example 4 Additional surface roughness measurements were carried out on films according to embodiments of the invention (Examples A-D), as well as Comparative Example E (not according to the invention). These measurements are given in terms of the root- mean-square surface roughness, that is, the root mean square average of the profile height deviations from the mean line of the surface. The results are set out in Table 4. Table 4

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EP4055656A4 (en) * 2019-11-08 2024-10-16 Enevate Corporation Si-anode-based semi-solid cells with solid separators
KR102939528B1 (ko) * 2019-11-08 2026-03-17 에네베이트 코포레이션 고체 분리막이 있는 Si-애노드 기반 반고체 전지
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