US20150137031A1 - Doped nickelate compounds - Google Patents

Doped nickelate compounds Download PDF

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US20150137031A1
US20150137031A1 US14/413,809 US201314413809A US2015137031A1 US 20150137031 A1 US20150137031 A1 US 20150137031A1 US 201314413809 A US201314413809 A US 201314413809A US 2015137031 A1 US2015137031 A1 US 2015137031A1
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lithium
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alkali metal
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Jeremy Barker
Richard Heap
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Faradion Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/66—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to novel doped nickelate compounds, their method of preparation, to novel electrodes which utilise an active material that comprises said doped nickelate compounds, and to the use of these electrodes, for example in an energy storage device.
  • Lithium-ion battery technology has enjoyed a lot of attention in recent years and provides the preferred portable battery for most electronic devices in use today.
  • Such batteries are “secondary” or rechargeable which means that they are capable of undergoing multiple charge/discharge cycles.
  • lithium-ion batteries are prepared using one or more lithium electrochemical cells containing electrochemically active materials. Such cells comprise an anode (negative electrode), a cathode (positive electrode) and an electrolyte material.
  • Li + ions de-intercalate from the cathode and insert into the anode. Meanwhile charge balancing electrons pass from the cathode through the external circuit containing the charger and into the anode of the battery. During discharge the same process occurs but in the opposite direction.
  • the present invention aims to provide novel compounds. Further the present invention aims to provide a cost effective electrode that contains an active material that is straightforward to manufacture and easy to handle and store. Another aim of the present invention is to provide an electrode that has a high initial specific discharge capacity and which is capable of being recharged multiple times without significant loss in charge capacity.
  • the first aspect of the present invention provides compounds of the formula:
  • the preferred alkali metal used in the compounds of present invention is lithium; this may either be used alone or as a mixture with sodium and/or potassium. In the case where the lithium is used with other alkali metals then preferably lithium is the major alkali metal constituent in the mixture.
  • V is in the range 0.3 ⁇ V ⁇ 0.45; W is in the range 0 ⁇ W ⁇ 0.5; X is in the range 0 ⁇ X ⁇ 0.3; Y is in the range 0 ⁇ Y ⁇ 0.4; and Z is in the range 0 ⁇ Z ⁇ 0.5.
  • Especially preferred compounds of the present invention include:
  • the present invention provides an electrode comprising an active compound of the formula:
  • Particularly preferred electrodes of the present invention comprise an active compound of the above formula, wherein V is in the range 0.3 ⁇ V ⁇ 0.45; W is in the range 0 ⁇ W ⁇ 0.5; X is in the range 0 ⁇ X ⁇ 0.3; Y is in the range 0 ⁇ Y ⁇ 0.4; and Z is in the range 0 ⁇ Z ⁇ 0.5.
  • NiO may be formed during the process of charging the electrode; at this time Ni2+ can be oxidized, using up energy that would normally be used to charge the active material. This is not only an irreversible reaction, but also has a detrimental effect on the cycling performance, resulting in a drop in capacity upon electrochemical cycling.
  • the formation of NiO by this route is found to be minimised by reducing the amount of alkali metal in the active compound and is the purpose for compounds of the invention which have less than 1 unit of alkali metal.
  • Electrodes of the present invention comprise an active compound as described above wherein M 2 ⁇ M 4 .
  • Especially preferred electrodes of the present invention comprise active compounds selected from one or more of:
  • the electrodes according to the present invention are suitable for use in many different applications, for example energy storage devices, rechargeable batteries, electrochemical devices and electrochromic devices.
  • the electrodes according to the invention are used in conjunction with a counter electrode and one or more electrolyte materials.
  • the electrolyte materials may be any conventional or known materials and may comprise either aqueous electrolyte(s) or non-aqueous electrolyte(s) or mixtures thereof.
  • the present invention provides an energy storage device that utilises an electrode comprising the active materials described above, and particularly an energy storage device for use as one or more of the following: an alkali metal ion cell; an alkali metal-metal cell; a non-aqueous electrolyte alkali metal ion cell; or an aqueous electrolyte alkali metal ion cell, wherein the alkali metal comprises lithium alone or a mixture of lithium and one or more other alkali metals wherein lithium is the major alkali metal constituent in the mixture.
  • novel compounds of the present invention may be prepared using any known and/or convenient method.
  • the precursor materials may be heated in a furnace so as to facilitate a solid state reaction process.
  • reaction is conducted under an atmosphere of ambient air, and alternatively under an inert gas.
  • lithium-ion materials from the sodium-ion derivatives by converting the sodium-ion materials into lithium-ion materials using an ion exchange process.
  • Typical ways to achieve Na to Li ion exchange include:
  • FIG. 1A is an XRD of NaNi 0.45 Mn 0.45 Cu 0.05 Ti 0.05 O 2 (lower profile) and LiNi 0.45 Mn 0.45 Cu 0.05 Ti 0.05 O 2 (upper profile) prepared according to Example 1;
  • FIG. 1B shows the Electrode Voltage (V vs Li) versus Cumulative Cathode Specific Capacity (mAh/g) for LiNi 0.45 Mn 0.45 Cu 0.05 Ti 0.05 O 2 prepared according to Example 1;
  • FIG. 1C shows the first cycle Differential Capacity (mAh/g/V) versus Electrode Voltage (v vs Li) for LiNi 0.45 Mn 0.45 Cu 0.05 Ti 0.05 O 2 prepared according to Example 1;
  • FIG. 2A is an XRD of NaNi 0.4 Mn 0.4 Ca 0.1 Ti 0.1 O 2 (lower profile) and LiNi 0.4 Mn 0.4 Ca 0.1 Ti 0.1 O 2 (upper profile) prepared according to Example 2;
  • FIG. 2B shows the Electrode Voltage (V vs Li) versus Cumulative Cathode Specific Capacity (mAh/g) for LiNi 0.40 Mn 0.40 Ca 0.1 Ti 0.1 O 2 prepared according to Example 2;
  • FIG. 2C shows the first cycle Differential Capacity (mAh/g/V) versus Electrode Voltage (v vs Li) for LiNi 0.40 Mn 0.40 Ca 0.1 Ti 0.1 O 2 prepared according to Example 2;
  • FIG. 3A is an XRD of NaNi 0.4 Mn 0.4 Cu 0.1 Ti 0.1 O 2 (lower profile) and LiNi 0.4 Mn 0.4 Cu 0.1 Ti 0.1 O 2 (upper profile) prepared according to Example 3;
  • FIG. 3B shows the Electrode Voltage (V vs Li) versus Cumulative Cathode Specific Capacity (mAh/g) for LiNi 0.40 Mn 0.40 Cu 0.1 Ti 0.1 O 2 prepared according to Example 3;
  • FIG. 3C shows the first cycle Differential Capacity (mAh/g/V) versus Electrode Voltage (v vs Li) for LiNi 0.40 Mn 0.40 Cu 0.1 Ti 0.1 O 2 prepared according to Example 3;
  • FIG. 4A is an XRD of NaNi 0.45 Mn 0.45 Mg 0.05 Ti 0.05 O 2 (lower profile) and LiNi 0.45 Mn 0.45 Mg 0.05 Ti 0.05 O 2 (upper profile) prepared according to Example 4;
  • FIG. 4B shows the Electrode Voltage (V vs Li) versus Cumulative Cathode Specific Capacity (mAh/g) for LiNi 0.45 Mn 0.45 Mg 0.05 Ti 0.05 O 2 prepared according to Example 4;
  • FIG. 4C shows the first cycle Differential Capacity (mAh/g/V) versus Electrode Voltage (v vs Li) for LiNi 0.45 Mn 0.45 Mg 0.05 Ti 0.05 O 2 prepared according to Example 4;
  • FIG. 5A is an XRD of NaNi 0.33 Mn 0.33 Mg 0.167 Ti 0.167 O 2 (lower profile) and LiNi 0.33 Mn 0.33 Mg 0.167 Ti 0.167 O 2 (upper profile) prepared according to Example 5
  • FIG. 5B shows the Electrode Voltage (V vs Li) versus Cumulative Cathode Specific Capacity (mAh/g) for LiNi 0.33 Mn 0.33 Mg 0.167 Ti 0.167 O 2 prepared according to Example 5;
  • FIG. 5C shows the first cycle Differential Capacity (mAh/g/V) versus Electrode Voltage (v vs Li) for LiNi 0.33 Mn 0.33 Mg 0.167 Ti 0.167 O 2 prepared according to Example 5;
  • FIG. 6A is an XRD of Li 0.95 Ni 0.3167 Ti 0.3167 Mg 0.1583 Mn 0.2083 O 2 prepared according to Example 6.
  • Stoichiometric amounts of the precursor materials are intimately mixed together and pressed into a pellet.
  • the resulting mixture is then heated in a tube furnace or a chamber furnace using either an ambient air atmosphere, or a flowing inert atmosphere (e.g. argon or nitrogen), at a furnace temperature of between 400° C. and 1500° C. until reaction product forms; for some materials a single heating step is used and for others more than one heating step is used.
  • argon or nitrogen e.g. argon or nitrogen
  • the target materials were tested using a lithium metal anode test cell. It is also possible to test using a Li-ion cell with a graphite anode. Cells may be made using the following procedures:
  • the positive electrode is prepared by solvent-casting a slurry of the active material, conductive carbon, binder and solvent.
  • the conductive carbon used is Super P (Timcal).
  • PVdF co-polymer e.g. Kynar Flex 2801, Elf Atochem Inc.
  • acetone is employed as the solvent.
  • the slurry is then cast onto glass and a free-standing electrode film is formed as the solvent evaporates.
  • the electrode is then dried further at about 80° C.
  • the electrode film contains the following components, expressed in percent by weight: 80% active material, 8% Super P carbon, and 12% Kynar 2801 binder.
  • an aluminium current collector may be used to contact the positive electrode.
  • the electrolyte comprises one of the following: (i) a 1 M solution of LiPF 6 in ethylene carbonate (EC) and dimethyl carbonate (DMC) in a weight ratio of 1:1; (ii) a 1 M solution of LiPF 6 in ethylene carbonate (EC) and diethyl carbonate (DEC) in a weight ratio of 1:1; or (iii) a 1 M solution of LiPF 6 in propylene carbonate (PC)
  • a glass fibre separator (Whatman, GF/A) or a porous polypropylene separator (e.g. Celgard 2400) wetted by the electrolyte is interposed between the positive and negative electrodes.
  • the positive electrode is prepared by solvent-casting a slurry of the active material, conductive carbon, binder and solvent.
  • the conductive carbon used is Super P (Timcal).
  • PVdF co-polymer e.g. Kynar Flex 2801, Elf Atochem Inc.
  • acetone is employed as the solvent.
  • the slurry is then cast onto glass and a free-standing electrode film is formed as the solvent evaporates.
  • the electrode is then dried further at about 80° C.
  • the electrode film contains the following components, expressed in percent by weight: 80% active material, 8% Super P carbon, and 12% Kynar 2801 binder.
  • an aluminium current collector may be used to contact the positive electrode.
  • the negative electrode is prepared by solvent-casting a slurry of the graphite active material (Crystalline Graphite, supplied by Conoco Inc.), conductive carbon, binder and solvent.
  • the conductive carbon used is Super P (Timcal).
  • PVdF co-polymer e.g. Kynar Flex 2801, Elf Atochem Inc.
  • acetone is employed as the solvent.
  • the slurry is then cast onto glass and a free-standing electrode film is formed as the solvent evaporates.
  • the electrode is then dried further at about 80° C.
  • the electrode film contains the following components, expressed in percent by weight: 92% active material, 2% Super P carbon, and 6% Kynar 2801 binder.
  • a copper current collector may be used to contact the negative electrode.
  • the cells are tested as follows, using Constant Current Cycling techniques.
  • the cell is cycled at a given current density between pre-set voltage limits.
  • a commercial battery cycler from Maccor Inc. (Tulsa, Okla., USA) is used.
  • On charge lithium ions are extracted from the cathode active material.
  • During discharge lithium ions are re-inserted into the cathode active material.
  • Air/900° C., dwell time of 8 hours Air/900° C., dwell time of 8 hours.
  • FIG. 1(A) shows the XRD obtained for the target material LiNi 0.45 Mn 0.45 Cu 0.05 Ti 0.05 O 2 , (upper profile) and the precursor material NaNi 0.45 Mn 0.45 Cu 0.05 Ti 0.05 O 2 (lower profile).
  • the presence and high purity of the lithium-containing target material is confirmed by the absence of any Na-containing phase being seen in the upper profile, and by the fact that the lithium-containing target material phase exhibits a substantial increase in peak angles. This suggests a smaller unit cell than for the precursor material and is consistent with the replacement of Na with Li.
  • the data shown in FIG. 1(B) (Electrode Voltage (V vs. Li) versus Cumulative Cathode Specific Capacity (mAh/g)) are derived from the constant current cycling data for the LiNi 0.45 Mn 0.45 Cu 0.05 Ti 0.05 O 2 (Sample X0453) active material in a metallic lithium half-cell.
  • the electrolyte used was a 1.0 M solution of LiPF 6 in ethylene carbonate/diethyl carbonate.
  • the constant current data were collected at an approximate current density of 0.20 mA/cm 2 between voltage limits of 3.00 and 4.30 V vs. Li.
  • the testing was carried out at 25° C. During the cell charging process, lithium ions are extracted from the cathode active material.
  • the first charge process corresponds to a cathode specific capacity of 151 mAh/g.
  • the first discharge process corresponds to a cathode specific capacity of 97 mAh/g.
  • FIG. 1(C) shows the first cycle differential capacity profile (Differential Capacity (mAh/g/V) versus Electrode Voltage (V vs. Li)] for the LiNi 0.45 Mn 0.45 Cu 0.05 Ti 0.05 O 2 (Sample X0453) derived from the constant current cycling data shown in FIG. 1(B) .
  • Differential capacity data have been shown to allow characterization of the reaction reversibility, order-disorder phenomenon and structural phase changes within the ion insertion system.
  • Air/900° C., dwell time of 8 hours 2) Air/900° C., dwell time of 8 hours. 3) Air/950° C., dwell time of 8 hours
  • FIG. 2(A) shows the XRD obtained for the target material LiNi 0.4 Mn 0.4 Ca 0.1 Ti 0.1 O 2 , (upper profile) and the precursor material NaNi 0.40 Mn 0.40 Ca 0.1 Ti 0.1 O 2 (lower profile).
  • the presence and high purity of the lithium-containing target material is confirmed by the absence of any Na-containing phase being seen in the upper profile, and by the fact that the lithium-containing target material phase exhibits a substantial increase in peak angles. This suggests a smaller unit cell than for the precursor material and is consistent with the replacement of Na with Li.
  • the data shown in FIG. 2(B) (Electrode Voltage (V vs. Li) versus Cumulative Cathode Specific Capacity (mAh/g)) are derived from the constant current cycling data for the LiNi 0.40 Mn 0.40 Ca 0.10 Ti 0.10 O 2 (Sample X0454) active material in a metallic lithium half-cell.
  • the electrolyte used was a 1.0 M solution of LiPF 6 in ethylene carbonate/diethyl carbonate.
  • the constant current data were collected at an approximate current density of 0.20 mA/cm 2 between voltage limits of 3.00 and 4.30 V vs. Li.
  • the testing was carried out at 25° C. During the cell charging process, lithium ions are extracted from the cathode active material.
  • the first charge process corresponds to a cathode specific capacity of 135 mAh/g.
  • the first discharge process corresponds to a cathode specific capacity of 108 mAh/g.
  • FIG. 2(C) shows the first cycle differential capacity profile (Differential Capacity [mAh/g/V versus Electrode Voltage (V vs. Li)] for the LiNi 0.40 Mn 0.40 Ca 0.10 Ti 0.10 O 2 (Sample X0454) derived from the constant current cycling data shown in FIG. 2(B) .
  • Differential capacity data have been shown to allow characterization of the reaction reversibility, order-disorder phenomenon and structural phase changes within the ion insertion system.
  • Air/900° C., dwell time of 8 hours Air/900° C., dwell time of 8 hours
  • FIG. 3(A) shows the XRD obtained for the target material LiNi 0.4 Mn 0.4 Cu 0.1 Ti 0.1 O 2 , (upper profile) and the precursor material NaNi 0.4 Mn 0.4 Cu 0.1 Ti 0.1 O 2 (lower profile).
  • the presence and high purity of the lithium-containing target material is confirmed by the absence of any Na-containing phase being seen in the upper profile, and by the fact that the lithium-containing target material phase exhibits a substantial increase in peak angles. This suggests a smaller unit cell than for the precursor material and is consistent with the replacement of Na with Li.
  • the data shown in FIG. 3(B) are derived from the constant current cycling data for the LiNi 0.40 Mn 0.40 Cu 0.10 Ti 0.10 O 2 (Sample X0455) active material in a metallic lithium half-cell.
  • the electrolyte used was a 1.0 M solution of LiPF 6 in ethylene carbonate/diethyl carbonate.
  • the constant current data were collected at an approximate current density of 0.20 mA/cm 2 between voltage limits of 3.00 and 4.30 V vs. Li.
  • the testing was carried out at 25° C. During the cell charging process, lithium ions are extracted from the cathode active material.
  • the first charge process corresponds to a cathode specific capacity of 139 mAh/g.
  • the first discharge process corresponds to a cathode specific capacity of 90 mAh/g.
  • FIG. 3(C) shows the first cycle differential capacity profile (Differential Capacity [mAh/g/V versus Electrode Voltage (V vs. Li)] for the LiNi 0.40 Mn 0.40 Cu 0.10 Ti 0.10 O 2 (Sample X0455) derived from the constant current cycling data shown in FIG. 3(B) .
  • Differential capacity data have been shown to allow characterization of the reaction reversibility, order-disorder phenomenon and structural phase changes within the ion insertion system.
  • Air/800° C., dwell time of 8 hours Air/900° C., dwell time of 8 hours.
  • FIG. 4(A) shows the XRD obtained for the target material LiNi 0.45 Mn 0.45 Mg 0.05 Ti 0.05 O 2 , (upper profile) and the precursor material NaNi 0.45 Mn 0.45 Mg 0.05 Ti 0.05 O 2 (lower profile).
  • the presence and high purity of the lithium-containing target material is confirmed by the absence of any Na-containing phase being seen in the upper profile, and by the fact that the lithium-containing target material phase exhibits a substantial increase in peak angles. This suggests a smaller unit cell than for the precursor material and is consistent with the replacement of Na with Li.
  • the data shown in FIG. 4(B) (Electrode Voltage (V vs. Li) versus Cumulative Cathode Specific Capacity (mAh/g)) are derived from the constant current cycling data for the LiNi 0.45 Mn 0.45 Mg 0.05 Ti 0.10 O 2 (Sample X0654) active material in a metallic lithium half-cell.
  • the electrolyte used was a 1.0 M solution of LiPF 6 in ethylene carbonate/diethyl carbonate.
  • the constant current data were collected at an approximate current density of 0.20 mA/cm 2 between voltage limits of 3.00 and 4.20 V vs. Li.
  • the testing was carried out at 25° C. During the cell charging process, lithium ions are extracted from the cathode active material.
  • the first charge process corresponds to a cathode specific capacity of 193 mAh/g.
  • the first discharge process corresponds to a cathode specific capacity of 115 mAh/g.
  • FIG. 4(C) shows the first cycle differential capacity profile (Differential Capacity [mAh/g/V versus Electrode Voltage (V vs. Li)] for the LiNi 0.45 Mn 0.45 Mg 0.05 Ti 0.10 O 2 (Sample X0654) derived from the constant current cycling data shown in FIG. 4(B) .
  • Differential capacity data have been shown to allow characterization of the reaction reversibility, order-disorder phenomenon and structural phase changes within the ion insertion system.
  • Air/900° C., dwell time of 8 hours Air/900° C., dwell time of 8 hours.
  • FIG. 5(A) shows the XRD obtained for the target material LiNi 0.333 Mn 0.333 Mg 0.167 Ti 0.167 O 2 (X0655), (upper profile) and the precursor material NaNi 0.333 Mn 0.333 Mg 0.167 Ti 0.167 O 2 (lower profile).
  • the presence and high purity of the lithium-containing target material is confirmed by the absence of any Na-containing phase being seen in the upper profile, and by the fact that the lithium-containing target material phase exhibits a substantial increase in peak angles. This suggests a smaller unit cell than for the precursor material and is consistent with the replacement of Na with Li.
  • the data shown in FIG. 5(B) (Electrode Voltage (V vs. Li) versus Cumulative Cathode Specific Capacity (mAh/g)) are derived from the constant current cycling data for the LiNi 0.333 Mn 0.333 Mg 0.167 Ti 0.167 O 2 (Sample X0655) active material in a metallic lithium half-cell.
  • the electrolyte used was a 1.0 M solution of LiPF 6 in ethylene carbonate/diethyl carbonate.
  • the constant current data were collected at an approximate current density of 0.20 mA/cm 2 between voltage limits of 3.00 and 4.20 V vs. Li.
  • the testing was carried out at 25° C. During the cell charging process, lithium ions are extracted from the cathode active material.
  • the first charge process corresponds to a cathode specific capacity of 132 mAh/g.
  • the first discharge process corresponds to a cathode specific capacity of 110 mAh/g.
  • FIG. 5(C) shows the first cycle differential capacity profile (Differential Capacity [mAh/g/V versus Electrode Voltage (V vs. Li)] for the LiNi 0.333 Mn 0.333 Mg 0.167 Ti 0.167 O 2 (Sample X0655) derived from the constant current cycling data shown in FIG. 5(B) .
  • Differential capacity data have been shown to allow characterization of the reaction reversibility, order-disorder phenomenon and structural phase changes within the ion insertion system.
  • FIG. 6(A) shows the XRD for the target product Li 0.95 Ni 0.3167 Ti 0.3167 Mg 0.1583 Mn 0.2083 O 2

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