Patent Application
20250226403
The present disclosure relates to a technique of a positive electrode active material for a non-aqueous electrolyte secondary battery.
As a secondary battery having a high output and a high energy density, a non-aqueous electrolyte secondary battery has been widely used, in which the non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, and performs charging and discharging by moving lithium ions and the like between the positive electrode and the negative electrode.
For example, Patent Literature 1 discloses, as a positive electrode active material used in a non-aqueous electrolyte secondary battery, a composite oxide that has a crystal structure belonging to a space group Fm-3m, contains lithium and molybdenum, and is substantially free of chromium.
An object of the present disclosure is to provide a positive electrode active material for a non-aqueous electrolyte secondary battery having a high discharge voltage.
A positive electrode active material for a non-aqueous electrolyte secondary battery according to an aspect of the present disclosure is a composite oxide that has a crystal structure belonging to a space group Fm-3m and is represented by a general formula: LixTMtmMyO2-fFf, and in the general formula, TM represents a transition metal, M represents a non-transition metal, x, tin, y, and f satisfy 1.75≤x+tm+y≤2 and 0<f≤0.7, and when Q=2×tm×{1−(1−f/2)5}, 0.8≤Q≤1.5 is satisfied.
According to an aspect of the present disclosure, it is possible to provide a positive electrode active material for a non-aqueous electrolyte secondary battery having a high discharge voltage.
Hereinafter, an example of a non-aqueous electrolyte secondary battery using a positive electrode active material for a non-aqueous electrolyte secondary battery of the present disclosure will be described.
The non-aqueous electrolyte contains, for example, a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent. Examples of the non-aqueous solvent include esters, ethers, nitriles, amides, and a mixed solvent of two or more thereof. The non-aqueous solvent may contain a halogen-substituted product in which at least some hydrogens in these solvents are substituted with halogen atoms such as fluorine. Examples of the electrolyte salt include lithium salts such as LiPF6. Note that the non-aqueous electrolyte is not limited to the liquid electrolyte, and may be a solid electrolyte using a gel polymer or the like.
The case body 16 is, for example, a bottomed cylindrical metal container. A gasket 28 is provided between the case body 16 and the sealing assembly 17 to secure a sealing property of the inside of the battery. The case body 16 has, for example, a projecting portion 22 in which a part of a side part thereof projects inside for supporting the sealing assembly 17. The projecting portion 22 is preferably formed in an annular shape along a circumferential direction of the case body 16, and supports the sealing assembly 17 on an upper surface thereof.
The sealing assembly 17 has a structure in which a filter 23, a lower vent member 24, an insulating member 25, an upper vent member 26, and a cap 27 are sequentially stacked from the electrode assembly 14. Each member constituting the sealing assembly 17 has, for example, a disk shape or a ring shape, and the respective members except for the insulating member 25 are electrically connected to each other. The lower vent member 24 and the upper vent member 26 are connected to each other at the respective central parts thereof, and the insulating member 25 is interposed between the respective circumferential parts of the vent members 24 and 26. When the internal pressure of the non-aqueous electrolyte secondary battery 10 is increased by heat generation due to an internal short circuit or the like, for example, the lower vent member 24 is deformed so as to push the upper vent member 26 up toward the cap 27 side and is broken, and thus, a current pathway between the lower vent member 24 and the upper vent member 26 is cut off. When the internal pressure is further increased, the upper vent member 26 is broken, and gas is discharged through an opening of the cap 27.
In the non-aqueous electrolyte secondary battery 10 illustrated in
Hereinafter, the positive electrode 11, the negative electrode 12, and the separator 13 will be described in detail.
The positive electrode 11 includes a positive electrode current collector and a positive electrode mixture layer disposed on the positive electrode current collector. As the positive electrode current collector, a foil of a metal stable in a potential range of the positive electrode, such as aluminum, a film in which the metal is disposed on a surface layer, or the like can be used. A thickness of the positive electrode current collector is preferably, for example, in a range of greater than or equal to 1 μm and less than or equal to 20 μm.
It is preferable that the positive electrode mixture layer contains a positive electrode active material and further contains a binding agent, a conductive agent, or the like. A thickness of the positive electrode mixture layer is preferably, for example, in a range of greater than or equal to 10 μm and less than or equal to 300 μm.
The positive electrode 11 is obtained by, for example, applying a positive electrode mixture slurry containing a positive electrode active material, a binding agent, a conductive agent, and the like onto a positive electrode current collector, drying the positive electrode current collector to form a positive electrode mixture layer on the positive electrode current collector, and rolling the positive electrode mixture layer.
The positive electrode active material includes a composite oxide having a crystal structure belonging to a space group Fm-3m.
The crystal structure belonging to the space group Fm-3m means having a peak attributable to the space group Fm-3m in a diffraction pattern obtained by X-ray diffraction (XRD) measurement. Note that “−3” in the space group “Fm-3m” represents a target element of a 3-fold rotation-inversion axis, and should be originally indicated by adding “3” with an upper bar “−”. The X-ray diffraction pattern of the composite oxide can be performed by powder X-ray diffraction measurement using an X-ray diffractometer (“MiniFlexII” manufactured by Rigaku Corporation) with a radiation source of CuKα rays, a tube voltage of 40 kV and a tube current of 15 mA. In this case, the diffracted X-ray passes through a Kβ filter having a thickness of 30 μm and is detected by a high-speed one-dimensional detector (D/teX Ultra 2). In addition, a sampling width is 0.02°, a scan speed is 10°/min, a divergence slit width is 0.625°, a light receiving slit width is 13 mm (OPEN), and a scattering slit width is 8 mm. Then, the crystal structure of the composite oxide can be identified by Rietveld analysis using a “RIETAN-FP” program (F. Izumi and K. Momma, Solid State Phenom., 130, 15-20 (2007)) based on the obtained X-ray diffraction pattern. Note that the X-ray diffractometer is not limited to the above apparatus, and the X-ray source is also not limited. The X-ray diffraction measurement conditions are not limited to the above conditions. In addition, a method for analyzing the obtained X-ray diffraction pattern is not limited to the above method.
The composite oxide having a crystal structure belonging to a space group Fm-3m is represented by a general formula: LixTMtmMyO2-fFf, and in the general formula, TM represents a transition metal, M represents a non-transition metal, x, tin, y, and f satisfy 1.75≤x+tm+y≤2 and 0<f≤0.7,and when Q=2×tm×{1−(1−f/2)5}, 0.8≤Q≤1.5 is satisfied. Here. Q represents the number of oxygen bonded to the transition metal bonded to fluorine. By using such a composite oxide, a discharge voltage of the positive electrode active material can be increased. Note that the crystal structure may have vacancies in which Li atoms, TM atoms, and M atoms are not disposed. Here, having vacancies means that vacancies not filled with Li atoms, TM atoms, and M atoms are present in the composite oxide in the positive electrode active material taken out immediately after manufacture or by disassembling the secondary battery in a discharged state. A molar ratio of the vacancies is preferably greater than or equal to 0.05 and less than or equal to 0.25.
In the general formula, x, tm, y, and f preferably satisfy, for example, 1.0<x≤1.4, 0.4≤tm<1.0, 0≤y≤0.2, and 0.2≤f≤0.6 in that a higher discharge voltage can be obtained.
The composite oxide preferably contains Mn as the transition metal (TM) in that, for example, a higher discharge voltage can be obtained or a discharge capacity can be improved, and in the general formula, a molar ratio tm_Mn of Mn in tm preferably is 0.6<tm_Mn<0.8.
The composite oxide preferably contains, for example, Mn and a transition metal other than Mn from the viewpoint of being able to obtain a higher discharge voltage or improving the discharge capacity. Examples of the transition metal other than Mn include Ni, Co, Fe, Ti, Y, Zr, Nb, Mo, Sc, W, V, Gd, Ce, and Ta, and Ce, Gd, and Nb are more preferable.
Examples of the non-transition metal (M) contained in the composite oxide include Al, Mg, Sb, Bi, Ca. Sr, Mg, K, Ga, Sn, and Zn, and Ga and Mg are more preferable.
The composite oxide contains, for example, Mn, from the viewpoint of being able to obtain a higher discharge voltage or improving the discharge capacity, and preferably contains at least one element of five elements of Gd, Ce, and Nb, which are the transition metals (TM), and Mg and Ga, which are the non-transition metals (M), and more preferably contains at least three elements of the five elements. In addition, a molar ratio of each of Mg, Gd, Ce, Nb, and Ga in the composite oxide is preferably greater than 0 and less than or equal to 0.025.
Confirmation of the composition of the composite oxide can be performed by, for example, Rietveld analysis on parameters obtained by inductively coupled plasma emission spectrometry, X-ray photoelectron spectroscopy, and powder X-ray diffraction.
A method for producing the composite oxide is not particularly limited, and may be a known method in synthesis of a positive electrode active material, and the composite oxide can be obtained by, for example, treating a lithium source, an additive element source, a fluorine source, or the like by a mechanochemical method. The mechanochemical method (also referred to as a mechanochemical treatment or the like) refers to a synthesis method using a mechanochemical reaction. The mechanochemical reaction refers to a chemical reaction such as a crystallization reaction, a solid solution reaction, or a phase transition reaction using high energy locally generated by mechanical energy such as friction or compression in a process of crushing a solid substance. Examples of an apparatus for performing the mechanochemical method include a pulverizer and a disperser such as a ball mill, a bead mill, a vibration mill, a turbo mill, a mechano-fision, or a disk mill. Among them, a ball mill is preferable. The mechanochemical treatment may be performed in an inert gas atmosphere such as argon gas, or may be performed in an oxygen-containing atmosphere or the like.
Examples of the lithium source include lithium carbonate and lithium hydroxide. The additive element source is a transition metal-containing compound and a non-transition metal-containing compound, and is, for example, a transition metal-containing oxide or hydroxide, a non-transition metal-containing oxide or hydroxide, a transition metal- or non-transition metal-containing composite oxide or hydroxide, and the like.
The fluorine source is a fluoride such as lithium fluoride, molybdenum fluoride, or magnesium fluoride. Note that lithium fluoride may be used as a lithium source, a transition metal fluoride such as molybdenum fluoride may be used as a transition metal-containing compound as an additive element source, and a non-transition metal fluoride such as magnesium fluoride may be used as a non-transition metal-containing compound as an additive element source.
The composite oxide obtained by the mechanochemical treatment may be subjected to a heat treatment. A heating temperature is not particularly limited, and may be, for example, in a range of greater than or equal to 500° C. and less than or equal to 1,000° C. In addition, a heating time is not particularly limited, and is, for example, greater than or equal to 1 hour and less than or equal to 20 hours. The heating may be performed in an inert gas atmosphere such as argon gas, or may be performed in an oxygen-containing atmosphere or the like.
The positive electrode active material may be composed of only the composite oxide, but may contain an active material other than the composite oxide. Examples of the other active material include a composite oxide represented by LixMOy (M represents at least one kind of transition metal)(LixCoO2, LixNiO2, LixMnO2, LixNiαCo(1-α)O2, LixNiαMnβCo(1-α-β)O2, or the like having a layered α—NaFeO2-type crystal structure, or LixMn2O4, LixNixMn(2-α)O4, or the like having a spinel-type crystal structure), and a polyanion compound represented by LiwM′x(XOy)z (M′ represents at least one kind of transition metal, and X represents, for example, P, Si, B, V, or the like) (LiFePO4, LiMnPO4, LiNiPO4, LiCoPO4, Li3V2(PO4)3, Li2MnSiO4, Li2CoPO4F, or the like).
A content of the composite oxide that has a crystal structure belonging to a space group Fm-3m and is represented by a general formula: LixTMtmMyO2-fFf, in which in the general formula, TM represents a transition metal, M represents a non-transition metal, x, tm, y, and f satisfy 1.75≤x+tm+y≤2 and 0<f≤0.7, and when Q=2×tm×{1-(1-f/2)5}, 0.8≤Q≤1.5 is satisfied, is preferably greater than or equal to 50 mass %, more preferably greater than or equal to 70 mass %, and still more preferably greater than or equal to 90 mass %, with respect to a total mass of the positive electrode active material.
Examples of the conductive agent contained in the positive electrode mixture layer include carbon powders such as carbon black, acetylene black, Ketjenblack, and graphite, and these conductive agents may be used alone or in combination of two or more thereof.
As the binding agent contained in the positive electrode mixture layer, for example, a fluorine-based resin such as polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVdF), PAN, a polyimide-based resin, an acrylic resin, a polyolefin-based resin, styrene-butadiene rubber (SBR), CMC or a salt thereof, a polyaciylic acid (PAA) or a salt thereof (PAA-Na, PAA-K. or the like), polyvinyl alcohol (PVA), and the like can be used. These materials may be used alone or in combination of two or more thereof.
The negative electrode 12 includes, for example, a negative electrode current collector such as a metal foil and a negative electrode mixture layer formed on the negative electrode current collector. The negative electrode current collector may be, for example, a foil of a metal, such as copper, that is stable in a potential range of the negative electrode, a film in which the metal is disposed on its surface layer. The negative electrode mixture layer contains, for example, a negative electrode active material, a binding agent, and the like.
The negative electrode active material contained in the negative electrode mixture layer is not particularly limited as long as it is a material capable of occluding and releasing lithium ions, and examples thereof include a carbon material, and an element capable of forming an alloy with lithium or a compound containing the element. As the carbon material, graphites such as natural graphite, non-graphitizable carbon, and artificial graphite, cokes, and the like can be used. Examples of the element capable of forming an alloy with lithium and the compound containing the element include silicon and tin, and silicon oxide and tin oxide formed by combining silicon and tin with oxygen. In addition to the above, a material having a higher charge-discharge potential with respect to metal lithium such as lithium titanate than a carbon material or the like can also be used. The binding agent contained in the negative electrode mixture layer may be the same as that in the positive electrode.
For example, a porous sheet having an ion permeation property and an insulation property is used for the separator 13. Specific examples of the porous sheet include a fine porous thin film, a woven fabric, and a non-woven fabric. As a material of the separator 13, an olefin-based resin such as polyethylene or polypropylene, cellulose, and the like are preferable. The separator 13 may be a laminate including a cellulose fiber layer and a thermoplastic resin fiber layer formed of an olefin-based resin or the like, and the separator 13 may have a surface coated with an aramid resin or the like.
Hereinafter, the present disclosure will be further described with reference to Examples, but the present disclosure is not limited to these Examples.
Lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), magnesium oxide (MgO), gadolinium oxide (Gd2O3), and cerium oxide (CeO2) were used as starting sources of a composite oxide, and the compounds were weighed and mixed so that a molar ratio of Li:Mn:Mg:Gd:Ce:F was 1.225:0.705:0.005:0.01:0.005:0.6. The mixed powder was charged into a planetary ball mill (Premium-Line P7 manufactured by Fritsch GmbH, rotation speed: 600 rpm, container: 45 mL pot formed of zirconia, ball: φ3 mm ball formed of zirconia) and treated in an Ar-atmosphere at room temperature for 35 hours (after 1 hour of the operation, a cycle of pausing for 10 minutes was repeated 35 times). In this way, a composite oxide represented by Li1.225Mn0.705Mg0.005Gd0.01Ce0.005O1.4F0.6 was obtained.
The obtained composite oxide was subjected to powder X-ray diffraction measurement, and the results are illustrated in
70 parts by mass of the composite oxide, 20 parts by mass of acetylene black, and 10 parts by mass of polyvinylidene fluoride were mixed in terms of proportion, and N-methyl-2-pyrrolidone (NMP) was used as a dispersion medium to prepare a slurry for a positive electrode mixture layer. Next, the slurry for a positive electrode mixture layer was applied to an aluminum foil having a thickness of 15 μm and dried, and the obtained coating film was rolled to manufacture a positive electrode in which a positive electrode mixture layer was formed on both surfaces of the aluminum foil.
Lithium hexafluorophosphate (LiPF6) was dissolved in a mixed solvent obtained by mixing fluoroethylene carbonate (FEC) and methyl propionate (FMP) at a volume ratio of 1:3 so that a concentration thereof was 1 mol/liter to prepare a non-aqueous electrolyte.
Electrode leads were attached to the metal lithium as the positive electrode and the negative electrode, respectively. Then, an electrode assembly with a separator interposed between the positive electrode and the negative electrode was produced, the electrode assembly was housed in an aluminum laminate film, and the non-aqueous electrolyte was injected and sealed. This was used as a test cell (non-aqueous electrolyte secondary battery) of Example 1.
A composite oxide represented by Li1.225Mn0.7Mg0.01Ga0.01Nb0.005O1.4F0.6 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), magnesium oxide (MgO), gallium oxide (Ga2O3), and niobium oxide (Nb2O5) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Mg:Ga:Nb:F was 1.225:0.7:0.01:0.01:0.005:0.6. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to a space group Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.225Mn0.7Mg0.01Ga0.01Nb0.005O1.4F0.6
A composite oxide represented by L1.143Mn0.765Mg0.02Nb0.01Ce0.005O1.553F0.447 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), magnesium oxide (MgO), niobium oxide (Nb2O5), and cerium oxide (CeO2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Mg:Nb:Ce:F was 1.143:0.765:0.02:0.01:0.005:0.447. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to a space group Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.143Mn0.765Mg0.02Nb0.01Ce0.005O1.553F0.447.
A composite oxide represented by Li1.168Mn0.755Gd0.005Nb0.01Ce0.005O1.553F0.447 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), gadolinium oxide (Gd2O3), niobium oxide (Nb2O5), and cerium oxide (CeO2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Gd:Nb:Ce:F was 1.168:0.755:0.005:0.01:0.005:0.447. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to a space group Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.168Mn0.755Gd0.005Nb0.01Ce0.005O1.553F0.447.
A composite oxide represented by Li1.175Mn0.76Ga0.005Nb0.005Ce0.005O1.55F0.45 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(II) oxide (Mn2O3), lithium peroxide (Li2O2), gallium oxide (Ga2O3), niobium oxide (Nb2O5), and cerium oxide (CeO2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Ga:Nb:Ce:F was 1.175:0.76:0.005:0.005:0.005:0.45. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to a space group Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by L1.2Mn0.685Ga0.05Nb0.005Ce0.005O1.5F0.5.
A composite oxide represented by Li1.2Mn0.685Ga0.005Nb0.005Ce0.005O1.5F0.5 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), gallium oxide (Ga2O3), niobium oxide (Nb2O5), and cerium oxide (CeO2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Ga:Nb:Ce:F was 1.2:0.685:0.005:0.005:0.005:0.5. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to a space group Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.2Mn0.685Ga0.005Nb0.005Ce0.005O1.5F0.5.
A composite oxide represented by Li1.175Mn0.7Mg0.025Ga0.025Ce0.025O1.55F0.45 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(II) oxide (Mn2O3), lithium peroxide (Li2O2), magnesium oxide (MgO), gallium oxide (Ga2O3), and cerium oxide (CeO2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Mg:Ga:Ce:F was 1.175:0.7:0.025:0.025:0.025:0.45. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to a space group Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.175Mn0.7Mg0.025Ga0.025Ce0.025O1.55F0.45.
A composite oxide represented by Li1.192Mn0.73Gd0.005Nb0.01Ce0.005O1.702F0.298 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), gadolinium oxide (Gd2O3), niobium oxide (Nb2O5), and cerium oxide (CeO2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Gd:Nb:Ce:F was 1.192:0.73:0.005:0.01:0.005:0.298. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to a space group Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.192Mn0.73Gd0.005Nb0.01Ce0.005O1.702F0.298.
A composite oxide represented by Li1.2Mn0.735Mg0.005Ga0.005Nb0.005O1.7F0.3 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), magnesium oxide (MgO), gallium oxide (Ga2O3), and niobium oxide (Nb2O5) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Mg:Ga:Nb:F was 1.2:0.735:0.005:0.005:0.005:0.3. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to a space group Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.2Mn0.735Mg0.005Ga0.005Nb0.005O1.7F0.3.
A composite oxide represented by Li1.25Mn0.73Mg0.005Gd0.005Nb0.01O1.702F0.298 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), magnesium oxide (MgO), gadolinium oxide (Gd2O3), and niobium oxide (Nb2O5) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Mg:Gd:Nb:F was 1.25:0.73:0.005:0.005:0.01:0.298. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to a space group Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by L1.25Mn0.73Mg0.005Gd0.005Nb0.01O1.702F0.298.
A composite oxide represented by Li1.15Mn0.785Mg0.005Nb0.005Ce0.005O1.8F0.2 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), magnesium oxide (MgO), niobium oxide (Nb2O5), and cerium oxide (CeO2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Mg:Nb:Ce:F was 1.15:0.785:0.005:0.005:0.005:0.2. The obtained composite oxide was subjected to powder X-ray diffraction measurement, and the results are illustrated in
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.15Mn0.785Mg0.005Nb0.005Ce0.005O1.8F0.2.
A composite oxide represented by Li1.25Mn0.485Ga0.005Nb0.005Ce0.005O1.5F0.5 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), gallium oxide (Ga2O3), niobium oxide (Nb2O5), and cerium oxide (CeO2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Ga:Nb:Ce:F was 1.25:0.485:0.005:0.005:0.005:0.5. The obtained composite oxide was subjected to powder X-ray diffraction measurement, and the results are illustrated in
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.25Mn0.485Ga0.005Nb0.005Ce0.005O1.5F0.5.
A composite oxide represented by Li1.25Mn0.45Mg0.025Ce0.025O1.5F0.5 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), magnesium oxide (MgO), and cerium oxide (CeO2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Mg:Ce:F was 1.25:0.45:0.025:0.025:0.5. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to a space group Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.25Mn0.45Mg0.025Ce0.025O1.5F0.5.
A composite oxide represented by Li1.667Mn0.333O0.667F1.333 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(II) oxide (Mn2O3), and lithium peroxide (Li2O2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:F was 1.667:0.333:1.333. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.667Mn0.333O0.667F1.333.
A composite oxide represented by Li1.2Mn0.6Ti0.2O1.8F0.2 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), lithium peroxide (Li2O2), and titanium dioxide (TiO2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:Ti:F was 1.2:0.6:0.2:0.2. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.2Mn0.6Ti0.2O1.8F0.2.
A composite oxide represented by LiMnO2 was obtained in the same manner as that of Example 1, except that LiMnO2 was used as the composite oxide. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by LiMnO2.
A composite oxide represented by Li1.1Mn0.6O1.3F0.7 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), and lithium peroxide (Li2O2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:F was 1.1:0.6:0.7. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by Li1.1Mn0.6O1.3F0.7.
A composite oxide represented by Li1.14MnO0.86O1.3F0.7 was obtained in the same operation as that of Example 1, except that lithium fluoride (LiF), lithium manganate (LiMnO2), manganese(III) oxide (Mn2O3), and lithium peroxide (Li2O2) were used as starting sources of a composite oxide, and the compounds were weighed so that a molar ratio of Li:Mn:F was 1.14:0.86:0.7. The obtained composite oxide was subjected to powder X-ray diffraction measurement and crystal structure analysis, and as a result, it was confirmed that the crystal structure of the composite oxide belonged to Fm-3m.
Then, a test cell was manufactured in the same manner as that of Example 1 using the composite oxide represented by L1.14Mn0.86O1.3F0.7.
Each of the test cells of the respective Examples and the respective Comparative Examples was subjected to constant current charge at a constant current of 0.1 C under a temperature environment of 25° C. until a battery voltage reached 4.95 V, and subjected to constant voltage charge at 4.95 V until a current value reached 0.05 C. Thereafter, the test cell was subjected to constant current discharge at a constant current of 0.1 C until a battery voltage reached 2.5 V. Then, a value obtained by dividing the total amount of power at the time of discharge by the total current was obtained as a discharge voltage. In addition, the discharge capacity (mAh/g) at the time of performing the constant current discharge was determined.
In Table 1, the compositions of the composite oxides, the values of x+tm+y of the compositions (LixTMtmMyO2-fFf′. TM represents a transition metal and M represents a non-transition metal), the values of f, the values of 2×m×{1−(1−f/2)5}=Q, and the results of the discharge capacity and the discharge voltage of the respective Examples and the respective Comparative Examples are summarized.
F0.2
Ga0.005Nb0.005Ce0.005O1.5F0.5
indicates data missing or illegible when filed
In all of Examples 1 to 11, a higher discharge voltage was exhibited and a higher discharge capacity was obtained, compared to Comparative Examples 1 to 7. From these results, it can be said that a high discharge voltage can be obtained by using a composite oxide that has a crystal structure belonging to a space group Fm-3m and is represented by a general formula: LixTMtmMyO2-fFf, in which in the general formula, TM represents a transition metal, M represents a non-transition metal, x, tm, y, and f satisfy 1.75≤x+tm+y≤2 and 0<f≤0.7, and when Q=2×tm×{1−(1−f/2)5}, 0.8≤Q≤1.5 is satisfied.
As can be seen from the drawing, in Comparative Example 1, the discharge voltage is low, and only a low discharge capacity is obtained. In the other Comparative Examples 2 to 7, the same charge and discharge curves were obtained, and the results shown in Table 1 were inferior to those of Examples.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-058486 | Mar 2022 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/045645 | 12/12/2022 | WO |
