WO2022270186A1 - 正極活物質、被覆正極活物質、正極材料、および電池 - Google Patents
正極活物質、被覆正極活物質、正極材料、および電池 Download PDFInfo
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- WO2022270186A1 WO2022270186A1 PCT/JP2022/020873 JP2022020873W WO2022270186A1 WO 2022270186 A1 WO2022270186 A1 WO 2022270186A1 JP 2022020873 W JP2022020873 W JP 2022020873W WO 2022270186 A1 WO2022270186 A1 WO 2022270186A1
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- positive electrode
- electrode active
- active material
- solid electrolyte
- battery
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- 239000007774 positive electrode material Substances 0.000 title claims description 183
- 239000013543 active substance Substances 0.000 title abstract 4
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
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- 239000000463 material Substances 0.000 claims description 47
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
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- 239000011572 manganese Substances 0.000 description 18
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- 230000000052 comparative effect Effects 0.000 description 13
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- 238000002360 preparation method Methods 0.000 description 8
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- 238000003801 milling Methods 0.000 description 2
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- 229910021382 natural graphite Inorganic materials 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
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- 239000002243 precursor Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
-
- 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
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- 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
- H01M10/0562—Solid materials
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H01M4/00—Electrodes
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/008—Halides
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- 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 disclosure relates to positive electrode active materials, coated positive electrode active materials, positive electrode materials, and batteries.
- Patent Document 1 discloses a positive electrode comprising a positive electrode active material made of a composite oxide containing lithium, nickel, cobalt, and manganese, a positive electrode mixture containing a solid electrolyte, and an all-solid-state battery comprising the positive electrode. doing.
- the present disclosure provides a positive electrode active material that can reduce battery resistance.
- the full width at half maximum of the peak having the highest intensity within the range of diffraction angles 2 ⁇ of 40° or more and 50° or less
- the ratio of the value to the value of the full width at half maximum of the peak corresponding to the (111) plane of the Si crystal powder measured under the same conditions is 2.00 or less.
- a cathode active material is provided.
- FIG. 1 is a cross-sectional view showing a schematic configuration of a positive electrode material 1000 according to Embodiment 3.
- FIG. FIG. 2 is a cross-sectional view showing a schematic configuration of battery 2000 according to Embodiment 4.
- FIG. 3 is a graph showing X-ray diffraction patterns of cathode active materials according to Examples 1 to 8 and Comparative Example 1;
- the present inventors have conducted intensive research on factors that increase the resistance of lithium ion batteries, and have found that the resistance of lithium ion batteries changes when the crystallinity of the active material changes. As a result of further studies based on this knowledge, the present inventors found that the resistance of lithium ion batteries can be reduced by increasing the crystallite size of the active material particles. At this time, the size of the crystallite size was judged from the size of the full width at half maximum of the peak in the diffraction pattern of the X-ray diffraction measurement.
- the present inventors arrived at the following positive electrode active material of the present disclosure as a new positive electrode active material capable of reducing battery resistance.
- the positive electrode active material according to the first aspect of the present disclosure is a positive electrode active material particle containing as a main component a composite oxide represented by the following compositional formula (1), LiNi x Me 1-x O 2 (1) here, x satisfies 0.5 ⁇ x ⁇ 1, Me is Co, Mn, Al, Mg, Ca, Sr, Ba, B, Ga, Y, Ce, Sm, Gd, Er, Ti, Zr, V, Nb, Ta, Sb, Bi, Cr, Mo, and is at least one selected from the group consisting of W,
- the full width at half maximum of the peak having the highest intensity within the range of diffraction angles 2 ⁇ of 40° or more and 50° or less
- the ratio of the value to the value of the full width at half maximum of the peak corresponding to the (111) plane of the Si crystal powder measured under the
- the resistance of the battery can be lowered.
- the full width at half maximum ratio of the peak may be 1.90 or less.
- the resistance of the battery can be further reduced.
- the coated positive electrode active material according to the third aspect of the present disclosure is A positive electrode active material according to the first or second aspect; a coating material that coats at least part of the surface of the positive electrode active material; including
- the coating material is Lithium element (Li); at least one selected from the group consisting of oxygen element (O), fluorine element (F), and chlorine element (Cl); including.
- the resistance of the battery can be reduced.
- the positive electrode material according to the fourth aspect of the present disclosure is At least one selected from the group consisting of the positive electrode active material according to the first or second aspect and the coated positive electrode active material according to the third aspect; a solid electrolyte; including.
- the resistance of the battery can be lowered.
- the solid electrolyte may contain at least one selected from the group consisting of a sulfide solid electrolyte and a halide solid electrolyte.
- the resistance of the battery can be further reduced.
- the halide solid electrolyte is represented by the following compositional formula (2), Li ⁇ M ⁇ X ⁇ Formula (2) here, ⁇ , ⁇ , and ⁇ are each independently a value greater than 0;
- the M is at least one selected from the group consisting of metal elements other than Li and metalloid elements,
- the X may be at least one selected from the group consisting of F, Cl, Br and I.
- the resistance of the battery can be further reduced.
- M may contain yttrium.
- the resistance of the battery can be further reduced.
- the resistance of the battery can be further reduced.
- the X may contain at least one selected from the group consisting of Cl and Br .
- a positive electrode comprising a positive electrode material according to any one of the fourth to ninth aspects; a negative electrode; an electrolyte layer disposed between the positive electrode and the negative electrode.
- the battery according to the tenth aspect can further reduce battery resistance.
- the electrolyte layer includes a solid electrolyte having the same composition as the solid electrolyte contained in the positive electrode material. You can stay.
- the battery according to the eleventh aspect can further improve charge-discharge efficiency.
- the electrolyte layer may contain a halide solid electrolyte having a composition different from that of the solid electrolyte contained in the positive electrode material.
- the battery according to the twelfth aspect can further reduce battery resistance.
- the electrolyte layer may contain a sulfide solid electrolyte.
- the battery according to the thirteenth aspect can further reduce battery resistance.
- the positive electrode active material according to Embodiment 1 contains a composite oxide represented by the following compositional formula (1).
- x satisfies 0.5 ⁇ x ⁇ 1.
- Me is Co, Mn, Al, Mg, Ca, Sr, Ba, B, Ga, Y, Ce, Sm, Gd, Er, Ti, Zr, V, Nb, Ta, Sb, Bi, Cr, Mo , and at least one selected from the group consisting of W.
- the ratio of the value of the full width at half maximum of to the value of the full width at half maximum of the peak corresponding to the (111) plane of the Si crystal powder measured under the same conditions is 2.00 or less.
- the value of the full width at half maximum of the peak having the highest intensity within the range of the diffraction angle 2 ⁇ of 40° or more and 50° or less is Called “FWHM”. Furthermore, the value of the full width at half maximum of the peak corresponding to the (111) plane of the Si crystal powder measured under the same conditions is called “FWHM Si ".
- a Si standard sample is used as the Si crystal powder measured under the same conditions as the X-ray diffraction measurement of the positive electrode active material according to the first embodiment.
- a standard Si crystal powder "NIST640d” manufactured by NIST National Institute of Standards and Technology: US National Institute of Standards and Technology
- the positive electrode active material according to Embodiment 1 the above condition that "the ratio of FWHM to FWHM Si is 2.00 or less" (that is, FWHM/FWHM Si ⁇ 2.00) is satisfied, so that crystallites size increases. As a result, in the positive electrode active material according to Embodiment 1, the grain boundaries can be reduced, so the grain boundary resistance is reduced. Therefore, the positive electrode active material in Embodiment 1 can reduce the resistance of the battery.
- the peak having the highest intensity within the range of diffraction angles 2 ⁇ of 40° or more and 50° or less is derived from the diffraction of the (104) plane.
- the (104) plane is known to be a crystal plane through which Li ions are inserted and extracted.
- the peak with the highest intensity within the range of diffraction angles 2 ⁇ of 15° or more and 20° or less originates from the (003) plane.
- the (003) plane is known to be a crystal plane in which Li ions are difficult to enter and exit. From the viewpoint of crystallite size, both peaks show similar trends, but considering the possibility of orientation, the peak of the (104) plane can more accurately evaluate the resistance of the battery.
- the ratio of FWHM to FWHM Si may be 1.90 or less.
- the positive electrode active material according to Embodiment 1 can have a larger crystallite size. Therefore, the grain boundaries are further reduced in the positive electrode active material according to Embodiment 1, and as a result, the grain boundary resistance can be further reduced. Therefore, by satisfying the condition of FWHM/FWHM Si ⁇ 1.90, the positive electrode active material according to Embodiment 1 can further reduce the resistance of the battery.
- the positive electrode active material according to Embodiment 1 is specified not by the value of FWHM but by the ratio of FWHM to FWHM Si . Therefore, when specifying the active material according to Embodiment 1, it is not necessary to consider the measurement error caused by the measurement device.
- the positive electrode active material according to Embodiment 1 may contain the composite oxide represented by the above compositional formula (1) as a main component.
- the "main component” is the component that is contained most in terms of mass ratio.
- the positive electrode active material according to Embodiment 1 may contain 75% by mass or more, or 90% by mass or more, of the composite oxide represented by the above compositional formula (1).
- the positive electrode active material according to Embodiment 1 may consist of only the composite oxide represented by the above compositional formula (1).
- the positive electrode active material according to Embodiment 1 may further contain, for example, a material that can be used as an active material for an all-solid-state lithium ion battery, in addition to the composite oxide represented by the above compositional formula (1).
- LiCoO2 LiNixCo1 - xO2 ( 0 ⁇ x ⁇ 0.5), LiNi1 / 3Co1 /3Mn1/ 3 .
- O 2 LiMnO 2
- heteroelement-substituted Li—Mn spinels e.g., LiMn 1.5 Ni 0.5 O 4 , LiMn 1.5 Al 0.5 O 4 , LiMn 1.5 Mg 0.5 O 4 , LiMn 1.5 Co 0.5 O 4 , LiMn 1.5 Fe 0.5 O 4 , or LiMn1.5Zn0.5O4
- LiMn 1.5 Ni 0.5 O 4 LiMn 1.5 Al 0.5 O 4
- LiMn 1.5 Mg 0.5 O 4 LiMn 1.5 Mg 0.5 O 4
- LiMn 1.5 Co 0.5 O 4 LiMn 1.5 Fe 0.5 O 4
- LiMn1.5Zn0.5O4 lithium titanates
- Li4Ti5O12 lithium metal phosphates (e.g. LiFePO4 , LiMnPO4 , LiCoPO4 , or LiNiPO4 ), transition metal oxides (e.g. V2 O5 , MoO3 ).
- LiFePO4 lithium metal phosphates
- LiMnPO4 LiMnPO4
- LiCoPO4 LiCoPO4
- LiNiPO4 transition metal oxides
- LiCoO 2 LiNi x Co 1-x O 2 (0 ⁇ x ⁇ 0.5), LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiMnO 2 , dissimilar element-substituted Li- At least one lithium-containing composite oxide selected from Mn spinel and lithium metal phosphate may be included.
- the positive electrode active material according to Embodiment 1 is produced, for example, by a coprecipitation method.
- the positive electrode active material according to Embodiment 1 can be produced by producing a precursor made of a metal oxide containing Ni and Me and sintering the precursor together with a lithium source.
- a positive electrode active material with a small full width at half maximum that satisfies the condition that "the ratio of FWHM to FWHM Si is 2.00 or less" can be produced, for example, by controlling firing conditions such as firing temperature and firing time.
- the firing temperature may be, for example, 760° C. or higher.
- the positive electrode active material may be annealed in an oxygen atmosphere or the like. Moreover, when producing the positive electrode active material, the ratio of the Li raw material may be increased more than the stoichiometric ratio of the active material, and the active material may be fired. Further, annealing may be performed by adding a Li raw material.
- Embodiment 2 (Embodiment 2) Embodiment 2 will be described below. Descriptions that duplicate those of the above-described first embodiment are omitted as appropriate.
- a coated positive electrode active material according to Embodiment 2 of the present disclosure includes a positive electrode active material and a coating material that coats at least part of the surface of the positive electrode active material.
- the positive electrode active material in the covering material that covers at least part of the surface is the positive electrode active material according to the first embodiment described in the first embodiment.
- the coating material contains lithium element (Li) and at least one selected from the group consisting of oxygen element (O), fluorine element (F), and chlorine element (Cl).
- the coated positive electrode active material according to Embodiment 2 contains the positive electrode active material according to Embodiment 1, it is possible to reduce the resistance of the battery. Furthermore, in the coated positive electrode active material according to Embodiment 2, at least part of the surface of the positive electrode active material is coated with a coating material. Therefore, the interfacial resistance between the positive electrode active material and, for example, the solid electrolyte can be reduced, so that the resistance of the battery can be further reduced. Moreover, by providing such a coating material on the surface, decomposition of the solid electrolyte due to contact between the solid electrolyte and the positive electrode active material can be suppressed.
- the coating material may partially cover the surface of the positive electrode active material, or may cover the entire surface.
- the coating material contains Li and at least one selected from the group consisting of O, F, and Cl.
- the coating material may be, for example, an oxide solid electrolyte.
- oxide solid electrolytes that can be used as coating materials include lithium niobate, lithium phosphate, lithium titanate, and lithium tungstate.
- Oxide solid electrolytes have high ionic conductivity. Oxide solid electrolytes have excellent high potential stability. Therefore, by using the oxide solid electrolyte as the coating material, the resistance of the battery can be further reduced.
- the coating material contains Li and at least one selected from the group consisting of F and Cl
- the coating material may be, for example, a halide solid electrolyte.
- the coating material may be, for example, an oxyhalide solid electrolyte.
- the coating material may contain Li, O, and F.
- the coating material may include at least one selected from the group consisting of lithium fluoride zirconate, lithium fluoride aluminumate, lithium fluoride titanate, and lithium fluoride magnesiumate.
- the thickness of the coating material may be 1 nm or more and 100 nm or less.
- the thickness of the coating material is 1 nm or more, direct contact of the positive electrode active material with, for example, the solid electrolyte can be suppressed, and reaction between the positive electrode active material and the solid electrolyte can be suppressed. Moreover, since the thickness of the coating material is 100 nm or less, the thickness of the coating material does not become too thick. Therefore, the resistance of the battery can be lowered.
- the coated positive electrode active material according to Embodiment 2 can be produced, for example, by forming a coating material on the surfaces of particles of the positive electrode active material.
- a known method can be used as a method for forming the coating material on the surface of the particles of the positive electrode active material.
- a liquid phase coating method, a vapor phase coating method, a dry particle compounding method, and the like can be used.
- a positive electrode material according to Embodiment 3 of the present disclosure includes at least one selected from the group consisting of a positive electrode active material and a coated positive electrode active material, and a solid electrolyte.
- a positive electrode active material the positive electrode active material described in Embodiment 1 is used.
- the coated positive electrode active material the coated positive electrode active material described in Embodiment 2 is used.
- FIG. 1 is a cross-sectional view showing a schematic configuration of a positive electrode material 1000 according to Embodiment 3.
- Cathode material 1000 includes a coated cathode active material including cathode active material 110 and coating material 120 , and solid electrolyte 100 .
- the solid electrolyte contained in the solid electrolyte 100 may contain at least one selected from the group consisting of sulfide solid electrolytes and halide solid electrolytes.
- the halide solid electrolyte may be a compound represented by the following compositional formula (2).
- M is at least one selected from the group consisting of metal elements other than Li and metalloid elements.
- X is at least one selected from the group consisting of F, Cl, Br and I;
- metal elements are B, Si, Ge, As, Sb and Te.
- Metallic element means all elements contained in Groups 1 to 12 of the periodic table except hydrogen, and B, Si, Ge, As, Sb, Te, C, N, P, O, S, and All elements contained in groups 13 to 16 of the periodic table except Se. That is, the term “semimetallic element” or “metallic element” refers to a group of elements that can become cations when an inorganic compound is formed with a halogen element.
- Li3YX6 Li2MgX4 , Li2FeX4 , Li ( Al, Ga, In )X4, Li3 ( Al, Ga, In ) X6 , etc.
- X is at least one selected from the group consisting of F, Cl, Br and I.
- (A, B, C) means "at least one selected from the group consisting of A, B, and C.”
- X may include at least one selected from the group consisting of Cl and Br.
- M may contain yttrium (Y).
- the Y -containing solid electrolyte may be, for example, a compound represented by the composition formula LiaM'bYcX6 .
- M' is at least one selected from the group consisting of metal elements other than Li and Y and metalloid elements.
- m indicates the valence of M'.
- X is at least one selected from the group consisting of F, Cl, Br and I;
- At least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb may be used as M'.
- solid electrolytes containing Y include Li3YF6 , Li3YCl6 , Li3YBr6 , Li3YI6 , Li3YBrCl5 , Li3YBr3Cl3 , Li3YBr5Cl , Li 3YBr5I , Li3YBr3I3 , Li3YBrI5 , Li3YClI5 , Li3YCl3I3 , Li3YCl5I , Li3YBr2Cl2I2 , Li3YBrCl4I , Li _ _ 2.7Y1.1Cl6 , Li2.5Y0.5Zr0.5Cl6 , Li2.5Y0.3Zr0.7Cl6 , etc. can be used .
- the resistance of the battery can be further reduced.
- the halide solid electrolyte does not have to contain sulfur. According to the above configuration, generation of hydrogen sulfide gas can be suppressed. Therefore, it is possible to realize a battery with improved safety.
- the shapes of the solid electrolyte 100 and the positive electrode active material 110 in Embodiment 3 are not particularly limited, and may be acicular, spherical, oval, or the like, for example.
- the shape of solid electrolyte 100 and positive electrode active material 110 may be particulate.
- the median diameter may be 100 ⁇ m or less.
- the positive electrode active material 110 and the solid electrolyte 100 can form a good dispersion state in the positive electrode material 1000 . This improves the charge/discharge characteristics of the battery.
- the median diameter of solid electrolyte 100 may be 10 ⁇ m or less.
- the positive electrode active material 110 and the solid electrolyte 100 can form a good dispersion state.
- the median diameter of solid electrolyte 100 may be smaller than the median diameter of positive electrode active material 110 .
- the solid electrolyte 100 and the positive electrode active material 110 can form a better dispersed state.
- the median diameter of the positive electrode active material 110 may be 0.1 ⁇ m or more and 100 ⁇ m or less.
- the positive electrode active material 110 When the median diameter of the positive electrode active material 110 is 0.1 ⁇ m or more, the positive electrode active material 110 and the solid electrolyte 100 can form a good dispersion state in the positive electrode material 1000 . As a result, the charge/discharge characteristics of the battery are improved.
- the median diameter of the positive electrode active material 110 is 100 ⁇ m or less, the diffusion rate of lithium in the positive electrode active material 110 is sufficiently ensured. Therefore, it is possible to operate the battery at a high output.
- volume diameter means the particle size when the cumulative volume in the volume-based particle size distribution is equal to 50%.
- the volume-based particle size distribution is measured by, for example, a laser diffraction measurement device or an image analysis device.
- the particles of the solid electrolyte 100 and the particles of the positive electrode active material 110 may be in contact with each other as shown in FIG. At this time, the coating material 120 and the positive electrode active material 110 are in contact with each other.
- the positive electrode material 1000 in Embodiment 3 may include a plurality of solid electrolyte 100 particles and a plurality of positive electrode active material 110 particles.
- the content of solid electrolyte 100 and the content of positive electrode active material 110 in positive electrode material 1000 in Embodiment 3 may be the same or different.
- Embodiment 4 will be described below. Descriptions overlapping those of the first to third embodiments described above will be omitted as appropriate.
- FIG. 2 is a cross-sectional view showing a schematic configuration of a battery 2000 according to Embodiment 4.
- FIG. 2 is a cross-sectional view showing a schematic configuration of a battery 2000 according to Embodiment 4.
- a battery 2000 according to Embodiment 4 includes a positive electrode 201 , an electrolyte layer 202 and a negative electrode 203 .
- the positive electrode 201 includes a positive electrode material 1000 .
- the positive electrode material 1000 is the positive electrode material described in the third embodiment.
- the electrolyte layer 202 is arranged between the positive electrode 201 and the negative electrode 203 .
- the volume ratio "v1:100-v1" of the positive electrode active material 110 and the solid electrolyte 100 contained in the positive electrode 201 may satisfy 30 ⁇ v1 ⁇ 95.
- 30 ⁇ v1 the energy density of battery 2000 is sufficiently ensured.
- v1 ⁇ 95 high output operation is possible.
- the thickness of the positive electrode 201 may be 10 ⁇ m or more and 500 ⁇ m or less. When the thickness of the positive electrode 201 is 10 ⁇ m or more, the energy density of the battery 2000 is sufficiently ensured. When the thickness of the positive electrode 201 is 500 ⁇ m or less, high output operation is possible.
- the electrolyte layer 202 is a layer containing an electrolyte material.
- the electrolyte material is, for example, a solid electrolyte material. That is, electrolyte layer 202 may be a solid electrolyte layer.
- the solid electrolyte the material exemplified as the material of the solid electrolyte 100 in the third embodiment may be used. That is, electrolyte layer 202 may contain a solid electrolyte having the same composition as solid electrolyte 100 contained in positive electrode material 1000 .
- the charging and discharging efficiency of the battery 2000 can be further improved.
- the electrolyte layer 202 may contain a halide solid electrolyte having a composition different from that of the solid electrolyte contained in the positive electrode material 1000 .
- the electrolyte layer 202 may contain a sulfide solid electrolyte.
- the electrolyte layer 202 may contain only one solid electrolyte selected from the group of solid electrolytes described above, or may contain two or more solid electrolytes selected from the group of solid electrolytes described above. .
- a plurality of solid electrolytes have compositions different from each other.
- electrolyte layer 202 may include a halide solid electrolyte and a sulfide solid electrolyte.
- the thickness of the electrolyte layer 202 may be 1 ⁇ m or more and 300 ⁇ m or less. When the thickness of electrolyte layer 202 is 1 ⁇ m or more, short circuit between positive electrode 201 and negative electrode 203 is unlikely to occur. When the thickness of the electrolyte layer 202 is 300 ⁇ m or less, operation at high output is possible.
- the negative electrode 203 includes a material that has the property of intercalating and deintercalating metal ions (eg, lithium ions).
- the negative electrode 203 contains, for example, a negative electrode active material.
- Metal materials, carbon materials, oxides, nitrides, tin compounds, silicon compounds, etc. can be used for the negative electrode active material.
- the metal material may be a single metal.
- the metal material may be an alloy.
- metallic materials include lithium metal, lithium alloys, and the like.
- carbon materials include natural graphite, coke, ungraphitized carbon, carbon fiber, spherical carbon, artificial graphite, amorphous carbon, and the like. From the viewpoint of capacity density, silicon (Si), tin (Sn), silicon compounds, or tin compounds can be preferably used.
- the negative electrode 203 may contain a solid electrolyte material. According to the above configuration, the lithium ion conductivity inside the negative electrode 203 is increased, and operation at high output becomes possible.
- the solid electrolyte the materials exemplified in Embodiment 3 may be used. That is, the negative electrode 203 may contain a solid electrolyte having the same composition as the solid electrolyte contained in the positive electrode material 1000 .
- the median diameter of the negative electrode active material may be 0.1 ⁇ m or more and 100 ⁇ m or less.
- the negative electrode active material and the solid electrolyte material can form a good dispersion state. As a result, the charge/discharge characteristics of the battery are improved.
- the median diameter of the negative electrode active material is 100 ⁇ m or less, the diffusion rate of lithium in the negative electrode active material is sufficiently ensured. Therefore, it is possible to operate the battery at a high output.
- the median diameter of the negative electrode active material may be larger than the median diameter of the solid electrolyte material. Thereby, a good dispersion state of the negative electrode active material and the solid electrolyte material can be formed.
- the volume ratio "v2:100-v2" of the negative electrode active material and the solid electrolyte material contained in the negative electrode 203 may satisfy 30 ⁇ v2 ⁇ 95.
- 30 ⁇ v2 the energy density of battery 2000 is sufficiently ensured.
- v2 ⁇ 95 high output operation is possible.
- the thickness of the negative electrode 203 may be 10 ⁇ m or more and 500 ⁇ m or less. When the thickness of the negative electrode 203 is 10 ⁇ m or more, the energy density of the battery 2000 is sufficiently ensured. When the thickness of the negative electrode 203 is 500 ⁇ m or less, high output operation is possible.
- At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder for the purpose of improving adhesion between particles.
- a binder is used to improve the binding properties of the material that constitutes the electrode.
- Binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, poly Acrylate hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene-butadiene rubber, carboxymethyl cellulose, and the like.
- Binders include tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene. Copolymers of two or more selected materials may be used. Also, two or more selected from these may be mixed and used as a binder.
- At least one selected from the group consisting of the positive electrode 201 and the negative electrode 203 may contain a conductive aid for the purpose of increasing electronic conductivity.
- conductive aids include graphites such as natural graphite or artificial graphite, carbon blacks such as acetylene black and Ketjen black, conductive fibers such as carbon fiber or metal fiber, carbon fluoride, and metal powder such as aluminum.
- conductive whiskers such as zinc oxide or potassium titanate, conductive metal oxides such as titanium oxide, conductive polymeric compounds such as polyaniline, polypyrrole, polythiophene, and the like. Cost reduction can be achieved when a carbon conductive aid is used.
- the battery in Embodiment 4 can be configured as batteries of various shapes such as coin type, cylindrical type, rectangular type, sheet type, button type, flat type, and laminated type.
- Example 1>> [Preparation of positive electrode active material] Nickel sulfate, cobalt sulfate, and manganese sulfate were dissolved in water, and nickel, cobalt, and manganese were coprecipitated with an alkaline aqueous solution containing sodium hydroxide to prepare hydroxides of nickel, cobalt, and manganese. The hydroxide was filtered, dried and pyrolyzed to produce an oxide containing nickel, cobalt and manganese in the desired proportions. This oxide and lithium hydroxide were mixed and fired at 850° C. in an oxygen atmosphere to prepare a positive electrode active material LiNi 0.8 (Co, Mn) 0.2 O 2 . The LiNi 0.8 (Co, Mn) 0.2 O 2 thus produced is hereinafter referred to as NCM-1. Thus, the positive electrode active material of Example 1 was obtained.
- FIG. 3 is a graph showing an X-ray diffraction pattern of the cathode active material according to Example 1.
- FIG. 3 is a graph showing the X-ray diffraction pattern of NCM-1 according to Example 1.
- FIG. 3 is a graph showing the X-ray diffraction pattern of NCM-1 according to Example 1.
- the X-ray diffraction pattern of the solid electrolyte material according to Example 1 was measured using an X-ray diffractometer (MiniFlex 600, manufactured by Rigaku) in a dry environment with a dew point of -50°C or lower. Measurements were performed by the ⁇ -2 ⁇ method using Cu-K ⁇ rays (wavelengths of 1.5405 ⁇ and 1.5444 ⁇ ) as the X-ray source. The measured angular interval was 0.01°. The divergence angle of the divergence slit was 0.25°. The slit width of the length limiting slit was 5 mm.
- the value of the diffraction angle 2 ⁇ of the peak having the highest intensity within the range of the diffraction angle 2 ⁇ of 40° or more and 50° or less was defined as 2 ⁇ top , and the intensity of the peak was defined as Itop .
- the average intensity at the diffraction angle 2 ⁇ from 40° to 41° was taken as I bg . That is, I bg represents the baseline intensity.
- the half value I htop of I top was set to [(I top ⁇ I bg )/2+I bg ].
- the diffraction angle 2 ⁇ at which the intensity is closest to Ihtop within the range of the diffraction angle 2 ⁇ of 40° or more and 2 ⁇ top or less was defined as 2 ⁇ L .
- the diffraction angle 2 ⁇ at which the intensity is closest to Ihtop within the range of 2 ⁇ top or more and 50° or less was defined as 2 ⁇ H .
- FWHM is the difference between 2 ⁇ H and 2 ⁇ L .
- the FWHM of the positive electrode active material according to Example 1 was 0.24 deg.
- the Si crystal powder was subjected to X-ray diffraction measurement under the same conditions as those of the positive electrode active material according to Example 1.
- the standard sample NIST640d was used as the Si crystal powder.
- the value of the diffraction angle 2 ⁇ of the peak having the highest intensity within the range of diffraction angles 2 ⁇ of 28.0° or more and 28.6° or less was defined as 2 ⁇ top , and the intensity of the peak was defined as Itop .
- the intensity at the diffraction angle 2 ⁇ of 28.0° was defined as I bg .
- the FWHM Si of the Si crystal powder was 0.16 deg.
- metal Li thinness: 200 ⁇ m
- this is pressure-molded at a pressure of 80 MPa, whereby the positive electrode, the solid electrolyte layer, and the negative electrode are separated from each other.
- a laminate was produced.
- Example 1 was produced by sealing the insulating outer cylinder with an insulating ferrule to isolate the inside of the insulating outer cylinder from the outside atmosphere.
- the battery was placed in a constant temperature bath at 25°C and connected to a charge/discharge device.
- Vo is the voltage before discharging for 5 seconds
- V is the voltage after discharging for 5 seconds
- S is the area where the positive electrode and the solid electrolyte layer are in contact
- I is 6.5 mA.
- the DCR of the battery of Example 1 was 58 ⁇ cm 2 .
- Examples 2 to 8>> [Preparation of positive electrode active material]
- a mixture of an oxide containing nickel, cobalt, and manganese and lithium hydroxide was prepared and fired at 825° C. in an oxygen atmosphere to form a positive electrode active material LiNi 0.8 (Co, Mn). ) 0.2 O 2 was made.
- the positive electrode active material NCM-2 of Example 2 was obtained.
- Example 3 A mixture of an oxide containing nickel, cobalt, and manganese and lithium hydroxide was prepared in the same manner as in Example 1 and fired at 800° C. in an oxygen atmosphere to form a positive electrode active material LiNi 0.8 (Co, Mn). 0.2 O2 was made. Thus, the positive electrode active material NCM-3 of Example 3 was obtained.
- Example 4 A mixture of an oxide containing nickel, cobalt, and manganese and lithium hydroxide was prepared in the same manner as in Example 1 and fired at 775° C. in an oxygen atmosphere to form a positive electrode active material LiNi 0.8 (Co, Mn). 0.2 O2 was made. Thus, the positive electrode active material NCM-4 of Example 4 was obtained.
- Nickel sulfate, cobalt sulfate, and sodium aluminate were dissolved in water, and nickel, cobalt, and aluminum were coprecipitated with an alkaline aqueous solution containing sodium hydroxide to prepare hydroxides of nickel, cobalt, and aluminum.
- the hydroxide was filtered, dried and pyrolyzed to produce an oxide containing the desired proportions of nickel, cobalt and aluminum.
- This oxide and lithium hydroxide were mixed and fired at 850° C. in an oxygen atmosphere to prepare a positive electrode active material LiNi 0.8 (Co, Al) 0.2 O 2 .
- the LiNi 0.8 (Co, Al) 0.2 O 2 thus produced is hereinafter referred to as NCA-1.
- NCA-1 the positive electrode active material of Example 5 was obtained.
- Example 6 A mixture of an oxide containing nickel, cobalt, and aluminum and lithium hydroxide was prepared in the same manner as in Example 5 and fired at 825° C. in an oxygen atmosphere to form a positive electrode active material LiNi 0.8 (Co, Al). 0.2 O2 was made. Thus, the positive electrode active material NCA-2 of Example 6 was obtained.
- Example 7 A mixture of an oxide containing nickel, cobalt, and aluminum and lithium hydroxide was prepared in the same manner as in Example 5 and fired at 800° C. in an oxygen atmosphere to form a positive electrode active material LiNi 0.8 (Co, Al). 0.2 O2 was made. Thus, the positive electrode active material NCA-3 of Example 7 was obtained.
- Example 8 A mixture of an oxide containing nickel, cobalt, and aluminum and lithium hydroxide was prepared in the same manner as in Example 5 and fired at 775° C. in an oxygen atmosphere to form a positive electrode active material LiNi 0.8 (Co, Al). 0.2 O2 was made. Thus, the positive electrode active material NCA-4 of Example 8 was obtained.
- FIG. 3 is a graph showing X-ray diffraction patterns of cathode active materials according to Examples 2-8.
- the full width at half maximum of the produced positive electrode active materials of Examples 2 to 8 was measured in the same manner as in Example 1.
- the full widths at half maximum of the positive electrode active materials of Examples 2 to 8 are shown in Table 1 below.
- Positive electrode materials of Examples 2 to 8 were produced in the same manner as in Example 1, except that the positive electrode active materials of Examples 2 to 8 were used as the positive electrode active materials, respectively.
- Batteries of Examples 2 to 8 were produced in the same manner as in Example 1, except that the positive electrode materials of Examples 2 to 8 were used as positive electrode materials.
- [Measurement of full width at half maximum] 3 is a graph showing an X-ray diffraction pattern of the positive active material according to Comparative Example 1.
- FIG. The full width at half maximum of the produced positive electrode active material of Comparative Example 1 was measured in the same manner as in Example 1.
- the full width at half maximum of the positive electrode active material of Comparative Example 1 is shown in Table 1 below.
- a positive electrode material of Comparative Example 1 was produced in the same manner as in Example 1, except that the positive electrode active material of Comparative Example 1 was used as the positive electrode active material.
- a battery of Comparative Example 1 was produced in the same manner as in Example 1, except that the positive electrode material of Comparative Example 1 was used as the positive electrode material.
- the positive electrode active material of the present disclosure can be used, for example, for the positive electrode of batteries such as all-solid-state batteries.
- Electrode material 100 Solid electrolyte 110 Positive electrode active material 120 Coating material 2000 Battery 201 Positive electrode 202 Electrolyte layer 203 Negative electrode
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Abstract
Description
下記の組成式(1)により表される複合酸化物を含む正極活物質であって、
LiNixMe1-xO2・・・(1)
ここで、
xは、0.5≦x<1を満たし、
Meは、Co、Mn、Al、Mg、Ca、Sr、Ba、B、Ga、Y、Ce、Sm、Gd、Er、Ti、Zr、V、Nb、Ta、Sb、Bi、Cr、Mo、およびWからなる群より選択される少なくとも1つであり、
Cu-Kα線を用いた前記正極活物質のX線回折測定によって得られるX線回折パターンにおいて、40°以上かつ50°以下の回折角2θの範囲内で最も高い強度を有するピークの半値全幅の値の、同一の条件で測定されたSi結晶粉末の(111)面に対応するピークの半値全幅の値に対する比は、2.00以下である、
正極活物質を提供する。
本発明者らは、リチウムイオン電池の抵抗を増大させる要因について鋭意研究を行い、活物質の結晶性が変化すると、リチウムイオン電池の抵抗が変化することを知見した。本発明者らは、当該知見に基づきさらなる検討を進めところ、活物質粒子の結晶子サイズを大きくすることで、リチウムイオン電池の抵抗を低減できることを知見した。このとき、結晶子サイズの大きさは、X線回折測定の回折パターンによるピークの半値全幅の大きさによって判断した。
本開示の第1態様に係る正極活物質は、下記の組成式(1)により表される複合酸化物を主成分として含む正極活物質粒子であって、
LiNixMe1-xO2・・・(1)
ここで、
xは、0.5≦x<1を満たし、
Meは、Co、Mn、Al、Mg、Ca、Sr、Ba、B、Ga、Y、Ce、Sm、Gd、Er、Ti、Zr、V、Nb、Ta、Sb、Bi、Cr、Mo、およびWからなる群より選択される少なくとも1つであり、
Cu-Kα線を用いた前記正極活物質のX線回折測定によって得られるX線回折パターンにおいて、40°以上かつ50°以下の回折角2θの範囲内で最も高い強度を有するピークの半値全幅の値の、同一の条件で測定されたSi結晶粉末の(111)面に対応するピークの半値全幅の値に対する比は、2.00以下である。
第1または第2態様に係る正極活物質と、
前記正極活物質の表面の少なくとも一部を被覆する被覆材料と、
を含み、
前記被覆材料は、
リチウム元素(Li)と、
酸素元素(O)、フッ素元素(F)、および塩素元素(Cl)からなる群より選択される少なくとも1つと、
を含む。
第1または第2態様に係る正極活物質、および、第3態様に係る被覆正極活物質からなる群より選択される少なくとも1つと、
固体電解質と、
を含む。
LiαMβXγ ・・・式(2)
ここで、
α、β、およびγは、それぞれ独立して、0より大きい値であり、
前記Mは、Li以外の金属元素および半金属元素からなる群より選択される少なくとも1つであり、
前記Xは、F、Cl、Br、およびIからなる群より選択される少なくとも1つであってもよい。
前記組成式(2)において、
2.5≦α≦3、
1≦β≦1.1、および
γ=6、
が満たされてもよい。
第4から第9態様のいずれかに1つの態様に係る正極材料を含む正極と、
負極と、
前記正極と前記負極との間に配置された電解質層と、を備える。
実施の形態1に係る正極活物質は、下記の組成式(1)により表される複合酸化物を含む。
LiNixMe1-xO2 ・・・(1)
ここで、上記組成式(1)において、xは、0.5≦x<1を満たす。また、Meは、Co、Mn、Al、Mg、Ca、Sr、Ba、B、Ga、Y、Ce、Sm、Gd、Er、Ti、Zr、V、Nb、Ta、Sb、Bi、Cr、Mo、およびWからなる群より選択される少なくとも1つである。
以下、実施の形態2が説明される。上述の実施の形態1と重複する説明は、適宜、省略される。
以下、実施の形態3が説明される。上述の実施の形態1および2と重複する説明は、適宜、省略される。
LiαMβXγ ・・・式(2)
ここで、α、β、およびγは、0より大きい値である。Mは、Li以外の金属元素および半金属元素からなる群より選択される少なくとも1つである。Xは、F、Cl、Br、およびIからなる群より選択される少なくとも1つである。
以下、実施の形態4が説明される。上述の実施の形態1から3と重複する説明は、適宜、省略される。
[正極活物質の作製]
硫酸ニッケル、硫酸コバルト、および硫酸マンガンを水に溶解させ、水酸化ナトリウムを含むアルカリ水溶液でニッケル、コバルト、およびマンガンを共沈させて、ニッケル、コバルト、およびマンガンの水酸化物を作製した。この水酸化物を濾過、乾燥、熱分解させ、ニッケル、コバルト、およびマンガンを所望の比率で含んだ酸化物を作製した。この酸化物と水酸化リチウムとを混合し、酸素雰囲気のもと850℃で焼成し、正極活物質LiNi0.8(Co、Mn)0.2O2を作製した。以下、作製したLiNi0.8(Co、Mn)0.2O2をNCM-1と表記する。このようにして実施例1の正極活物質を得た。
図3は、実施例1による正極活物質のX線回折パターンを示すグラフである。すなわち、図3は、実施例1によるNCM-1のX線回折パターンを示すグラフである。
露点-60℃以下のアルゴングローブボックス内で、原料粉LiClおよびYCl3をモル比で、LiCl:YCl3=3:1となるように秤量した。これらを乳鉢で粉砕して混合した。その後、遊星型ボールミルを用い、12時間、600rpmでミリング処理した。
露点-60℃以下のアルゴングローブボックス内で、ハロゲン化物固体電解質Li3YCl6、および実施例1の正極活物質であるNCM-1を、Li3YCl6:NCM-1=25:75の質量比率で秤量した。これらをメノウ乳鉢で混合することで、実施例1の正極材料を作製した。
露点-60℃以下のアルゴングローブボックス内で、Li2SおよびP2S5を、モル比でLi2S:P2S5=75:25となるように、秤量した。これらを乳鉢で粉砕して混合した。その後、遊星型ボールミル(フリッチュ製、P-7型)を用い、10時間、510rpmでミリング処理することで、ガラス状の固体電解質を得た。ガラス状の固体電解質について、不活性雰囲気中で、270℃で、2時間熱処理した。これにより、ガラスセラミックス状の硫化物固体電解質を得た。
上述の実施例1の正極材料、および硫化物固体電解質それぞれを用いて、下記の工程を実施した。
実施例1の電池を用いて、以下の条件で、充放電試験が実施された。
[正極活物質の作製]
実施例1と同様の手順で、ニッケル、コバルト、およびマンガンを含む酸化物と水酸化リチウムとの混合物を作製し、酸素雰囲気のもと825℃で焼成し、正極活物質LiNi0.8(Co、Mn)0.2O2を作製した。このようにして実施例2の正極活物質NCM-2を得た。
図3は、実施例2から8による正極活物質のX線回折パターンを示すグラフである。作製した実施例2から8の正極活物質の半値全幅を、実施例1と同様にして測定した。実施例2から8の正極活物質の半値全幅は下記の表1に示す。
正極活物質としてそれぞれ実施例2から8の正極活物質を用いたこと以外は、実施例1と同様にして、実施例2から8の正極材料を作製した。
正極材料としてそれぞれ実施例2から8の正極材料を用いたこと以外は、実施例1と同様にして、実施例2から8の電池を作製した。
実施例2から8の電池を用いて、実施例1と同様にして、充放電試験が実施された。実施例2から8の電池のDCRは下記の表1に示す。
[正極活物質の作製]
実施例1と同様の手順でニッケル、コバルト、およびマンガンを含む酸化物と水酸化リチウムとの混合物を作製し、酸素雰囲気のもと750℃で焼成し、正極活物質LiNi0.8(Co、Mn)0.2O2を作製した。このようにして比較例1の正極活物質NCM-Ref.を得た。
図3は、比較例1による正極活物質のX線回折パターンを示すグラフである。作製した比較例1の正極活物質の半値全幅を、実施例1と同様にして測定した。比較例1の正極活物質の半値全幅は下記の表1に示す。
正極活物質として比較例1の正極活物質を用いたこと以外は、実施例1と同様にして比較例1の正極材料を作製した。
正極材料として比較例1の正極材料を用いたこと以外は、実施例1と同様にして比較例1の電池を作製した。
比較例1の電池を用いて、実施例1と同様にして、充放電試験が実施された。比較例の電池のDCRは下記の表1に示す。
表1に示す結果から、実施例1から8と比較例1とを比較すると、FWHM/FWHMSi≦2.00の条件を満たす実施例1から8の電池は、FWHM/FWHMSiが2.0を超えていた比較例1の電池よりもDCRを低減できることがわかった。さらに、表1に示す結果から、FWHM/FWHMSiが1.90以下の場合に、DCRがより低減されることもわかった。また、同じ組成を有する正極活物質NCMが用いられた実施例1から4の電池を比較すると、半値全幅の値FWHMが小さいほど、DCRが低減できることがわかった。このことは、正極活物質NCAが用いられた実施例5から8の電池でも同様であった。
100 固体電解質
110 正極活物質
120 被覆材料
2000 電池
201 正極
202 電解質層
203 負極
Claims (13)
- 下記の組成式(1)により表される複合酸化物を含む正極活物質であって、
LiNixMe1-xO2・・・(1)
ここで、
xは、0.5≦x<1を満たし、
Meは、Co、Mn、Al、Mg、Ca、Sr、Ba、B、Ga、Y、Ce、Sm、Gd、Er、Ti、Zr、V、Nb、Ta、Sb、Bi、Cr、Mo、およびWからなる群より選択される少なくとも1つであり、
Cu-Kα線を用いた前記正極活物質のX線回折測定によって得られるX線回折パターンにおいて、40°以上かつ50°以下の回折角2θの範囲内で最も高い強度を有するピークの半値全幅の値の、同一の条件で測定されたSi結晶粉末の(111)面に対応するピークの半値全幅の値に対する比は、2.00以下である、
正極活物質。 - 前記ピークの半値全幅の比が、1.90以下である、
請求項1に記載の正極活物質。 - 請求項1または2に記載の正極活物質と、
前記正極活物質の表面の少なくとも一部を被覆する被覆材料と、
を含み、
前記被覆材料は、
リチウム元素(Li)と、
酸素元素(O)、フッ素元素(F)、および塩素元素(Cl)からなる群より選択される少なくとも1つと、
を含む、
被覆正極活物質。 - 請求項1または2に記載の正極活物質、および、請求項3に記載の被覆正極活物質からなる群より選択される少なくとも1つと、
固体電解質と、
を含む、正極材料。 - 前記固体電解質は、硫化物固体電解質およびハロゲン化物固体電解質からなる群より選択される少なくとも1つを含む、
請求項4に記載の正極材料。 - 前記ハロゲン化物固体電解質は、下記の組成式(2)により表され、
LiαMβXγ ・・・式(2)
ここで、
α、β、およびγは、それぞれ独立して、0より大きい値であり、
前記Mは、Li以外の金属元素および半金属元素からなる群より選択される少なくとも1つであり、
前記Xは、F、Cl、Br、およびIからなる群より選択される少なくとも1つであり、
請求項5に記載の正極材料。 - 前記Mは、イットリウムを含む、
請求項6に記載の正極材料。 - 前記組成式(2)において、
2.5≦α≦3、
1≦β≦1.1、および
γ=6、
が満たされる、
請求項6または7に記載の正極材料。 - 前記Xは、ClおよびBrからなる群より選択される少なくとも1つを含む、
請求項6から8のいずれか一項に記載の正極材料。 - 請求項4から9のいずれか一項に記載の正極材料を含む正極と、
負極と、
前記正極と前記負極との間に配置された電解質層と、を備える、
電池。 - 前記電解質層は、前記正極材料に含まれる前記固体電解質と同じ組成を有する固体電解質を含む、
請求項10に記載の電池。 - 前記電解質層は、前記正極材料に含まれる前記固体電解質と異なる組成を有するハロゲン化物固体電解質を含む、
請求項10または11に記載の電池。 - 前記電解質層は、硫化物固体電解質を含む、
請求項10から12のいずれか一項に記載の電池。
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CN202280042949.0A CN117561620A (zh) | 2021-06-24 | 2022-05-19 | 正极活性物质、覆盖型正极活性物质、正极材料和电池 |
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JP2015018803A (ja) * | 2013-07-08 | 2015-01-29 | 三星エスディアイ株式会社Samsung SDI Co.,Ltd. | 正極活物質、その製造方法、それを採用した正極及びリチウム二次電池 |
JP2018206609A (ja) * | 2017-06-05 | 2018-12-27 | 株式会社Gsユアサ | 非水電解質二次電池 |
WO2019135322A1 (ja) * | 2018-01-05 | 2019-07-11 | パナソニックIpマネジメント株式会社 | 正極材料、および、電池 |
JP2019125510A (ja) | 2018-01-17 | 2019-07-25 | トヨタ自動車株式会社 | 全固体電池用正極合剤、全固体電池用正極、全固体電池及びこれらの製造方法 |
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JP2015018803A (ja) * | 2013-07-08 | 2015-01-29 | 三星エスディアイ株式会社Samsung SDI Co.,Ltd. | 正極活物質、その製造方法、それを採用した正極及びリチウム二次電池 |
JP2018206609A (ja) * | 2017-06-05 | 2018-12-27 | 株式会社Gsユアサ | 非水電解質二次電池 |
WO2019135322A1 (ja) * | 2018-01-05 | 2019-07-11 | パナソニックIpマネジメント株式会社 | 正極材料、および、電池 |
JP2019125510A (ja) | 2018-01-17 | 2019-07-25 | トヨタ自動車株式会社 | 全固体電池用正極合剤、全固体電池用正極、全固体電池及びこれらの製造方法 |
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