WO2022138104A1 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
- Publication number
- WO2022138104A1 WO2022138104A1 PCT/JP2021/044687 JP2021044687W WO2022138104A1 WO 2022138104 A1 WO2022138104 A1 WO 2022138104A1 JP 2021044687 W JP2021044687 W JP 2021044687W WO 2022138104 A1 WO2022138104 A1 WO 2022138104A1
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- Prior art keywords
- negative electrode
- composite oxide
- positive electrode
- transition metal
- content
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- 239000000203 mixture Substances 0.000 claims abstract description 46
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 37
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- -1 lithium transition metal Chemical class 0.000 claims description 38
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 62
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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
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
-
- 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 a non-aqueous electrolyte secondary battery, and particularly to a non-aqueous electrolyte secondary battery containing a lithium transition metal composite oxide containing Ni as a positive electrode active material.
- Patent Document 1 comprises a lithium transition metal composite oxide represented by the general formula Li x Ni 1- y -z-v-w Coy Al z M 1 v M 2 w O 2 , and in the formula, A positive electrode active material is disclosed in which the element M 1 is at least one selected from Mn, Ti, Y, Nb, Mo and W, and the element M 2 is at least Mg and Ca. Further, Patent Document 2 discloses a composite oxide containing at least one selected from Mo, W, Nb, Ta, and Re in a lithium transition metal composite oxide containing Ni, Mn, and Co. There is.
- the object of the present disclosure is to suppress a decrease in capacity due to charging and discharging in a non-aqueous electrolyte secondary battery using a lithium transition metal composite oxide having a high Ni content as a positive electrode active material.
- the non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte
- the positive electrode is a lithium transition metal composite oxide containing at least Ni and Mo having a layered structure.
- the content of Ni is 80 mol% to 95 mol% with respect to the total number of moles of the metal element excluding Li
- the content of Mo is the content of the metal element excluding Li.
- the negative electrode has a negative electrode mixture layer containing a negative electrode active material and a coating film containing Mo formed on the surface of the negative electrode mixture layer, and Mo in the negative electrode.
- the content of the above is 0.5 ppm to 120 ppm with respect to the total mass of the lithium transition metal composite oxide in the positive electrode.
- non-aqueous electrolyte secondary battery using a lithium transition metal composite oxide having a high Ni content as a positive electrode active material it is possible to suppress a capacity decrease due to charging and discharging.
- the non-aqueous electrolyte secondary battery according to the present disclosure is excellent in charge / discharge cycle characteristics.
- the lithium transition metal composite oxide having a high Ni content has high activity on the surface of the lithium transition metal composite oxide particles, and the structure of the particle surface is unstable. It is considered that the layered structure starting from the surface is easily deteriorated, and the charge / discharge cycle characteristics of the battery are deteriorated due to this.
- the present inventors generate and erode a structurally deteriorated layer on the surface of the lithium transition metal composite oxide on the positive electrode by reaction with an electrolytic solution or the like. It has been found that the charge / discharge cycle characteristics are improved by forming a high-quality film containing Mo derived from the positive electrode on the surface of the negative electrode while suppressing the above.
- a cylindrical battery in which the wound electrode body 14 is housed in a bottomed cylindrical outer can 16 is illustrated, but the outer body is not limited to the cylindrical outer can, for example, a square outer can. It may be an exterior body made of a laminated sheet including a metal layer and a resin layer. Further, the electrode body may be a laminated electrode body in which a plurality of positive electrodes and a plurality of negative electrodes are alternately laminated via a separator.
- FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery 10 which is an example of an embodiment.
- the non-aqueous electrolyte secondary battery 10 includes a winding type electrode body 14, a non-aqueous electrolyte, and an outer can 16 for accommodating the electrode body 14 and the electrolyte.
- the electrode body 14 has a positive electrode 11, a negative electrode 12, and a separator 13, and has a wound structure in which the positive electrode 11 and the negative electrode 12 are spirally wound via the separator 13.
- the outer can 16 is a bottomed cylindrical metal container having an opening on one side in the axial direction, and the opening of the outer can 16 is closed by a sealing body 17.
- the battery sealing body 17 side is on the top and the bottom side of the outer can 16 is on the bottom.
- the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
- the non-aqueous solvent for example, esters, ethers, nitriles, amides, and a mixed solvent of two or more of these are used.
- the non-aqueous solvent may contain a halogen-substituted product in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
- the electrolyte salt for example, a lithium salt such as LiPF 6 is used.
- the electrolyte is not limited to the liquid electrolyte, and may be a solid electrolyte using a gel-like polymer or the like.
- the positive electrode 11, the negative electrode 12, and the separator 13 constituting the electrode body 14 are all strip-shaped long bodies, and are alternately laminated in the radial direction of the electrode body 14 by being wound in a spiral shape.
- the negative electrode 12 is formed to have a size one size larger than that of the positive electrode 11 in order to prevent the precipitation of lithium. That is, the negative electrode 12 is formed longer than the positive electrode 11 in the longitudinal direction and the width direction (short direction).
- the two separators 13 are formed at least one size larger than the positive electrode 11, and are arranged so as to sandwich the positive electrode 11, for example.
- the electrode body 14 has a positive electrode lead 20 connected to the positive electrode 11 by welding or the like, and a negative electrode lead 21 connected to the negative electrode 12 by welding or the like.
- Insulating plates 18 and 19 are arranged above and below the electrode body 14, respectively.
- the positive electrode lead 20 extends to the sealing body 17 side through the through hole of the insulating plate 18, and the negative electrode lead 21 extends to the bottom side of the outer can 16 through the outside of the insulating plate 19.
- the positive electrode lead 20 is connected to the lower surface of the internal terminal plate 23 of the sealing body 17 by welding or the like, and the cap 27, which is the top plate of the sealing body 17 electrically connected to the internal terminal plate 23, serves as the positive electrode terminal.
- the negative electrode lead 21 is connected to the inner surface of the bottom of the outer can 16 by welding or the like, and the outer can 16 serves as a negative electrode terminal.
- a gasket 28 is provided between the outer can 16 and the sealing body 17 to ensure the airtightness inside the battery.
- the outer can 16 is formed with a grooved portion 22 that supports the sealing body 17, with a part of the side surface portion protruding inward.
- the grooved portion 22 is preferably formed in an annular shape along the circumferential direction of the outer can 16, and the sealing body 17 is supported on the upper surface thereof.
- the sealing body 17 is fixed to the upper part of the outer can 16 by the grooved portion 22 and the opening end portion of the outer can 16 crimped to the sealing body 17.
- the sealing body 17 has a structure in which an internal terminal plate 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are laminated in this order from the electrode body 14 side.
- Each member constituting the sealing body 17 has, for example, a disk shape or a ring shape, and each member except the insulating member 25 is electrically connected to each other.
- the lower valve body 24 and the upper valve body 26 are connected at the central portion of each, and an insulating member 25 is interposed between the peripheral portions of each.
- the positive electrode 11, the negative electrode 12, and the separator 13 constituting the electrode body 14 will be described in detail, and in particular, the positive electrode active material constituting the positive electrode 11 will be described in detail.
- the positive electrode 11 has a positive electrode core and a positive electrode mixture layer provided on the surface of the positive electrode core.
- a metal foil stable in the potential range of the positive electrode 11 such as aluminum, a film in which the metal is arranged on the surface layer, or the like can be used.
- the positive electrode mixture layer contains a positive electrode active material, a binder, and a conductive material, and is preferably provided on both sides of the positive electrode core body excluding the portion to which the positive electrode lead 20 is connected.
- a positive electrode mixture slurry containing a positive electrode active material, a binder, a conductive material, and the like is applied to the surface of a positive electrode core, the coating film is dried, and then compressed to form a positive electrode mixture layer. It can be manufactured by forming it on both sides of the core body.
- Examples of the conductive material contained in the positive electrode mixture layer include carbon materials such as carbon black, acetylene black, ketjen black, carbon nanotubes (CNT), graphene, and graphite.
- Examples of the binder contained in the positive electrode mixture layer include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimides, acrylic resins, and polyolefins. These resins may be used in combination with cellulose derivatives such as carboxymethyl cellulose (CMC) or salts thereof, polyethylene oxide (PEO) and the like.
- the positive electrode 11 contains a lithium transition metal composite oxide having a layered structure and containing at least Ni and Mo.
- the lithium transition metal composite oxide will be referred to as “composite oxide (Z)”.
- the composite oxide (Z) functions as a positive electrode active material.
- the positive electrode active material may contain the composite oxide (Z) as a main component and may be substantially composed of only the composite oxide (Z).
- the positive electrode active material may contain a composite oxide other than the composite oxide (Z) or other compounds as long as the object of the present disclosure is not impaired.
- Examples of the layered structure of the composite oxide (Z) include a layered structure belonging to the space group R-3m, a layered structure belonging to the space group C2 / m, and the like. Among these, a layered structure belonging to the space group R-3m is preferable in terms of high capacity, stability of crystal structure, and the like.
- the composite oxide (Z) is, for example, a secondary particle formed by aggregating a plurality of primary particles.
- the particle size of the primary particles is generally 0.05 ⁇ m to 1 ⁇ m.
- the volume-based median diameter (D50) of the composite oxide (Z) is, for example, 3 ⁇ m to 30 ⁇ m, preferably 5 ⁇ m to 25 ⁇ m.
- D50 means a particle size in which the cumulative frequency is 50% from the smaller size in the volume-based particle size distribution, and is also called a medium diameter.
- the particle size distribution of the composite oxide (Z) can be measured using a laser diffraction type particle size distribution measuring device (for example, MT3000II manufactured by Microtrac Bell Co., Ltd.) and water as a dispersion medium.
- the composite oxide (Z) contains 80 mol% to 95 mol% Ni with respect to the total number of moles of metal elements excluding Li. By setting the Ni content to 80 mol% or more, a battery having a high energy density can be obtained. On the other hand, when the Ni content exceeds 95 mol%, the content of Mo and other metal elements becomes too small, and the stability of the layered structure of the composite oxide (Z) cannot be ensured, so that the composite oxide (Z) cannot be secured. The formation and erosion of structurally deteriorated layers on the surface of the surface cannot be suppressed.
- the Ni content may be 85 mol% or more, or 90 mol% or more. When the Ni content is 80 mol% or more, the structure of the composite oxide becomes unstable, and a side reaction with the electrolyte is likely to occur on the particle surface of the composite oxide.
- the content of Mo in the composite oxide (Z) is less than 3 mol%, preferably 2 mol% or less, and more preferably 1 mol% or less with respect to the total number of moles of the metal element excluding Li. ..
- the lower limit of the Mo content in the composite oxide (Z) is not particularly limited, but is, for example, 0.05 mol%.
- the Mo content is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and particularly preferably 1 mol% or more. In this case, the effect of improving the charge / discharge cycle characteristics becomes more remarkable.
- Mo contained in the composite oxide (Z) suppresses the formation and erosion of a structurally deteriorated layer on the surface of the composite oxide (Z) due to a reaction with an electrolytic solution or the like at the positive electrode. It is considered that a high number of Mo retains oxygen contained in the layered structure of the composite oxide (Z) during charging and discharging, and suppresses oxygen release. Further, Mo contained in the composite oxide (Z) is a Mo source of a film formed on the surface of the negative electrode, and a part of the Mo is eluted by charging and discharging and deposited on the surface of the negative electrode, and is contained in the film of the negative electrode. Will be done.
- Mo may be dissolved in a solid solution and may be present in a layered structure, or may be present on the surface of primary particles or secondary particles.
- Mo may be combined with other elements such as Li to form a compound.
- the amount of solid dissolved Mo can be measured by an inductively coupled plasma emission spectrophotometer (ICP-AES), an electron probe microanalyzer (EPMA), an energy dispersive X-ray analyzer (EDX), or the like.
- the composite oxide (Z) may contain a metal element other than Li, Ni, and Mo.
- the metal element include Mn, Co, Al, Zr, B, Mg, Fe, Cu, Zn, Sn, Na, K, Ca, Sr, Ba, Nb, W, Mo, Si and the like.
- the composite oxide (Z) preferably contains at least one of Al and Mn. Since neither Al nor Mn causes a change in the oxidation number during charging and discharging, it is considered that the layered structure of the transition metal layer is stabilized.
- the Al content is preferably 1 to 10 mol% with respect to the total number of moles of the metal element excluding Li
- the Mn content is preferably 3 to 20 mol% with respect to the total number of moles of the metal element excluding Li.
- the composite oxide (Z) may further contain at least one of W and Zr.
- the state of existence of W or Zr in the composite oxide (Z) is not particularly limited, and may be present on, for example, the surface of the primary particles and the surface of the secondary particles of the composite oxide (Z), or the composite oxide (Z). It may be solidly dissolved in Z).
- the content of the elements constituting the composite oxide (Z) is measured by an inductively coupled plasma emission spectrophotometer (ICP-AES), an electron probe microanalyzer (EPMA), an energy dispersive X-ray analyzer (EDX), or the like. can do.
- ICP-AES inductively coupled plasma emission spectrophotometer
- EPMA electron probe microanalyzer
- EDX energy dispersive X-ray analyzer
- the crystallite size s of the composite oxide (Z) calculated by Scherrer's equation from the half width of the diffraction peak on the (104) plane of the X-ray diffraction pattern by X-ray diffraction can be used to increase the capacity of the battery and to increase the capacity of the battery. From the viewpoint of improving output characteristics, it is preferably in the range of 250 ⁇ to 800 ⁇ .
- Scherrer's equation is expressed by the following equation.
- s is the crystallite size
- ⁇ is the wavelength of the X-ray
- B is the half width of the diffraction peak on the (104) plane
- ⁇ is the diffraction angle (rad)
- K is the Scherrer constant.
- K is 0.9.
- s K ⁇ / Bcos ⁇
- the BET specific surface area of the composite oxide (Z) is preferably in the range of 1 m 2 / g to 5 m 2 / g.
- the energy density of the positive electrode can be improved.
- the BET specific surface area can be measured by, for example, a commercially available measuring device such as HM model-1201 manufactured by Macsorb.
- the composite oxide (Z) can be synthesized, for example, by mixing and firing a transition metal oxide containing Ni, Co, Mn, Al and the like, a Mo raw material, and a Li raw material such as lithium hydroxide (LiOH). ..
- a transition metal oxide containing Ni, Co, Mn, Al and the like a Mo raw material
- a Li raw material such as lithium hydroxide (LiOH).
- the composite oxide (Z) contains Zr, Ti, Nb, Ca and the like, Zr raw materials such as ZrO 2 , Ti raw materials such as TiO 2 and Nb such as Nb 2 O 5 and nH 2 O, respectively.
- the raw material, a Ca raw material such as Ca (OH) 2 , and the like may be mixed and fired together with the transition metal oxide, the Mo raw material, and the Li raw material.
- Transition metal oxides containing Ni, Co, Mn, Al, etc., Mo raw materials, Zr raw materials, Ti raw materials, Nb raw materials, Ca raw materials, etc. are mixed and fired, and composite oxides containing Ni, Mo, etc.
- the composite oxide (Z) may be synthesized by adding a Li raw material and firing again.
- the firing is performed by the first firing step of firing in a firing furnace at a first heating rate to a first set temperature of 450 ° C. or higher and 680 ° C. or lower under an oxygen stream, and the fired product obtained by the first firing step.
- a multi-step firing step including a second firing step of firing at a second heating rate to a second set temperature of more than 680 ° C and 800 ° C or less in a firing furnace under an oxygen stream is provided.
- the first temperature rise rate is in the range of 1.5 ° C./min or more and 5.5 ° C./min or less
- the second temperature rise rate is slower than the first temperature rise rate. , 0.1 ° C / min or more and 3.5 ° C / min or less.
- the lithium transition metal composite oxide calculated by Scherrer's equation from the half width of the diffraction peak of the (104) plane.
- Each parameter such as crystallite size, BET specific surface area, and Mo supply amount to the negative electrode can be adjusted within the above-mentioned predetermined range.
- the first set temperature in the first firing step may be in the range of 450 ° C. or higher and 680 ° C. or lower in that the above parameters of the lithium transition metal oxide are adjusted to the above-mentioned predetermined range, but is preferably 550 ° C. or higher.
- the temperature is in the range of 680 ° C or lower.
- the first temperature rising rate in the first firing step is in the range of 1.5 ° C./min or more and 5.5 ° C./min or less in that each of the above parameters of the lithium transition metal oxide is adjusted to the above-mentioned predetermined range. However, it is preferably in the range of 2.0 ° C./min or more and 5.0 ° C. min or less.
- a plurality of first temperature rising rates may be set for each temperature region as long as they are within the above range.
- the firing start temperature (initial temperature) of the first firing step is, for example, in the range of room temperature to 200 ° C. or lower.
- the holding time of the first set temperature in the first firing step is preferably 0 hours or more and 5 hours or less, and 0 hours or more and 3 hours or less in terms of adjusting each of the above parameters of the lithium transition metal oxide to the above-mentioned predetermined range. More preferred.
- the holding time of the first set temperature is the time for maintaining the first set temperature after reaching the first set temperature.
- the second set temperature in the second firing step may be in the range of more than 680 ° C. and 800 ° C. or lower, preferably 680 ° C. or higher, in that the above parameters of the lithium transition metal oxide are adjusted to the above-mentioned predetermined range.
- the temperature is in the range of 750 ° C. or lower.
- the second heating rate in the second firing step is slower than the first heating rate in that each of the above parameters of the lithium transition metal oxide is adjusted to the above-mentioned predetermined range, and is 0.1 ° C./min or more 3.5.
- the range may be in the range of ° C./min or less, but preferably in the range of 0.2 ° C./min or more and 2.5 ° C./min or less.
- a plurality of second temperature rise rates may be set for each temperature range as long as they are within the above range. For example, when the first set temperature is less than 680 ° C, the second temperature rise rate is set to the temperature rise rate A from the first set temperature to 680 ° C and the temperature rise rate B from 680 ° C to the second set temperature. It may be divided into.
- the temperature rising rate B is preferably slower than the temperature rising rate A.
- the holding time of the second set temperature in the second firing step is preferably 1 hour or more and 10 hours or less, preferably 1 hour or more and 5 hours or less, in terms of adjusting each of the above parameters of the lithium transition metal oxide to the above-mentioned predetermined range. More preferred.
- the holding time of the second set temperature is the time for maintaining the second set temperature after reaching the second set temperature.
- the oxygen concentration in the oxygen stream is set to 60% or more, and the flow rate of the oxygen stream is set to adjust the parameters of the lithium transition metal oxide to the predetermined range. It is preferably in the range of 0.2 mL / min to 4 mL / min per 10 cm3 of the firing furnace and 0.3 L / min or more per 1 kg of the mixture. Further, the maximum pressure applied to the inside of the firing furnace is preferably in the range of 0.1 kPa or more and 1.0 kPa or less in addition to the pressure outside the firing furnace.
- the composite oxide (Z) may contain W or B by washing the composite oxide (Z) obtained in the above step with water, mixing the W raw material or the B raw material, and heat-treating the composite oxide (Z). Further, W or B may be contained in the composite oxide (Z) by mixing the W raw material or the B raw material with the composite oxide (Z) obtained in the above step and then heat-treating the composite oxide (Z). The heat treatment is performed at a temperature of 150 ° C. to 600 ° C., for example, in a vacuum, an oxygen stream, or the atmosphere.
- the W raw material include tungsten oxide (WO 3 ), lithium tungstate (Li 2 WO 4 , Li 4 WO 5 , Li 6 W 2 O 9 ) and the like.
- the B raw material include boric acid (H 3 BO 3 ), lithium borate (Li 2 B 4 O 7 , Li 3 BO 3 , Li B 3 O 5 , Li BO 2 ) and the like.
- the negative electrode 12 has a negative electrode core and a negative electrode mixture layer provided on the surface of the negative electrode core.
- a metal foil stable in the potential range of the negative electrode 12 such as copper, a film on which the metal is arranged on the surface layer, or the like can be used.
- the negative electrode mixture layer contains a negative electrode active material and a binder, and is preferably provided on both sides of the negative electrode core body excluding the portion to which the negative electrode lead 21 is connected, for example.
- a negative electrode mixture slurry containing a negative electrode active material, a binder, and the like is applied to the surface of the negative electrode core, the coating film is dried, and then compressed to form a negative electrode mixture layer of the negative electrode core. It can be manufactured by forming it on both sides.
- the negative electrode mixture layer contains, for example, a carbon-based active material that reversibly stores and releases lithium ions as a negative electrode active material.
- Suitable carbon-based active materials are natural graphite such as scaly graphite, massive graphite and earthy graphite, and graphite such as artificial graphite such as massive artificial graphite (MAG) and graphitized mesophase carbon microbeads (MCMB).
- a Si-based active material composed of at least one of Si and a Si-containing compound may be used, or a carbon-based active material and a Si-based active material may be used in combination.
- the binder contained in the negative electrode mixture layer fluororesin, PAN, polyimide, acrylic resin, polyolefin or the like can be used as in the case of the positive electrode 11, but styrene-butadiene rubber (SBR) should be used. Is preferable.
- the negative electrode mixture layer preferably further contains CMC or a salt thereof, polyacrylic acid (PAA) or a salt thereof, polyvinyl alcohol (PVA) and the like. Above all, it is preferable to use SBR in combination with CMC or a salt thereof, PAA or a salt thereof.
- the negative electrode 12 has a coating containing Mo formed on the surface of the negative electrode mixture layer (hereinafter, may be referred to as “negative electrode coating”). It is considered that the negative electrode coating is formed by depositing Mo in the composite oxide (Z) eluted by charging and discharging on the surface of the negative electrode mixture layer. That is, the negative electrode coating contains Mo derived from the composite oxide (Z). The negative electrode coating is formed by, for example, charging / discharging for 10 cycles or less. By using the composite oxide (Z) containing a predetermined amount of Mo and forming a high-quality film containing Mo derived from the positive electrode on the surface of the negative electrode, the capacity decrease due to charging and discharging is suppressed, and good cycle characteristics are obtained. Is obtained. The presence of the negative electrode coating can be confirmed, for example, by X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- the content of Mo in the negative electrode is 0.5 ppm to 120 ppm with respect to the total mass of the lithium transition metal composite oxide in the positive electrode.
- the Mo content in the negative electrode can be controlled by the composition of the composite oxide (Z), particularly the firing conditions of the lithium transition metal composite oxide, the Mo content, the charge / discharge conditions, and the like. For example, when the charge termination voltage is increased and the discharge depth is increased, the Mo content in the negative electrode tends to increase.
- the Mo content in the negative electrode mixture layer and the coating can be calculated by the following method. Further, the Ni content in the negative electrode, which will be described later, can be calculated by the same method.
- Ion-exchanged water is added to the negative electrode 12 to separate the negative electrode mixture layer and the coating film from the negative electrode core.
- Aqua regia and hydrofluoric acid are added to the desorbed negative electrode mixture layer and coating to dissolve them by heating, and insoluble components such as carbon are filtered off to prepare an aqueous solution. The volume of the aqueous solution is adjusted with ion-exchanged water, and the result of measuring the Mo concentration by ICP-AES is taken as the Mo content in the negative electrode.
- the Mo content in the negative electrode measured in (2) was divided by the weight of the lithium transition metal composite oxide in the positive electrode to obtain the Mo content in the negative electrode.
- the negative electrode coating may further contain Ni. It is considered that Ni in the composite oxide (Z) eluted by charging and discharging is deposited on the surface of the negative electrode mixture layer together with Nb and M to form a negative electrode film. That is, the negative electrode coating contains Ni derived from the composite oxide (Z).
- the mass ratio (Mo / Ni) of the Mo content to the Ni content is preferably 0.5 to 20, and more preferably 2 to 18.
- Mo / Ni ratio is 0.5 to 20, the effect of improving the cycle characteristics can be enhanced. Further, when the Mo / Ni ratio is 2 to 18, the effect of improving the cycle characteristics can be further enhanced.
- Mo / Ni can be controlled by the composition of the composite oxide (Z), the firing conditions of the lithium transition metal composite oxide, the charging / discharging conditions, and the like.
- the negative electrode coating may contain a metal element other than Mo and Ni.
- the negative electrode coating when the composite oxide (Z) contains at least one of Al and Mn, the negative electrode coating further contains at least one of Al and Mn. Further, for example, when the composite oxide (Z) contains W, the negative electrode coating further contains W.
- the negative electrode coating may contain an organic substance which is a decomposition product of an electrolyte, in addition to a metal element such as Mo and Ni.
- a porous sheet having ion permeability and insulating property is used as the separator 13.
- the porous sheet include a microporous thin film, a woven fabric, and a non-woven fabric.
- polyolefins such as polyethylene and polypropylene, cellulose and the like are suitable.
- the separator 13 may have either a single-layer structure or a laminated structure. A heat-resistant layer or the like may be formed on the surface of the separator.
- Example 1 [Synthesis of Lithium Transition Metal Composite Oxide (Positive Electrode Active Material)]
- the composite oxide represented by the general formula Ni 0.85 Mn 0.15 O 2 , Li 2 MoO 4 , and lithium hydroxide monohydrate (LiOH ⁇ H 2 O) are mixed with Ni, Mn, and The total amount of Mo and the molar ratio of Li were mixed so as to be 1: 1.08.
- the mixture was put into a firing furnace, and under an oxygen stream with an oxygen concentration of 95% (flow rate of 2 mL / min per 10 cm 3 and 5 L / min per 1 kg of the mixture), the heating rate was 2.0 ° C./min, and the temperature was 650 ° C. from room temperature. Baked up to.
- the above lithium transition metal composite oxide was used as the positive electrode active material.
- the positive electrode active material, acetylene black, and polyvinylidene fluoride (PVdF) are mixed at a solid content mass ratio of 95: 3: 2, an appropriate amount of N-methyl-2-pyrrolidone (NMP) is added, and then the mixture is kneaded.
- NMP N-methyl-2-pyrrolidone
- the positive electrode mixture slurry is applied to both sides of a positive electrode core made of aluminum foil, the coating film is dried, and then the coating film is rolled using a roller and cut to a predetermined electrode size to form the positive electrode core.
- a positive electrode having a positive electrode mixture layer formed on both sides was obtained. An exposed portion where the surface of the positive electrode core was exposed was provided on a part of the positive electrode.
- Natural graphite was used as the negative electrode active material.
- the negative electrode active material sodium carboxymethyl cellulose (CMC-Na), and styrene-butadiene rubber (SBR) were mixed in an aqueous solution at a solid content mass ratio of 100: 1: 1 to prepare a negative electrode mixture slurry.
- the negative electrode mixture slurry is applied to both sides of the negative electrode core made of copper foil, the coating film is dried, and then the coating film is rolled using a roller and cut to a predetermined electrode size to obtain the negative electrode core body.
- a negative electrode having a negative electrode mixture layer formed on both sides was obtained.
- An exposed portion where the surface of the negative electrode core was exposed was provided in a part of the negative electrode.
- Lithium hexafluorophosphate LiPF 6
- EC ethylene carbonate
- MEC methyl ethyl carbonate
- DMC dimethyl carbonate
- a non-aqueous electrolyte solution was prepared by dissolving at a concentration of 1.2 mol / liter.
- test cell non-aqueous electrolyte secondary battery
- An aluminum lead is attached to the exposed portion of the positive electrode
- a nickel lead is attached to the exposed portion of the negative electrode.
- the positive electrode and the negative electrode are spirally wound via a polyolefin separator, and then press-molded in the radial direction to form a flat shape.
- a wound electrode body was produced. This electrode body was housed in an exterior body made of an aluminum laminated sheet, and after injecting the non-aqueous electrolytic solution, the opening of the exterior body was sealed to obtain a test cell.
- Example 2 In the synthesis of the positive electrode active material, Ni 0.85 Mn 0.15 O 2 and Li 2 Mo O 4 are used so that the total amount of Ni, Mn, and Mo and the molar ratio of Li are 1: 1.01.
- a test cell was prepared in the same manner as in Example 1 except that LiOH and H2O were mixed and the firing temperature was set to 750 ° C., and the performance was evaluated.
- Example 3 In the synthesis of the positive electrode active material, Ni 0.85 Mn 0.15 O 2 and Li 2 Mo O 4 are used so that the total amount of Ni, Mn, and Mo and the molar ratio of Li are 1: 1.05. A test cell was prepared in the same manner as in Example 1 except that LiOH and H2O were mixed, and the performance was evaluated.
- Example 4 In the synthesis of the positive electrode active material, the composite oxide represented by the general formula Ni 0.91 Co 0.04 Al 0.05 O 2 , Li 2 MoO 4 and LiOH ⁇ H 2 O are Ni, Co, Al.
- a test cell was prepared in the same manner as in Example 1 except that the total amount of Mo and Mo was mixed so that the molar ratio of Li was 1: 1.05 and the firing temperature was 720 ° C., and the performance was evaluated. gone.
- Example 5 In the synthesis of the positive electrode active material, the composite oxide represented by the general formula Ni 0.94 Co 0.06 O 2 , Li 2 MoO 4 , Ti (OH) 4 , and LiOH / H 2 O are Ni, A test cell was prepared in the same manner as in Example 1 except that the total amount of Co, Mo and Ti was mixed so that the molar ratio of Li was 1: 1.05 and the firing temperature was 720 ° C. Performance evaluation was performed.
- the composite oxide represented by the general formula Ni 0.955 Al 0.045 O 2 , Li 2 MoO 4 , Nb 2 O 5 , and LiOH / H 2 O are Ni, Co. , Mo and Nb were mixed so that the molar ratio of Li was 1: 1.03, and the mixture was fired at a heating rate of 2.0 ° C./min from room temperature to 600 ° C. Then, a test cell was prepared in the same manner as in Example 1 except that the cells were fired at a heating rate of 0.5 ° C./min from 600 ° C. to 700 ° C., and the performance was evaluated.
- Example 7 In the synthesis of the positive electrode active material, the composite oxide represented by the general formula Ni 0.955 Al 0.045 O 2 , Li 2 MoO 4 , Ca (OH) 2 , and LiOH / H 2 O are Ni, The total amount of Co, Mo and Ca was mixed so that the molar ratio of Li was 1: 1.03, and the mixture was fired from room temperature to 600 ° C. at a heating rate of 2.0 ° C./min. Then, a test cell was prepared in the same manner as in Example 1 except that firing was performed from 600 ° C. to 700 ° C. at a heating rate of 0.5 ° C./min, and the performance was evaluated.
- the composite oxide represented by the general formula Ni 0.85 Mn 0.15 O 2 , Li 2 MoO 4 and LiOH ⁇ H 2 O are used as the total amount of Ni, Mn, and Mo.
- Li was mixed so as to have a molar ratio of 1: 1.12, and fired at a heating rate of 6.0 ° C./min from room temperature to 600 ° C.
- a test cell was prepared in the same manner as in Example 1 except that the cells were fired at a heating rate of 3 ° C./min from 600 ° C. to 730 ° C.
- the composite oxide represented by the general formula Ni 0.89 Co 0.06 Al 0.05 O 2 , Li 2 MoO 4 and LiOH ⁇ H 2 O are Ni, Co, Al.
- the total amount of Mo and the molar ratio of Li were mixed so as to be 1: 1.05, and the mixture was fired from room temperature to 600 ° C. at a heating rate of 2.0 ° C./min.
- a test cell was prepared in the same manner as in Example 1 except that firing was performed from 600 ° C. to 800 ° C. at a heating rate of 3 ° C./min, and the performance was evaluated.
- Example 5 In the synthesis of the positive electrode active material, the composite oxide represented by the general formula Ni 0.94 Co 0.01 Al 0.05 O 2 and LiOH ⁇ H 2 O are used as the total amount of Ni, Co, and Al, and Li.
- a test cell was prepared in the same manner as in Example 1 except that the mixture was mixed so that the molar ratio of the above was 1: 1.02.
- Table 1 shows the capacity retention rates of Examples and Comparative Examples. Table 1 also shows the composition and characteristics of the positive electrode active material, as well as the Mo content and Mo / Ni ratio in the negative electrode. The Mo content and Mo / Ni ratio in the negative electrode were determined by measuring the negative electrode taken out by disassembling the test cell after the cycle test. Further, it was confirmed by XPS that the negative electrode coating was formed on the surface of the negative electrode mixture layer in any of the negative electrodes of Examples 1 to 7.
- test cells of the examples have a higher capacity retention rate after the cycle test and are excellent in charge / discharge cycle characteristics as compared with the test cells of the comparative example.
- a positive electrode active material containing Mo in a proportion of less than 3 mol% was used, and a film containing Mo derived from the positive electrode active material in a proportion of 0.5 ppm to 120 ppm was formed on the surface of the negative electrode.
- Mo is not contained in the positive electrode active material, and the coating film containing Mo is not present on the surface of the negative electrode.
- the test cell of Comparative Example 4 Mo is contained in the positive electrode active material, but a film containing Mo is not sufficiently formed on the surface of the negative electrode. Further, it is considered that the test cell of Comparative Example 3 had an unstable structure due to the inhibition of the formation of the layered structure of the positive electrode active material because the Mo content in the positive electrode active material was too high. Further, it is considered that the test cell of Comparative Example 1 had an excessively high Mo content in the negative electrode, so that a film was formed too much and the resistance increased. Therefore, the charge / discharge cycle characteristics of the battery are greatly improved by the positive electrode active material containing a predetermined amount of Mo and the negative electrode coating containing a predetermined amount of Mo derived from the positive electrode active material.
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Abstract
Description
正極11は、正極芯体と、正極芯体の表面に設けられた正極合材層とを有する。正極芯体には、アルミニウムなどの正極11の電位範囲で安定な金属の箔、当該金属を表層に配置したフィルム等を用いることができる。正極合材層は、正極活物質、結着材、及び導電材を含み、正極リード20が接続される部分を除く正極芯体の両面に設けられることが好ましい。正極11は、例えば正極芯体の表面に正極活物質、結着材、及び導電材等を含む正極合材スラリーを塗布し、塗膜を乾燥させた後、圧縮して正極合材層を正極芯体の両面に形成することにより作製できる。
測定範囲:15-120°
スキャン速度:4°/min
解析範囲:30-120°
バックグラウンド:B-スプライン
プロファイル関数:分割型擬Voigt関数
束縛条件:Li(3a)+Ni(3a)=1
Ni(3a)+Ni(3b)=α(αは各々のNi含有割合)
ICSD No.:98-009-4814
s=Kλ/Bcosθ
負極12は、負極芯体と、負極芯体の表面に設けられた負極合材層とを有する。負極芯体には、銅などの負極12の電位範囲で安定な金属の箔、当該金属を表層に配置したフィルム等を用いることができる。負極合材層は、負極活物質及び結着材を含み、例えば負極リード21が接続される部分を除く負極芯体の両面に設けられることが好ましい。負極12は、例えば負極芯体の表面に負極活物質、及び結着材等を含む負極合材スラリーを塗布し、塗膜を乾燥させた後、圧縮して負極合材層を負極芯体の両面に形成することにより作製できる。
(1)負極12にイオン交換水を加えて、負極芯体から負極合材層及び被膜を離脱させる。
(2)脱離させた負極合材層及び被膜に王水及びフッ酸を加えて加熱溶解し、炭素等の不溶分を濾別して、水溶液を作製する。当該水溶液をイオン交換水で定容し、ICP-AESでMo濃度を測定した結果を、負極中のMoの含有量とする。
(3)(2)で測定した負極中のMoの含有量を、正極中のリチウム遷移金属複合酸化物の重さで除して、負極中のMo含有率とした。
セパレータ13には、イオン透過性及び絶縁性を有する多孔性シートが用いられる。多孔性シートの具体例としては、微多孔薄膜、織布、不織布等が挙げられる。セパレータ13の材質としては、ポリエチレン、ポリプロピレン等のポリオレフィン、セルロースなどが好適である。セパレータ13は、単層構造、積層構造のいずれであってもよい。セパレータの表面には、耐熱層などが形成されていてもよい。
[リチウム遷移金属複合酸化物(正極活物質)の合成]
一般式Ni0.85Mn0.15O2で表される複合酸化物と、Li2MoO4と、水酸化リチウム・一水和物(LiOH・H2O)とを、Ni、Mn、及びMoの総量と、Liのモル比が1:1.08となるように混合した。当該混合物を焼成炉に投入し、酸素濃度95%の酸素気流下(10cm3あたり2mL/min及び混合物1kgあたり5L/minの流量)、昇温速度2.0℃/minで、室温から650℃まで焼成した。その後、昇温速度1℃/minで、650℃から780℃まで焼成し、当該焼成物を水洗して、リチウム遷移金属複合酸化物を得た。ICP-AESにより、リチウム遷移金属複合酸化物の組成を分析した結果、Li0.97Ni0.84Mo0.01Mn0.15O2であった。
正極活物質として上記リチウム遷移金属複合酸化物を用いた。正極活物質と、アセチレンブラックと、ポリフッ化ビニリデン(PVdF)を、95:3:2の固形分質量比で混合し、N-メチル-2-ピロリドン(NMP)を適量加えた後、これを混練して正極合材スラリーを調製した。当該正極合材スラリーをアルミニウム箔からなる正極芯体の両面に塗布し、塗膜を乾燥させた後、ローラーを用いて塗膜を圧延し、所定の電極サイズに切断して、正極芯体の両面に正極合材層が形成された正極を得た。なお、正極の一部に正極芯体の表面が露出した露出部を設けた。
負極活物質として天然黒鉛を用いた。負極活物質と、カルボキシメチルセルロースナトリウム(CMC-Na)と、スチレン-ブタジエンゴム(SBR)を、100:1:1の固形分質量比で水溶液中において混合し、負極合材スラリーを調製した。当該負極合材スラリーを銅箔からなる負極芯体の両面に塗布し、塗膜を乾燥させた後、ローラーを用いて塗膜を圧延し、所定の電極サイズに切断して、負極芯体の両面に負極合材層が形成された負極を得た。なお、負極の一部に負極芯体の表面が露出した露出部を設けた。
エチレンカーボネート(EC)と、メチルエチルカーボネート(MEC)と、ジメチルカーボネート(DMC)を、3:3:4の体積比で混合した混合溶媒に対して、六フッ化リン酸リチウム(LiPF6)を1.2モル/リットルの濃度で溶解させて非水電解液を調製した。
上記正極の露出部にアルミニウムリードを、上記負極の露出部にニッケルリードをそれぞれ取り付け、ポリオレフィン製のセパレータを介して正極と負極を渦巻き状に巻回した後、径方向にプレス成形して扁平状の巻回型電極体を作製した。この電極体をアルミラミネートシートで構成される外装体内に収容し、上記非水電解液を注入した後、外装体の開口を封止して試験セルを得た。
上記試験セルを、25℃の温度環境下、0.5Itの定電流で電池電圧が4.2Vになるまで定電流充電を行い、4.2Vで電流値が1/50Itになるまで定電圧充電を行った。その後、0.5Itの定電流で電池電圧が2.85Vになるまで定電流放電を行った。この充放電サイクルを100サイクル繰り返した。サイクル試験の1サイクル目の放電容量と、100サイクル目の放電容量を求め、下記式により容量維持率を算出した。
容量維持率(%)=(100サイクル目放電容量÷1サイクル目放電容量)×100
正極活物質の合成において、Ni、Mn、及びMoの総量と、Liのモル比が1:1.01となるように、Ni0.85Mn0.15O2と、Li2MoO4と、LiOH・H2Oとを混合し、焼成温度を750℃としたこと以外は、実施例1と同様にして試験セルを作製し、性能評価を行った。
正極活物質の合成において、Ni、Mn、及びMoの総量と、Liのモル比が1:1.05となるように、Ni0.85Mn0.15O2と、Li2MoO4と、LiOH・H2Oとを混合したこと以外は、実施例1と同様にして試験セルを作製し、性能評価を行った。
正極活物質の合成において、一般式Ni0.91Co0.04Al0.05O2で表される複合酸化物と、Li2MoO4と、LiOH・H2OとをNi、Co、Al及びMoの総量と、Liのモル比が1:1.05となるように混合し、焼成温度を720℃としたこと以外は、実施例1と同様にして試験セルを作製し、性能評価を行った。
正極活物質の合成において、一般式Ni0.94Co0.06O2で表される複合酸化物と、Li2MoO4と、Ti(OH)4と、LiOH・H2OとをNi、Co、Mo及びTiの総量と、Liのモル比が1:1.05となるように混合し、焼成温度を720℃としたこと以外は、実施例1と同様にして試験セルを作製し、性能評価を行った。
正極活物質の合成において、一般式Ni0.955Al0.045O2で表される複合酸化物と、Li2MoO4と、Nb2O5と、LiOH・H2OとをNi、Co、Mo及びNbの総量と、Liのモル比が1:1.03となるように混合し、昇温速度2.0℃/minで、室温から600℃まで焼成した。その後、昇温速度0.5℃/minで、600℃から700℃まで焼成したこと以外は、実施例1と同様にして試験セルを作製し、性能評価を行った。
正極活物質の合成において、一般式Ni0.955Al0.045O2で表される複合酸化物と、Li2MoO4と、Ca(OH)2と、LiOH・H2OとをNi、Co、Mo及びCaの総量と、Liのモル比が1:1.03となるように混合し、昇温速度2.0℃/minで、室温から600℃まで焼成した。その後、昇温速度0.5℃/minで、600℃から700℃まで焼成しを用いたこと以外は、実施例1と同様にして試験セルを作製し、性能評価を行った。
正極活物質の合成において、一般式Ni0.85Mn0.15O2で表される複合酸化物と、Li2MoO4と、LiOH・H2OとをNi、Mn、及びMoの総量と、Liのモル比が1:1.12となるように混合し、昇温速度6.0℃/minで、室温から600℃まで焼成した。その後、昇温速度3℃/minで、600℃から730℃まで焼成したこと以外は、実施例1と同様にして試験セルを作製した。
正極活物質の合成において、一般式Ni0.85Mn0.15O2で表される複合酸化物と、LiOH・H2OとをNi、及びMnの総量と、Liのモル比が1:1.08となるように混合したこと以外は、実施例1と同様にして試験セルを作製し、性能評価を行った。
正極活物質の合成において、一般式Ni0.91Co0.04Al0.05O2で表される複合酸化物と、Li2MoO4と、LiOH・H2OとをNi、Co、Al、及びMoの総量と、Liのモル比が1:1.05となるように混合し、焼成温度を730℃としたこと以外は、実施例1と同様にして試験セルを作製し、性能評価を行った。
正極活物質の合成において、一般式Ni0.89Co0.06Al0.05O2で表される複合酸化物と、Li2MoO4と、LiOH・H2OとをNi、Co、Al、及びMoの総量と、Liのモル比が1:1.05となるように混合し、昇温速度2.0℃/minで、室温から600℃まで焼成した。その後、昇温速度3℃/minで、600℃から800℃まで焼成しを用いたこと以外は、実施例1と同様にして試験セルを作製し、性能評価を行った。
正極活物質の合成において、一般式Ni0.94Co0.01Al0.05O2で表される複合酸化物と、LiOH・H2OとをNi、Co、及びAlの総量と、Liのモル比が1:1.02となるように混合したこと以外は、実施例1と同様にして試験セルを作製した。
Claims (7)
- 正極と、負極と、非水電解質とを備えた非水電解質二次電池であって、
前記正極は、層状構造を有し少なくともNiとMoとを含有するリチウム遷移金属複合酸化物を含み、
前記リチウム遷移金属複合酸化物において、
Niの含有率は、Liを除く金属元素の総モル数に対して80モル%~95モル%であり、
Moの含有率は、Liを除く金属元素の総モル数に対して3モル%未満であり、
前記負極は、負極活物質を含む負極合材層と、前記負極合材層の表面に形成されたMoを含有する被膜とを有し、
前記負極におけるMoの含有率は、前記正極中の前記リチウム遷移金属複合酸化物の総質量に対して0.5ppm~120ppmである、非水電解質二次電池。 - 前記被膜は、さらにNiを含有する、請求項1に記載の非水電解質二次電池。
- 前記負極におけるMoの含有率とNiの含有率の質量比(Mo/Ni)は、0.5~20である、請求項2に記載の非水電解質二次電池。
- 前記負極におけるMoの含有率とNiの含有率の質量比(Mo/Ni)は、2~18である、請求項2に記載の非水電解質二次電池。
- 前記リチウム遷移金属複合酸化物は、さらにAlもしくはMnの少なくともどちらか一方を含有し、
前記被膜は、さらにAlもしくはMnの少なくともどちらか一方を含有する、請求項1~4のいずれか1項に記載の非水電解質二次電池。 - X線回折によるX線回折パターンの(104)面の回折ピークの半値幅からシェラーの式により算出される前記リチウム遷移金属複合酸化物の結晶子サイズは、250Å~800Åの範囲である、請求項1~5のいずれか1項に記載の非水電解質二次電池。
- 前記リチウム遷移金属複合酸化物のBET比表面積は、1m2/g~5m2/gの範囲である、請求項1~6のいずれか1項に記載の非水電解質二次電池。
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