WO2022114233A1 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
- Publication number
- WO2022114233A1 WO2022114233A1 PCT/JP2021/043967 JP2021043967W WO2022114233A1 WO 2022114233 A1 WO2022114233 A1 WO 2022114233A1 JP 2021043967 W JP2021043967 W JP 2021043967W WO 2022114233 A1 WO2022114233 A1 WO 2022114233A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composite oxide
- positive electrode
- aqueous electrolyte
- negative electrode
- secondary battery
- Prior art date
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Images
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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
- This disclosure relates to a non-aqueous electrolyte secondary battery.
- the non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte, and has a structure in which these are housed in an exterior body. Since the configuration of the positive electrode, which is a main component of the non-aqueous electrolyte secondary battery, greatly affects the battery characteristics including the charge / discharge cycle characteristics, many studies have been made on the positive electrode. For example, Patent Documents 1 and 2 disclose positive electrode active materials for the purpose of improving performance such as charge / discharge cycle characteristics.
- the positive electrode active material disclosed in Patent Document 1 is a composite oxide represented by the general formula Li x Ni 1- y -z-v-w Coy Al z M1 V M2 w O 2 in the formula.
- the element M1 is at least one selected from Mn, Ti, Y, Nb, Mo, and W
- the element M2 is at least two selected from Mg, Ca, Sr, Ba, and Ra, and is an element.
- M2 contains at least Mg and Ca.
- non-aqueous electrolyte secondary batteries are required to have higher performance, especially to improve charge / discharge cycle characteristics.
- the conventional techniques including the techniques of Patent Documents 1 and 2 still have room for improvement in improving the cycle characteristics.
- the non-aqueous electrolyte secondary battery according to the present disclosure is a non-aqueous electrolyte secondary battery including a positive electrode having a positive electrode mixture layer, a negative electrode, and a non-aqueous electrolyte .
- Ni 1-y-z Co y M z O 2 (in the formula, 0.8 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.2, 0 ⁇ z ⁇ 0.5, M is Li, Ni, Co.
- b ⁇ 0.5, Me is a second lithium transition metal composite oxide represented by at least one metal element excluding Li and Ni), and the non-aqueous electrolyte contains a sulfonylimide salt. It is characterized by that.
- the non-aqueous electrolyte secondary battery according to the present disclosure has excellent charge / discharge cycle characteristics.
- the second lithium transition metal composite oxide is the first lithium transition metal. It is considered to protect the surface of the composite oxide and suppress deterioration. Furthermore, by adding a sulfonylimide salt to the non-aqueous electrolyte, a good quality protective film is formed on the particle surface of the positive electrode active material, the side reaction of the electrolyte on the particle surface is suppressed, and as a result, the cycle characteristics are greatly improved. Conceivable.
- the first lithium transition metal composite oxide contains Ni as an essential component, but by increasing the Ni content, it becomes easy to achieve both high capacity and good cycle characteristics.
- the effect of adding the second lithium transition metal composite oxide is more effective when the first lithium transition metal composite oxide having a high Ni content is used.
- the outer body of the battery is not limited to the cylindrical outer can, and is, for example, a square shape. It may be an outer can (square battery), a coin-shaped outer can (coin-shaped battery), or an outer body (laminated battery) composed 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 diagram schematically showing a cross section 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 non-aqueous 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 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 separator 13 is formed to have a size at least one size larger than that of the positive electrode 11, and two separators 13 are arranged so as to sandwich the positive electrode 11.
- 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.
- the outer can 16 is a bottomed cylindrical metal container having one side open in the axial direction.
- a gasket 28 is provided between the outer can 16 and the sealing body 17 to ensure the airtightness inside the battery and the insulating property between the outer can 16 and the sealing body 17.
- 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.
- FIG. 2 is a schematic view showing an enlarged part of a cross section of the electrode body 14.
- the positive electrode 11 has a positive electrode core body 30 and a positive electrode mixture layer 31 formed on at least one surface of the positive electrode core body 30.
- a metal foil stable in the potential range of the positive electrode 11, such as aluminum or an aluminum alloy, a film on which the metal is arranged on the surface layer, or the like can be used.
- the positive electrode mixture layer 31 contains a positive electrode active material, a conductive agent, and a binder, and is preferably formed on both surfaces of the positive electrode core body 30.
- a lithium transition metal composite oxide is used as the positive electrode active material.
- the positive electrode 11 is formed by applying a positive electrode mixture slurry containing a positive electrode active material, a conductive agent, a binder and the like on a positive electrode core 30, drying the coating film, and then compressing the positive electrode mixture layer 31 into a positive electrode. It can be manufactured by forming it on both sides of the core body 30.
- binder contained in the positive electrode mixture layer 31 examples include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimides, acrylic resins, and polyolefins. Further, these resins may be used in combination with a cellulose derivative such as carboxymethyl cellulose (CMC) or a salt thereof, polyethylene oxide (PEO) and the like.
- the content of the binder is, for example, 0.1 to 5% by mass or 0.5 to 3% by mass with respect to the total mass of the positive electrode mixture layer 31.
- the positive electrode mixture layer 31 contains at least two types of lithium transition metal composite oxides.
- the first lithium transition metal composite oxide (hereinafter referred to as “composite oxide (A)”) is a general formula Li x Ni 1-y-z Coy M z O 2 (in the formula, 0.8 ⁇ x ⁇ ). 1.2, 0 ⁇ y ⁇ 0.2, 0 ⁇ z ⁇ 0.5, M is a composite oxide represented by at least one metal element excluding Li, Ni, and Co).
- composite oxide (B) is a general formula Li a Ni 2-ab Me b O 2 (in the formula, 0 ⁇ a ⁇ 0.5, 0 ⁇ b ⁇ 0.5, Me is a composite oxide represented by at least one metal element excluding Li and Ni).
- the coexistence of the composite oxides (A and B) in the positive electrode mixture layer 31 specifically improves the charge / discharge cycle characteristics.
- the composite oxide (B) is considered to protect the particle surface of the composite oxide (A) and effectively suppress the deterioration of the particle surface, and as a result, the cycle characteristics are greatly improved.
- the composite oxide (B) may be mixed with the composite oxide (A) by applying a strong shearing force and a compressive force, and may be immobilized on the surface of the composite oxide (A).
- the composite oxide (B) exerts the above effect with a small amount of addition, but there is a preferable range in the addition amount of the composite oxide (B) in order to improve the cycle characteristics while maintaining a high battery capacity. do.
- the content of the composite oxide (B) is preferably 0.05 to 10% by mass, more preferably 0.1 to 7% by mass, or 0.1 to 5 with respect to the total mass of the positive electrode mixture layer 31. It is mass%. Similarly, it is preferably 0.05 to 10% by mass, more preferably 0.1 to 7% by mass, or 0.1 to 5% by mass with respect to the total mass of the positive electrode active material. When the amount of the composite oxide (B) is within the range, the cycle characteristics can be efficiently improved.
- the positive electrode mixture layer 31 contains a composite oxide other than the composite oxide (A, B) (for example, a lithium transition metal composite oxide that does not satisfy the above general formula) to the extent that the object of the present disclosure is not impaired. May be.
- the composite oxide (A, B) is preferably contained in an amount of 50% by mass or more with respect to the total mass of the positive electrode mixture layer 31.
- the total content of the composite oxides (A, B) is, for example, 85% by mass or more, 90% by mass or more, or 95% by mass or more with respect to the total mass of the positive electrode mixture layer 31.
- An example of a suitable content is 90 to 99% by mass, or 95 to 99% by mass.
- the composite oxide (A) is a composite oxide represented by the above general formula, and contains at least one metal element M excluding Li, Ni, and Co as essential constituent elements. Further, the composite oxide (A) preferably contains Co. However, since Co is particularly rare and expensive, the composite oxide (A) may be substantially free of Co. When the composite oxide (A) contains Co, the Co content is 20 mol% or less, more preferably 0.1 to 10 mol%, or 0.5, based on the total molar amount of the metal element excluding Li. It is ⁇ 5 mol%. The mole fraction of the metal element in the composite oxide can be measured by inductively coupled plasma (ICP) emission spectroscopy.
- ICP inductively coupled plasma
- the composite oxide (A) preferably has the highest Ni content among the metal elements other than Li.
- the Ni content is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol% or more, based on the total molar amount of the metal element excluding Li.
- a suitable example of Ni content is 80-97 mol%, or 85-95 mol%. That is, a preferable example of (1-yz) indicating the Ni content in the above general formula is 0.80 ⁇ (1-yz) ⁇ 0.97 or 0.85 ⁇ (1-y-). z) ⁇ 0.95.
- the composite oxide (A) is a composite oxide containing 80 mol% or more of Ni with respect to the total molar amount of the metal element excluding Li.
- the Ni-rich composite oxide (A) has good compatibility with the composite oxide (B) and is also effective in improving the cycle characteristics.
- x indicating the Li content is 0.8 ⁇ x ⁇ 1.2 or 0.97 ⁇ x ⁇ 1.2
- the composite oxide (A) has a molar ratio of Li to the transition metal. It may be a lithium excess type composite oxide exceeding 1.
- the composite oxide (A) contains at least one metal element M other than Li, Ni, and Co.
- the metal element M is at least one selected from, for example, Mn, W, Mg, Mo, Nb, Ti, Si, Al, Zr, B, Fe, Cu, Zn, Sn, Na, K, Ba, Sr, and Ca. It is a species, more preferably at least one selected from Mn, W, Mg, Mo, Nb, Ti, Si, Sr, Ca and Al. Above all, it is preferable to contain at least one of Mn and Al.
- the content of the metal element M is 50 mol% or less, more preferably 0.1 to 20 mol%, or 0.5, based on the total molar amount of the metal elements excluding Li. It is ⁇ 10 mol%, or 1 ⁇ 5 mol%.
- the composite oxide (A) has, for example, a crystal structure belonging to the space group R3-m.
- the composite oxide (A) has a layered structure including a transition metal layer, a Li layer, and an oxygen layer.
- the protective effect of the composite oxide (B) works more effectively, a stable crystal structure is maintained even after repeated charging and discharging, and the cycle characteristics can be improved more effectively.
- the BET specific surface area of the composite oxide (A) is, for example, 0.2 to 2.0 m 2 / g.
- the BET specific surface area is measured according to the BET method (nitrogen adsorption method) described in JIS R1626.
- the composite oxide (A) is, for example, a secondary particle formed by aggregating a plurality of primary particles.
- An example of the volume-based median diameter (D50) of the composite oxide (A) is 3 to 20 ⁇ m, or 5 to 15 ⁇ 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 secondary particles of the composite oxide 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 particle size of the primary particles of the composite oxide (A) is, for example, 0.05 ⁇ m to 1 ⁇ m.
- the particle size of the primary particle is measured as the diameter of the circumscribing circle in the cross-sectional image of the secondary particle observed by a scanning electron microscope (SEM).
- a compound containing at least one selected from Sr, Ca, W, Mg, Nb, and Al (hereinafter referred to as "metal element M2") is adhered to the particle surface of the composite oxide (A). You may be doing it.
- the M2 compound containing the metal element M2 may be scattered on the particle surface of the composite oxide (A), or may be present in layers so as to cover the entire particle surface.
- the thickness of the layer of the M2 compound is, for example, 0.1 to 5 nm.
- the M2 compound is thought to protect the surface of the composite oxide (A) as well as the surface of the composite oxide (B), which causes side reactions of the electrolyte on the particle surface of the composite oxide (A, B). It is suppressed.
- the M2 compound is an oxide, a hydroxide, or a carbonate.
- Specific examples of the M2 compound include SrO, CaO, Sr (OH) 2 , Ca (OH) 2 , SrCO 3 , CaCO 3 , and the like.
- the amount of the M2 compound is, for example, 0.05 to 0.5 mol% in terms of the metal element M2 with respect to the total number of moles of the metal element excluding Li constituting the composite oxide (A).
- the presence of the M2 compound can be confirmed by energy dispersive X-ray spectroscopy (TEM-EDX). Further, the metal element M2 can be measured by ICP emission spectroscopic analysis of a solution in which the composite oxide (A) is dissolved in fluorinated nitric acid.
- the composite oxide (A) has, for example, a first step of obtaining a composite oxide containing Ni, a metal element M, etc., a second step of mixing the composite oxide and a Li raw material to obtain a mixture, and firing the mixture. It is manufactured through the third step.
- a raw material containing the metal element M2 hereinafter referred to as “M2 raw material”.
- M2 raw material a raw material containing the metal element M2
- the composition, particle size, BET specific surface area, etc. of the composite oxide (A) and the M2 compound can be adjusted by controlling the mixing ratio of the raw materials, the firing conditions in the third step, and the like.
- an alkaline solution such as sodium hydroxide is added dropwise while stirring a solution of a metal salt containing a metal element such as Ni or metal element M, and the pH is adjusted to the alkaline side (for example, 8.5 to 12.5).
- a metal salt containing a metal element such as Ni or metal element M
- the firing temperature is not particularly limited, but is, for example, 300 to 600 ° C.
- the composite oxide obtained in the first step, the Li raw material, and, if necessary, the M2 raw material are mixed to obtain a mixture.
- Li raw materials include Li 2 CO 3 , LiOH, Li 2 O 2 , Li 2 O, LiNO 3 , LiNO 2 , Li 2 SO 4 , LiOH / H 2 O, LiH, LiF and the like.
- M2 raw material include oxides, hydroxides, carbonates, nitrates, sulfates and the like of M2.
- the mixing ratio of the composite oxide obtained in the first step and the Li raw material is adjusted so that, for example, the molar ratio of the metal element excluding Li: Li is 1: 0.98 to 1: 1.22. .. Further, the mixing ratio of the composite oxide and the M2 raw material is adjusted so that, for example, the molar ratio of the metal element excluding Li: M2 is 1: 0.0005 to 1: 0.005.
- the mixture obtained in the second step is calcined at a predetermined temperature and time to obtain a calcined product.
- the calcination of the mixture is performed, for example, in a calcination furnace, a first calcination step of calcination 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 a calcination furnace after the first calcination step. It is carried out by a multi-step firing 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 under an oxygen stream.
- the first temperature rise rate is 1.5 to 5.5 ° C./min
- the second temperature rise rate is slower than the first temperature rise rate, and may be 0.1 to 3.5 ° C./min.
- a plurality of heating rates may be set in each firing step.
- the holding time of the first set temperature in the first firing step is, for example, 0 to 5 hours or 0 to 3 hours.
- the holding time of the set temperature is the time for maintaining the set temperature after reaching the set temperature.
- the holding time of the second set temperature in the second firing step is, for example, 1 to 10 hours or 1 to 5 hours.
- the mixture may be calcined in an oxygen stream having an oxygen concentration of 60% or more, and the flow rate of the oxygen stream may be 0.2 to 4 mL / min per 10 cm 3 of the calcining furnace and 0.3 L / min or more per 1 kg of the mixture. ..
- the fired product may be washed with water, dehydrated and dried to remove impurities.
- the M2 raw material was not added in the second step, but the M2 raw material was added in the third step, when the fired product was washed with water or when it was dried. For example, in a vacuum atmosphere, 150 to 400 ° C. for 0.5 to 15 hours.
- the M2 compound may be fixed to the surface of the particles of the composite oxide (A) by performing the heat treatment of.
- the composite oxide (B) has the general formula Li a Ni 2-ab Me b O 2 (in the formula, 0 ⁇ a ⁇ 0.5, 0 ⁇ b ⁇ 0.5, Me is Li, It is a composite oxide represented by at least one metal element excluding Ni).
- the content of the metal element Me is preferably less than the content of Li and Ni, and is, for example, less than 10 mol% or less than 5 mol% with respect to the total molar amount of the metal element.
- the metal element Me include at least one selected from Cu, Sr, Ca, Nb, Si, and Al.
- the composition of the composite oxide (B) does not change due to the release and occlusion of Li by charging and discharging.
- the composite oxide (B) may contain a plurality of types of composite oxides having similar compositions.
- a in the above general formula is more preferably 0.1 ⁇ a ⁇ 0.5 or 0.2 ⁇ a ⁇ 0.4. When a is within the range, the cycle characteristics are improved more effectively.
- the composition of the composite oxide (B) can be identified from the X-ray diffraction pattern and can be analyzed using ICP emission spectroscopic analysis.
- the composite oxide (B) is, for example, a composite oxide having at least one diffraction peak having a peak top at a diffraction angle (2 ⁇ ) of 21.40 ° to 21.65 ° of synchrotron radiation X-ray diffraction (light energy 16 keV). Is.
- the X-ray diffraction pattern of the composite oxide (B) is obtained by a powder X-ray diffraction method under the following conditions using a synchrotron radiation facility (Beamline BL5S2 of Aichi Synchrotron Radiation Center). Light energy; 16 keV Scan range; 10-90 ° Analytical optical system: Devi-Sheller type
- the obtained data is peak-searched with the identification analysis software PDXL (manufactured by Rigaku) to identify the composite oxide (B).
- NiO has a peak at 21.36 °, and the peak shifts to the high angle side as a in the general formula increases. If a in the above general formula is within the above range, the main peak exists at 21.40 ° to 21.65 °.
- the composite oxide (B) can be identified by collating with the JCPDS card including other peaks.
- the composite oxide (B) is, for example, particles having a smaller particle size than the composite oxide (A) and is a secondary particle formed by aggregating a plurality of primary particles.
- An example of D50 of the composite oxide (B) is 1 to 15 ⁇ m, or 1 to 10 ⁇ m, or 2 to 7 ⁇ m.
- the D50 of the composite oxide (B) may be 1/2 or less of the D50 of the composite oxide (A), preferably 1/5 to 1/2 of the D50 of the composite oxide (A), or 1 It is / 3 to 1/2.
- the BET specific surface area of the composite oxide (B) is, for example, 0.5 to 2.5 m 2 / g.
- the composite oxide (B) exists in the positive electrode mixture layer 31 in a state of being surrounded by, for example, a plurality of composite oxides (A). Then, the particle surfaces of the composite oxides (A, B) are in contact with each other. In this case, it is considered that the interaction of the composite oxides (A and B) is more effectively expressed and the effect of improving the cycle characteristics is enhanced.
- the composite oxide (B) is not limited to the one intentionally added, and may be mixed as a by-product of the composite oxide (A) or an impurity of another positive electrode material. ..
- the composite oxide (B) has, for example, a first step of mixing a predetermined amount of a Li raw material and a Ni raw material to obtain a mixture, and a second step of calcining the mixture at 500 to 800 ° C. for 10 to 30 hours. Manufactured after.
- the raw material may be crushed if necessary, or the raw material containing the metal element Me may be added as long as the X-ray diffraction pattern of the composite oxide (B) satisfies the above conditions.
- the mixture may be formed into pellets and then fired, or may be crushed after firing. The firing in the second step is performed, for example, in the atmosphere or in an oxygen atmosphere.
- Li raw materials include Li 2 CO 3 , LiOH, Li 2 O 2 , Li 2 O, LiNO 3 , LiNO 2 , Li 2 SO 4 , LiOH / H 2 O, LiH, LiF and the like.
- Ni raw materials include NiO, Ni (OH) 2 , NiCO 3 , NiSO 4 , Ni (NO 3 ) 2 , and the like.
- the mixing ratio of the Li raw material and the Ni raw material is, for example, such that the X-ray diffraction pattern of the composite oxide (B) satisfies the above condition and that a in the above general formula is 0 ⁇ a ⁇ 0.5. Adjusted to meet.
- the positive electrode mixture layer 31 contains a conductive agent.
- the conductive agent forms a good conductive path in the positive electrode mixture layer 31, and contributes to lowering the resistance of the positive electrode mixture layer 31.
- the positive electrode mixture layer 31 contains carbon nanotubes (CNTs) as a conductive agent.
- CNTs carbon nanotubes
- a particulate conductive agent such as carbon black, acetylene black, ketjen black, graphite, gas phase grown carbon fiber (VGCF), electrospun carbon fiber, polyacrylonitrile (PAN).
- Fibrous conductive agents such as carbon fibers, pitch carbon fibers, and conductive agents such as graphene may be contained.
- CNTs form a good conductive path in the positive electrode mixture layer 31 and connect the particles of the composite oxide (A, B) to improve the surface protection effect of the composite oxide (B).
- the content of CNT is, for example, 0.01 to 5% by mass, more preferably 0.04 to 2% by mass, or 0.06 to 0.8% by mass with respect to the total mass of the positive electrode mixture layer 31. Is. When the content of CNT is within the range, the cycle characteristics can be efficiently improved.
- the positive electrode mixture layer 31 may contain only CNT as a conductive agent.
- the CNT may be either a single-walled CNT (SWCNT) or a multi-walled CNT (MWCNT).
- MWCNTs for example, a CNT having a tubular structure in which a graphene sheet made of a carbon 6-membered ring is wound parallel to the fiber axis, and a graphene sheet made of a carbon 6-membered ring are arranged perpendicular to the fiber axis.
- a CNT having a poolet structure, a CNT having a herringbone structure in which a graphene sheet composed of a carbon six-membered ring is wound at an oblique angle with respect to the fiber axis, or the like can be used. Two or more types of CNTs may be added to the positive electrode mixture layer 31.
- the average diameter of CNTs is, for example, 50 nm or less, preferably 40 nm or less, more preferably 25 nm or less, or 20 nm or less.
- the lower limit of the average diameter of CNTs is not particularly limited, but is, for example, 1 nm or 5 nm.
- An example of a suitable range of average diameters of CNTs is 1-20 nm, or 5-20 nm.
- the average fiber length of CNT is, for example, 0.5 ⁇ m or more, preferably 0.7 ⁇ m or more, more preferably 0.8 ⁇ m or more, or 1 ⁇ m or more.
- the upper limit of the average fiber length of CNT is not particularly limited, but as an example, it is 10 ⁇ m or 5 ⁇ m.
- An example of a suitable range of average fiber length of CNTs is 1-10 ⁇ m, or 1-5 ⁇ m. When the average fiber length of CNTs is within the range, the effect of improving the cycle characteristics is enhanced as compared with the case of using CNTs whose average fiber length is out of the range.
- the average fiber length of CNTs is, for example, shorter than the length corresponding to D50 of the composite oxide (B).
- the average diameter of the CNTs was measured from the surface TEM image of the positive electrode mixture layer 31, and the average fiber length was measured by selecting 100 CNTs from the cross-sectional SEM image of the positive mixture layer 31 and measuring the diameter and fiber length. It is obtained by averaging these measured values.
- the negative electrode 12 has a negative electrode core body 40 and a negative electrode mixture layer 41 formed on at least one surface of the negative electrode core body 40.
- a foil of a metal stable in the potential range of the negative electrode such as copper or a copper alloy, a film in which the metal is arranged on the surface layer, or the like can be used.
- the negative electrode mixture layer 41 contains a negative electrode active material and a binder, and is preferably formed on both sides of the negative electrode core 40. Further, a conductive agent such as CNT may be added to the negative electrode mixture layer 41.
- the negative electrode 12 is formed by applying a negative electrode mixture slurry containing a negative electrode active material, a binder and the like on the negative electrode core 40, drying the coating film, and then compressing the negative electrode mixture layer 41 of the negative electrode core 40. It can be manufactured by forming it on both sides.
- the negative electrode mixture layer 41 contains a carbon-based active material, at least one selected from Si, Sn, Sb, Mg, and Ge (hereinafter referred to as “metal element M3”) and a metal element as the negative electrode active material. It contains at least one of the M3 compounds containing M3.
- the contents of the metal elements M3 and the M3 compound are, for example, 0.5 to 30% by mass, preferably 1 to 15% by mass, based on the total mass of the negative electrode active material.
- the metal element M3 may be added to the negative electrode mixture layer 41, but the M3 compound is preferably added.
- M3 compounds include SiC, SnO 2 , a silicon oxide phase and a first silicon material (SiO) containing Si dispersed in the silicon oxide phase, a lithium silicate phase and a dispersion in the lithium silicate phase.
- SiO silicon oxide phase
- a first silicon material SiO
- LSX second silicon material
- Si—C silicon material
- the carbon-based active material for example, natural graphite such as scaly graphite, massive artificial graphite, artificial graphite such as graphitized mesophase carbon microbeads, and the like are used.
- the content of the carbon-based active material (graphite) is, for example, 70 to 99.5% by mass or 85 to 99% by mass with respect to the mass of the negative electrode active material.
- an example of the carbon-based active material D50 is 1 to 20 ⁇ m or 2 to 15 ⁇ m.
- SiO and LSX are, for example, particles in which D50 is smaller than D50 of graphite.
- An example of the SiO and LSX D50 is 1 ⁇ m to 15 ⁇ m, or 3 ⁇ m to 10 ⁇ m.
- a conductive layer made of a highly conductive material may be formed on the surface of the particles of SiO and LSX.
- An example of a suitable conductive layer is a carbon film made of a carbon material.
- the thickness of the conductive layer is preferably 1 to 200 nm or 5 to 100 nm in consideration of ensuring conductivity and diffusing lithium ions into the particles.
- SiO has a particle structure in which fine Si particles are dispersed in a silicon oxide phase.
- a suitable SiO has a sea-island structure in which fine Si particles are substantially uniformly dispersed in an amorphous silicon oxide matrix, and is represented by the general formula SiO x (0 ⁇ x ⁇ 2).
- the silicon oxide phase is composed of a set of particles finer than Si particles.
- the content of Si particles is preferably 35 to 75% by mass with respect to the total mass of SiO, from the viewpoint of achieving both battery capacity and cycle characteristics.
- the average particle size of the Si particles dispersed in the silicon oxide phase is, for example, 500 nm or less, preferably 200 nm or less, or 50 nm or less before charging / discharging. After charging and discharging, it is, for example, 400 nm or less, or 100 nm or less.
- the average particle size of the Si particles is determined as the average value of the longest diameters of 100 Si particles by observing the particle cross section of SiO using a SEM or a transmission electron microscope (TEM).
- LSX has a particle structure in which fine Si particles are dispersed in a lithium silicate phase.
- a suitable LSX has a sea-island structure in which fine Si particles are substantially uniformly dispersed in a matrix of lithium silicate.
- the lithium silicate phase is composed of a set of particles finer than Si particles.
- the content of Si particles is preferably 35 to 75% by mass with respect to the total mass of LSX, as in the case of SiO.
- the average particle size of the Si particles is, for example, 500 nm or less, preferably 200 nm or less, or 50 nm or less before charging / discharging.
- the content of the main component is preferably more than 50% by mass with respect to the total mass of the lithium silicate phase, and 80% by mass or more. More preferred.
- Si-C has a carbon phase and silicon particles dispersed in the carbon phase.
- the content of the silicon particles of suitable Si—C is preferably 30% by mass or more and 80% by mass or less, and preferably 35% by mass or more and 75% by mass or less in terms of increasing the capacity and the like. , 55% by mass or more and 70% by mass or less is more preferable.
- the average particle size of suitable silicon particles is generally 500 nm or less, preferably 200 nm or less, and more preferably 100 nm or less before charging / discharging. After charging and discharging, 400 nm or less is preferable, and 100 nm or less is more preferable.
- the average particle size of the silicon particles is measured by observing the particle cross section of Si—C using SEM or TEM, and specifically, it is obtained as the average value of the longest diameters of 100 silicon particles.
- the binder contained in the negative electrode mixture layer 41 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) is particularly used. It is preferable to use it.
- the negative electrode mixture layer 41 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 content of the binder is, for example, 0.1 to 5% by mass with respect to the mass of the negative electrode active material.
- the separator 13 has a porous base material 50 and a surface layer 51 formed on the surface of the base material 50 facing the positive electrode 11 side.
- the surface layer 51 is a layer containing inorganic particles and a binder.
- the surface layer 51 may be formed on both sides of the base material 50, but is preferably formed on only one side of the base material 50 facing the positive electrode 11 side from the viewpoint of increasing the capacity and the like.
- the separator 13 is a porous sheet interposed between the positive electrode 11 and the negative electrode 12 to prevent electrical contact between the two electrodes, and has ion permeability and insulating properties.
- the porosity of the separator 13 is, for example, 30% to 70%.
- the porosity of the separator 13 is determined by the porosity of the base material 50.
- the base material 50 is a resin-made porous sheet.
- the thickness of the base material 50 is, for example, 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
- the resin constituting the base material 50 is not particularly limited, and specific examples thereof include polyolefins such as polyethylene, polypropylene, and a copolymer of ethylene and ⁇ -olefin, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ether ketone, and polyimide. , Fluororesin, cellulose and the like.
- the base material 50 may have a single-layer structure, or may have a laminated structure such as a three-layer structure of polyethylene / polypropylene / polyethylene.
- the surface layer 51 is porous like the base material 50, and has ion permeability and insulating properties.
- the thickness of the surface layer 51 is not particularly limited, but is preferably thinner than the thickness of the base material 50, for example, 0.5 to 10 ⁇ m, and preferably 1 to 6 ⁇ m.
- the surface layer 51 is in contact with the surface of the positive electrode mixture layer 31, and is preferably formed over substantially the entire surface of one side of the base material 50.
- the surface layer 51 can be formed, for example, by applying a slurry containing inorganic particles and a binder to the entire surface of the base material 50 and then drying the coating film.
- the surface layer 51 is a layer containing inorganic particles as a main component.
- the content of the inorganic particles is, for example, 70% by mass or more, preferably 80% by mass or more, based on the total mass of the surface layer 51.
- a suitable range of the content of the inorganic particles is 70 to 99% by mass, 80 to 98% by mass, or 85 to 95% by mass.
- the surface layer 51 has a function of suppressing damage to the separator 13 due to a conductive foreign substance, deformation of the separator 13 at the time of abnormal heat generation, and the like.
- the surface layer 51 in contact with the positive electrode 11 suppresses the side reaction of the electrolyte in the positive electrode 11 by the interaction with the composite oxide (B), and by providing the surface layer 51, the cycle characteristics and the storage characteristics of the battery are peculiar. To improve.
- Examples of the inorganic particles contained in the surface layer 51 include metal oxides, metal nitrides, metal fluorides, metal carbides, aluminum hydroxide (bemite), metal hydroxides such as magnesium hydroxide, calcium carbonate, magnesium carbonate, and barium carbonate. Examples thereof include particles such as metal carbonates such as calcium sulfate, magnesium sulfate, and metal sulfates such as barium sulfate.
- One type of inorganic particles may be used alone, or two or more types may be used in combination.
- the D50 of the inorganic particles is, for example, 0.01 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m.
- metal oxides are aluminum oxide (alumina), titanium oxide, magnesium oxide, zirconium oxide, nickel oxide, silicon oxide, manganese oxide and the like.
- metal nitrides are titanium nitride, boron nitride, aluminum nitride, magnesium nitride, silicon nitride and the like.
- metal fluorides are aluminum fluoride, lithium fluoride, sodium fluoride, magnesium fluoride, calcium fluoride, barium fluoride and the like.
- metal carbides are silicon carbide, boron carbide, titanium carbide, tungsten carbide and the like. From the viewpoint of improving cycle characteristics and storage characteristics, an example of suitable inorganic particles is at least one selected from alumina, boehmite, and barium sulfate.
- the binder contained in the surface layer 51 is not particularly limited as long as it can fix the inorganic particles to each other, can fix the inorganic particles to the base material 50, and has electrolytic solution resistance.
- a positive electrode combination is used.
- the same type of binder as that used for the agent layer 31 and the negative electrode mixture layer 41 can be used.
- Specific examples include fluororesins such as PVdF and PTFE, PAN, acrylic resins and the like.
- a resin having high heat resistance such as an aramid resin may be used.
- a suitable binder at least one selected from an aramid resin and an acrylic resin can be mentioned.
- 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 such as acetonitrile, amides such as dimethylformamide, and a mixed solvent of two or more of these can be 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.
- halogen substituent examples include a fluorinated cyclic carbonate ester such as fluoroethylene carbonate (FEC), a fluorinated chain carbonate ester, and a fluorinated chain carboxylic acid ester such as methyl fluoropropionate (FMP).
- FEC fluoroethylene carbonate
- FMP fluorinated chain carboxylic acid ester
- the non-aqueous electrolyte is not limited to the liquid electrolyte, and may be a solid electrolyte.
- the non-aqueous electrolyte contains a sulfonylimide salt as an electrolyte salt.
- a sulfonylimide salt as an electrolyte salt.
- the concentration of the sulfonylimide salt is preferably 0.05 to 2.5 mol / L, more preferably 0.1 to 2.0 mol / L, or 0.1 to 1.5 mol / L. When the content of the sulfonylimide salt is within the range, the cycle characteristics can be improved more effectively.
- the sulfonylimide salt added to the non-aqueous electrolyte is preferably lithium sulfonylimide.
- Lithium sulfonyl imides include, for example, lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonyl) imide, lithium bis (nonafluorobutane sulfonyl) imide, lithium bis (pentafluoroethanesulfonyl) imide (LIBETI) and the like.
- LiFSI lithium bis (fluorosulfonyl) imide
- LiFSI lithium bis (trifluoromethanesulfonyl) imide
- LIBETI lithium bis (pentafluoroethanesulfonyl) imide
- One type of sulfonylimide salt may be used alone, or two or more types may be used in combination.
- the non-aqueous electrolyte may further contain other lithium salts.
- other lithium salts include LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , Li (P (C 2 O 4 ) F 4 ). ), LiPF 6-x (Cn F 2n + 1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2), LiB 10 Cl 10 , LiCl, LiBr, LiI, lithium chloroborane, lithium lower aliphatic carboxylate, Li Examples thereof include borates such as 2 B 4 O 7 and Li (B (C 2 O 4 ) F 2 ). Above all, it is preferable to use LiPF 6 from the viewpoint of ionic conductivity, electrochemical stability and the like.
- the non-aqueous electrolyte contains a lithium sulfonylimide and a second lithium salt.
- the combination of LiFSI and LiPF 6 is particularly preferable.
- the concentration of lithium sulfonylimide is adjusted to the above range, for example, even when a second lithium salt is contained.
- the concentration of lithium sulfonylimide is 0.1 to 1.5 mol / L, and the total concentration of lithium salts is 1.5 to 2.5 mol / L.
- the concentration of lithium sulfonylimide is, for example, 30 to 70% of the concentration of the lithium salt contained in the non-aqueous electrolyte.
- the non-aqueous electrolyte may contain additives such as vinylene carbonate (VC), ethylene sulphite (ES), cyclohexylbenzene (CHB), orthoterphenyl (OTP), and propane sultone-based compounds.
- VC vinylene carbonate
- ES ethylene sulphite
- CHB cyclohexylbenzene
- OTP orthoterphenyl
- propane sultone-based compounds propane sultone-based compounds.
- concentration of the additive is not particularly limited, but as an example, it is 0.1 to 5% by mass.
- esters and ethers are used as the non-aqueous solvent.
- esters include cyclic carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methylpropyl carbonate, and the like.
- Chained carbonate esters such as ethylpropyl carbonate and methylisopropylcarbonate, cyclic carboxylic acid esters such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL), methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP) , Chain carboxylic acid esters such as ethyl propionate (EP) and the like.
- GBL ⁇ -butyrolactone
- VTL ⁇ -valerolactone
- MP methyl propionate
- EP ethyl propionate
- ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahexyl, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4-.
- Cyclic ethers such as dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineole, crown ether, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, Dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methylphenyl ether, ethylphenyl ether, butylphenyl ether, pentylphenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxyethane , 1,2-Dibutoxyetane, Diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, Diethylene glycol dibutyl ether, 1,1-dimethoxymethane,
- the compound containing the metal element M2 instead of the compound containing the metal element M2, another compound such as a lanthanoid-containing compound may be adhered to the particle surface of the composite oxide (A).
- the adhered matter may not be substantially present on the particle surface of the composite oxide (A).
- the composite oxide (B) having a small particle size may be adhered to the particle surface of the composite oxide (A).
- the positive electrode mixture layer may not contain CNTs, and may contain carbon black, acetylene black, ketjen black, graphite or the like as a conductive agent. Further, the negative electrode mixture layer may not contain the metal elements M3 and the M3 compound, and may contain only a carbon-based active material such as graphite as the negative electrode active material.
- the separator may be a porous sheet containing inorganic particles as a main component and having no surface layer.
- a surface layer containing inorganic particles as a main component may be provided on the surface of the positive electrode mixture layer.
- the composition of the composite oxide (A1) was LiNi 0.91 Co 0.04 Al 0.05 O 2 as a result of ICP analysis. Further, it was identified by the X-ray diffraction method that the crystal structure of the first lithium transition metal composite oxide belongs to the space group R-3m.
- the D50 of the composite oxide (A1) measured using water as a dispersion medium using MT3000II manufactured by Microtrac Bell Co., Ltd. was 10 ⁇ m.
- composition of the composite oxide (B1) was Li 0.3 Ni 1.7 O 2 by collation with the JCPDS card including other peaks.
- the D50 of the composite oxide (B1) measured using water as a dispersion medium using MT3000II manufactured by Microtrac Bell Co., Ltd. was 5 ⁇ m.
- a mixture of composite oxides (A1 and B1) at a mass ratio of 99.9: 0.1 was used as a positive electrode active material.
- the positive electrode active material, acetylene black (AB), and polyvinylidene fluoride (PVdF) are mixed at a solid content mass ratio of 92: 5: 3, an appropriate amount of N-methylpyrrolidone (NMP) is added, and then this is added. Kneading was performed to prepare a positive electrode mixture slurry.
- the positive electrode mixture slurry is applied to a positive electrode core made of aluminum foil, the coating film is dried, and then the coating film is rolled using a rolling roller, cut to a predetermined electrode size, and applied to both sides of the positive electrode core body.
- a positive electrode having a positive electrode mixture layer formed was obtained. An exposed portion where the surface of the positive electrode current collector was exposed was provided on a part of the positive electrode.
- SBR styrene-butadiene rubber
- CMC-Na sodium carboxymethyl cellulose
- LiPF LiPF at a concentration of 0.5 mol / L with respect to a mixed solvent in which ethylene carbonate (EC) and ethylmethyl carbonate (EMC) are mixed at a volume ratio of 3: 7 (25 ° C., 1 atm). 6 was dissolved at a concentration of 1.0 mol / L to prepare a non-aqueous electrolyte.
- EC ethylene carbonate
- EMC ethylmethyl carbonate
- the positive electrode to which the aluminum positive electrode lead is attached and the negative electrode to which the nickel negative electrode lead is attached are spirally wound through a polyethylene separator and molded into a flat shape to form a wound electrode body. Made.
- This electrode body was housed in an exterior body made of an aluminum laminate, and after injecting the non-aqueous electrolytic solution, the opening of the exterior body was sealed to prepare a test cell for evaluation.
- Example 2 A test cell was prepared in the same manner as in Example 1 except that the composite oxides (A1 and B1) were mixed at a mass ratio of 99.8: 0.2 in the preparation of the positive electrode.
- Example 3 A test cell was prepared in the same manner as in Example 1 except that the composite oxides (A1 and B1) were mixed at a mass ratio of 99.7: 0.3 in the preparation of the positive electrode.
- Example 4 A test cell was prepared in the same manner as in Example 2 except that LiFSI was dissolved at a concentration of 1.0 mol / L and LiPF 6 was dissolved at a concentration of 0.5 mol / L in the preparation of the non-aqueous electrolyte.
- Example 5 The test cell was the same as in Example 2 except that Li 2 O and Ni O were mixed so that the molar ratio of Li and Ni was 0.2: 1.8 to synthesize a composite oxide (B2). Was produced.
- Example 6 The test cell was the same as in Example 2 except that Li 2 O and Ni O were mixed so that the molar ratio of Li and Ni was 0.5: 1.5 to synthesize a composite oxide (B3). Was produced.
- Example 1 A test cell was prepared in the same manner as in Example 4 except that the composite oxide (B1) was not used in the preparation of the positive electrode.
- Comparative Example 2 A test cell was prepared in the same manner as in Comparative Example 1 except that LiFSI was dissolved at a concentration of 0.5 mol / L and LiPF 6 was dissolved at a concentration of 1.0 mol / L in the preparation of the non-aqueous electrolyte.
- Example 3 A test cell was prepared in the same manner as in Example 2 except that LiPF 6 was dissolved at a concentration of 1.5 mol / L without using LiFSI in the preparation of the non-aqueous electrolyte.
- Example 5 A test cell was prepared in the same manner as in Example 2 except that the following composite oxide (B10) was used instead of the composite oxide (B1) in the preparation of the positive electrode. [Synthesis of composite oxide (B10)] Li 2 O and Ni O were weighed so that the molar ratio of Li and Ni was 0.7: 1.3, and these were mixed while being pulverized to prepare a mixture. Next, this mixture was calcined at 650 ° C. for 20 hours in an oxygen atmosphere and further crushed to obtain a composite oxide (B10).
- the composite oxide (A1) and the general formula Li a Ni 2-ab Me b O 2 in the formula, 0 ⁇ a ⁇ 0.5, 0 ⁇ b ⁇ 0.5, Me is Li, Ni.
- a positive electrode containing a composite oxide (B1 to B3) represented by (excluding at least one metal element) and a non-aqueous electrolyte to which LiFSI is added is used, a specific improvement in cycle characteristics can be seen.
- 10 non-aqueous electrolyte secondary battery 11 positive electrode, 12 negative electrode, 13 separator, 14 electrode body, 16 exterior can, 17 sealing body, 18, 19 insulating plate, 20 positive electrode lead, 21 negative electrode lead, 22 grooving part, 23 internal terminal Plate, 24 lower valve body, 25 insulating member, 26 upper valve body, 27 cap, 28 gasket, 30 positive electrode core, 31 positive electrode mixture layer, 40 negative electrode core, 41 negative electrode mixture layer, 50 base material, 51 surface layer
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Abstract
Description
図2に示すように、正極11は、正極芯体30と、正極芯体30の少なくとも一方の面に形成された正極合剤層31とを有する。正極芯体30には、アルミニウム、アルミニウム合金など、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。正極合剤層31は、正極活物質、導電剤、及び結着剤を含み、正極芯体30の両面に形成されることが好ましい。正極活物質には、リチウム遷移金属複合酸化物が用いられる。正極11は、正極芯体30上に正極活物質、導電剤、及び結着剤等を含む正極合剤スラリーを塗布し、塗膜を乾燥させた後、圧縮して正極合剤層31を正極芯体30の両面に形成することにより製造できる。
複合酸化物(A)は、上記一般式で表される複合酸化物であって、必須構成元素としてLi、Ni、Coを除く少なくとも1種の金属元素Mを含有する。また、複合酸化物(A)はCoを含有することが好ましい。但し、Coは特に希少で高価であることから、複合酸化物(A)は実質的にCoを含有しないものであってもよい。複合酸化物(A)がCoを含有する場合、Co含有量は、Liを除く金属元素の総モル量に対して20mol%以下であり、より好ましくは0.1~10mol%、又は0.5~5mol%である。なお、複合酸化物中の金属元素のモル分率は、誘導結合プラズマ(ICP)発光分光分析により測定できる。
複合酸化物(B)は、上述の通り、一般式LiaNi2-a-bMebO2(式中、0<a≦0.5、0≦b≦0.5、MeはLi、Niを除く少なくとも1種の金属元素)で表される複合酸化物である。金属元素Meの含有量は、Li、Niの含有量より少ないことが好ましく、例えば、金属元素の総モル量に対して10mol%未満、又は5mol%未満である。金属元素Meの一例としては、Cu、Sr、Ca、Nb、Si、及びAlから選ばれる少なくとも1種が挙げられる。
光エネルギー;16keV
スキャン範囲;10~90°
解析光学系:デバイシェラー型
得られたデータを同定解析ソフトPDXL(リガク社製)でピークサーチし、複合酸化物(B)の同定を行う。
上記の装置での測定では、NiOは21.36°にピークを持ち、上記一般式中のaが増えるに従いピークは高角度側にシフトする。上記一般式中のaが上記の範囲内であれば、21.40°~21.65°にメインピークが存在する。他のピークも含めてJCPDSカードと照合することにより複合酸化物(B)を同定することができる。
正極合剤層31には、上述の通り、導電剤が含まれている。導電剤は、正極合剤層31中に良好な導電パスを形成し、正極合剤層31の低抵抗化に寄与する。正極合剤層31には、導電剤として、カーボンナノチューブ(CNT)が含まれている。また、正極合剤層31には、CNTと共に、カーボンブラック、アセチレンブラック、ケッチェンブラック、黒鉛等の粒子状導電剤、気相成長炭素繊維(VGCF)、電界紡糸法炭素繊維、ポリアクリロニトリル(PAN)系炭素繊維、ピッチ系炭素繊維、グラフェン等の導電剤等の繊維状導電剤などが含まれていてもよい。
図2に示すように、負極12は、負極芯体40と、負極芯体40の少なくとも一方の面に形成された負極合剤層41とを有する。負極芯体40には、銅、銅合金などの負極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。負極合剤層41は、負極活物質及び結着剤を含み、負極芯体40の両面に形成されることが好ましい。また、負極合剤層41には、CNT等の導電剤が添加されていてもよい。負極12は、負極芯体40上に負極活物質及び結着剤等を含む負極合剤スラリーを塗布し、塗膜を乾燥させた後、圧縮して負極合剤層41を負極芯体40の両面に形成することにより製造できる。
図2に示すように、セパレータ13は、多孔質の基材50と、基材50の表面のうち正極11側を向いた表面に形成された表層51とを有する。表層51は、無機粒子及び結着剤を含む層である。表層51は、基材50の両面に形成されてもよいが、高容量化等の観点から正極11側を向いた基材50の片面のみに形成されることが好ましい。セパレータ13は、正極11と負極12の間に介在して両極の電気的接触を防止する多孔質シートであって、イオン透過性及び絶縁性を有する。セパレータ13の空隙率は、例えば30%~70%である。なお、セパレータ13の空隙率は基材50の空隙率によって決定される。
非水電解質は、非水溶媒と、非水溶媒に溶解した電解質塩とを含む。非水溶媒には、例えばエステル類、エーテル類、アセトニトリル等のニトリル類、ジメチルホルムアミド等のアミド類、及びこれらの2種以上の混合溶媒等を用いることができる。非水溶媒は、これら溶媒の水素の少なくとも一部をフッ素等のハロゲン原子で置換したハロゲン置換体を含有していてもよい。ハロゲン置換体としては、フルオロエチレンカーボネート(FEC)等のフッ素化環状炭酸エステル、フッ素化鎖状炭酸エステル、フルオロプロピオン酸メチル(FMP)等のフッ素化鎖状カルボン酸エステルなどが挙げられる。なお、非水電解質は、液体電解質に限定されず、固体電解質であってもよい。
複合酸化物(A)の粒子表面には、金属元素M2を含有する化合物の代わりに、ランタノイド含有化合物等の他の化合物が固着していてもよい。或いは、複合酸化物(A)の粒子表面には、固着物が実質的に存在していなくてもよい。また、複合酸化物(A)の粒子表面には、粒径の小さな複合酸化物(B)が固着していてもよい。
[複合酸化物(A1)の合成]
共沈法により得られた[Ni0.91Co0.04Al0.05](OH)2で表される複合水酸化物を500℃で8時間焼成し、複合酸化物(Ni0.91Co0.04Al0.05O2)を得た(第1工程)。次に、水酸化リチウム(LiOH)及び上記複合酸化物を、Liと、Ni、Co、及びAlの総量とのモル比が、1.02:1になるように混合して混合物を得た。この混合物を、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℃/minで、室温から650℃まで焼成した後、昇温速度0.5℃/minで、650℃から720℃まで焼成した。この焼成物を水洗し、不純物を除去して、複合酸化物(A1)を得た。
Li2O、NiOを、LiとNiのモル比が0.3:1.7となるように秤量し、これらを粉砕しつつ混合して混合物を作製した。次に、この混合物を、酸素雰囲気下、650℃で20時間焼成し、さらに解砕することで複合酸化物(B1)を得た。上記放射光施設を用いて複合酸化物(B1)の粉末X線回折測定を行ったところ、得られたX線回折パターンの2θ=21.40°~21.65°の範囲には、21.48°にピークトップを有する1本のピークが確認された。また、複合酸化物(B1)の組成は、他のピークも含めたJCPDSカードとの照合により、Li0.3Ni1.7O2であることが確認された。マイクロトラック・ベル株式会社製、MT3000IIを用い、水を分散媒として測定した複合酸化物(B1)のD50は5μmであった。
複合酸化物(A1,B1)を99.9:0.1の質量比で混合したものを正極活物質とした。正極活物質と、アセチレンブラック(AB)と、ポリフッ化ビニリデン(PVdF)とを、92:5:3の固形分質量比で混合し、N-メチルピロリドン(NMP)を適量加えた後、これを混練して正極合剤スラリーを調製した。当該正極合剤スラリーをアルミニウム箔からなる正極芯体に塗布し、塗膜を乾燥した後、圧延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剤層が形成された正極を得た。なお、正極の一部に正極集電体の表面が露出した露出部を設けた。
負極活物質として、黒鉛と、SiOx(X=1.0)で表されるSiOとを、95:5の質量比で混合したものを用いた。負極活物質と、スチレン-ブタジエンゴム(SBR)のディスパージョンと、カルボキシメチルセルロースナトリウム(CMC-Na)とを、98:1:1の固形分質量比で混合し、分散媒として水を用いて、負極合剤スラリーを調製した。次に、この負極合剤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、圧縮した後、所定の電極サイズに切断し、負極芯体の両面に負極合剤層が形成された負極を作製した。
エチレンカーボネート(EC)と、エチルメチルカーボネート(EMC)とを、3:7の体積比(25℃、1気圧)で混合した混合溶媒に対して、LiFSIを0.5mol/Lの濃度で、LiPF6を1.0mol/Lの濃度でそれぞれ溶解し、非水電解質を調製した。
アルミニウム製の正極リードを取り付けた上記正極、およびニッケル製の負極リードを取り付けた上記負極を、ポリエチレン製のセパレータを介して渦巻状に巻回し、扁平状に成形して巻回型の電極体を作製した。この電極体をアルミニウムラミネ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後、外装体の開口部を封止して評価用の試験セルを作製した。
正極の作製において、複合酸化物(A1,B1)を99.8:0.2の質量比で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。
正極の作製において、複合酸化物(A1,B1)を99.7:0.3の質量比で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。
非水電解質の調製において、LiFSIを1.0mol/Lの濃度で、LiPF6を0.5mol/Lの濃度でそれぞれ溶解したこと以外は、実施例2と同様にして試験セルを作製した。
Li2O、NiOを、LiとNiのモル比が0.2:1.8となるように混合して複合酸化物(B2)を合成したこと以外は、実施例2と同様にして試験セルを作製した。
Li2O、NiOを、LiとNiのモル比が0.5:1.5となるように混合して複合酸化物(B3)を合成したこと以外は、実施例2と同様にして試験セルを作製した。
正極の作製において、複合酸化物(B1)を用いなかったこと以外は、実施例4と同様にして試験セルを作製した。
非水電解質の調製において、LiFSIを0.5mol/Lの濃度で、LiPF6を1.0mol/Lの濃度でそれぞれ溶解したこと以外は、比較例1と同様にして試験セルを作製した。
非水電解質の調製において、LiFSIを用いず、LiPF6を1.5mol/Lの濃度で溶解したこと以外は、実施例2と同様にして試験セルを作製した。
非水電解質の調製において、LiFSIを用いず、LiPF6を1.5mol/Lの濃度で溶解したこと以外は、比較例1と同様にして試験セルを作製した。
正極の作製において、複合酸化物(B1)の代わりに、下記複合酸化物(B10)を用いたこと以外は、実施例2と同様にして試験セルを作製した。
[複合酸化物(B10)の合成]
Li2O、NiOを、LiとNiのモル比が0.7:1.3となるように秤量し、これらを粉砕しつつ混合して混合物を作製した。次に、この混合物を、酸素雰囲気下、650℃で20時間焼成し、さらに解砕することで複合酸化物(B10)を得た。
試験セルを、40℃の温度環境下、0.3Cで電池電圧が4.3Vになるまで定電流充電を行い、4.3Vで電流値が0.02Cになるまで定電圧充電を行った。その後、0.05Cで電池電圧が2.5Vになるまで定電流放電を行った。この充放電を30サイクル行い、下記式に基づいて30サイクル後の容量維持率を求めた。表1に示す容量維持率は、比較例4の試験セルの容量維持率を基準(100)としたときの相対値である。
容量維持率=(30サイクル目の放電容量/1サイクル目の放電容量)×100
Claims (6)
- 正極合剤層を有する正極と、負極と、非水電解質とを備えた非水電解質二次電池において、
前記正極合剤層には、
一般式LixNi1-y-zCoyMzO2(式中、0.8≦x≦1.2、0≦y≦0.2、0<z≦0.5、MはLi、Ni、Coを除く少なくとも1種の金属元素)で表される第1リチウム遷移金属複合酸化物と、
一般式LiaNi2-a-bMebO2(式中、0<a≦0.5、0≦b≦0.5、MeはLi、Niを除く少なくとも1種の金属元素)で表される第2リチウム遷移金属複合酸化物と、
が含まれ、
前記非水電解質には、スルホニルイミド塩が含まれる、非水電解質二次電池。 - 前記第2リチウム遷移金属複合酸化物の含有量は、前記正極合剤層の総質量に対して0.1~10質量%である、請求項1に記載の非水電解質二次電池。
- 前記第2リチウム遷移金属複合酸化物は、放射光X線回折(光エネルギー16keV)の回折角(2θ)21.40°~21.65°にピークトップを有する少なくとも1つの回折ピークをもつ複合酸化物である、請求項1又は2に記載の非水電解質二次電池。
- 前記スルホニルイミド塩は、リチウムビス(フルオロスルホニル)イミド及びリチウムビス(トリフルオロメタンスルホニル)イミドから選択される少なくとも1種のリチウムスルホニルイミドである、請求項1~3のいずれか1項に記載の非水電解質二次電池。
- 前記スルホニルイミド塩は、前記非水電解質中において、0.1~1.5mol/Lの濃度で含有されている、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。
- 前記負極には、負極活物質として、炭素系活物質と、Si、Sn、Sb、Mg、及びGeから選択される少なくとも1種の金属元素及び当該金属元素を含有する化合物の少なくとも一方である第2の活物質とが含まれ、
前記第2の活物質の含有量は、前記負極活物質の総質量に対して1~15質量%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。
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