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WO2018123604A1 - Matériau actif d'électrode positive pour cellule secondaire à électrolyte non aqueux - Google Patents

Matériau actif d'électrode positive pour cellule secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2018123604A1
WO2018123604A1 PCT/JP2017/044813 JP2017044813W WO2018123604A1 WO 2018123604 A1 WO2018123604 A1 WO 2018123604A1 JP 2017044813 W JP2017044813 W JP 2017044813W WO 2018123604 A1 WO2018123604 A1 WO 2018123604A1
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transition metal
mol
metal oxide
positive electrode
lithium transition
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PCT/JP2017/044813
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English (en)
Japanese (ja)
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良憲 青木
元治 斉藤
正信 竹内
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パナソニックＩｐマネジメント株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • 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 positive electrode active material for a non-aqueous electrolyte secondary battery.
  • Ni-containing lithium transition metal oxide positive electrode active material of a lithium ion secondary battery e.g., LiNiO 2
  • Co-containing lithium transition metal oxides e.g., LiCoO 2
  • Nickel is expected to be a next-generation positive electrode material because it has advantages such as being cheaper than cobalt and being stably available.
  • Patent Document 1 includes a lithium transition metal oxide in which the ratio of Ni to the total molar amount of metal elements excluding lithium is more than 30 mol%, and the lithium transition metal oxide has an average particle size of 0.5 ⁇ m or more.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery which is a particle formed by aggregation of primary particles, and at least one of boron (B) and phosphorus (P) is fixed to the surface of the particle. It is disclosed. According to the positive electrode active material for a non-aqueous electrolyte secondary battery of Patent Document 1, it is disclosed that a non-aqueous electrolyte secondary battery excellent in thermal stability can be provided.
  • the initial charge / discharge efficiency is the ratio of the initial discharge capacity to the initial charge capacity.
  • the present disclosure provides a positive electrode active material for a non-aqueous electrolyte secondary battery that can improve initial charge / discharge efficiency and charge / discharge cycle characteristics while containing a lithium transition metal oxide having a high Ni content.
  • the purpose is to do.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery that is one embodiment of the present disclosure includes a Ni-containing lithium transition metal oxide having a layered structure, and the Ni-containing lithium transition metal oxide includes B (boron) and Si ( Silicon).
  • the Ni ratio ⁇ is in the range of 80 mol% ⁇ ⁇
  • the Si ratio ⁇ is in the range of 0 mol% ⁇ ⁇ 1 mol%.
  • a positive electrode active for a nonaqueous electrolyte secondary battery that can improve initial charge / discharge efficiency and charge / discharge cycle characteristics while containing a lithium transition metal oxide having a high Ni content.
  • a substance can be provided.
  • the initial charge / discharge efficiency and charge / discharge cycle characteristics of Ni-containing lithium transition metal oxides decrease with an increase in nickel content. This is because when the Ni content is high, the change in the crystal structure and the expansion and contraction of the crystal lattice of the Ni-containing lithium transition metal oxide accompanying the lithium desorption / insertion during the charging / discharging of the battery are increased, and the crystal structure associated therewith This is considered to be caused by the disappearance of lithium insertion sites, the decrease in diffusibility of lithium ions, and the like due to the decay of particles and particle destruction.
  • Ni-containing lithium transition metal oxide in which the ratio of Ni to the total molar amount of metal elements excluding lithium is 80 mol% or more is added to a predetermined amount of B ( It has been found that the presence / absence of boron and Si (silicon) improves the initial charge / discharge efficiency and charge / discharge cycle characteristics. Although this mechanism is not sufficiently clear, the following is presumed.
  • the presence of a predetermined amount of B and Si in the Ni-containing lithium transition metal oxide not only strengthens the crystal structure, but also changes the electronic state of the crystal structure, thereby reducing the crystal lattice due to lithium ion desorption. It is thought that expansion and contraction are suppressed. In addition, it is considered that the destruction of the crystal structure and particle destruction accompanying this are suppressed, and the disappearance of the lithium insertion site and the decrease in the diffusibility of lithium ions are also suppressed. From these facts, it is considered that the initial charge / discharge efficiency and the charge / discharge cycle characteristics are improved.
  • the initial charge / discharge efficiency is improved as compared with the Ni-containing lithium transition metal oxide not containing B and Si, but the charge / discharge cycle The characteristics are degraded. This is because, for example, when a predetermined amount of B is present in the Ni-containing lithium transition metal oxide, for example, lithium ion desorption and lithium ion diffusibility are improved, but on the other hand, the strength of the crystal structure is reduced. This is considered to be the cause.
  • the charge / discharge cycle characteristics are improved as compared with the Ni-containing lithium transition metal oxide not containing B and Si, but the initial charge / discharge efficiency is improved. Decreases. This is because the presence of a predetermined amount of Si in the Ni-containing lithium transition metal oxide improves, for example, the strength of the crystal structure, while the Li diffusibility in the crystal structure decreases. It is believed that there is. That is, both the effects of improving the initial charge / discharge efficiency and the charge / discharge cycle characteristics are brought about only when a predetermined amount of B and Si coexist in the Ni-containing lithium transition metal oxide.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery that is one embodiment of the present disclosure includes a Ni (nickel) -containing lithium transition metal oxide having a layered structure.
  • the said Ni containing lithium transition metal oxide contains B (boron) and Si (silicon), and the ratio (alpha) of Ni with respect to the total molar amount of the metal element except the lithium in the said lithium transition metal oxide is 80 mol%.
  • ⁇ ⁇ the B ratio ⁇ is in the range of 0 mol% ⁇ ⁇ 0.5 mol%
  • the Si ratio ⁇ is in the range of 0 mol% ⁇ ⁇ 1 mol%.
  • the predetermined amount of B, Si and Ni-containing lithium transition metal oxide is simply referred to as Ni-containing lithium transition metal oxide.
  • B and Si contained in the Ni-containing lithium transition metal oxide may be uniformly dispersed in the crystal structure of the Ni-containing lithium transition metal oxide, or may exist in a part of the crystal structure. Also good. Further, in the production stage of the Ni-containing lithium transition metal oxide, a part of B contained in the crystal structure may be deposited on the particle surface of the Ni-containing lithium transition metal oxide as lithium borate. B in the obtained lithium borate is also B contained in the Ni-containing lithium transition metal oxide. Similarly, Si may be deposited on the particle surface as lithium silicon oxide, and Si in the deposited lithium silicon oxide is Si contained in the Ni-containing lithium transition metal oxide.
  • the Ni ratio ⁇ in the Ni-containing lithium transition metal oxide is preferably in the range of 80 mol% ⁇ ⁇ ⁇ 100 mol%, for example, in view of increasing the capacity of the battery, stability of the crystal structure, and the like, and 85 mol% ⁇ ⁇ ⁇ 100 mol% is more preferable.
  • the ratio ⁇ of B in the Ni-containing lithium transition metal oxide may be in the range of 0 mol% ⁇ ⁇ 0.5 mol%, for example, in that the initial charge / discharge efficiency can be further improved.
  • the range is 0 mol% ⁇ ⁇ 0.3 mol%.
  • the proportion ⁇ of Si in the Ni-containing lithium transition metal oxide is preferably in the range of 0 mol% ⁇ ⁇ 1 mol%, for example, in that the charge / discharge cycle characteristics can be further improved. More preferably, the range is 0 mol% ⁇ ⁇ 0.8 mol%.
  • Examples of the layered structure of the Ni-containing lithium transition metal oxide 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 from the viewpoint of increasing the capacity and stability of the crystal structure.
  • Ni-containing lithium transition metal oxide is not particularly limited as long as it is a lithium transition metal oxide containing the above-mentioned predetermined amounts of Ni, B, and Si, but may contain other metal elements, for example, A Ni-containing lithium transition metal oxide represented by the following composition formula is preferable.
  • M is a metal element other than Ni, Co, B, and Si.
  • M is a metal element other than Ni, Co, B, and Si.
  • M is a metal element other than Ni, Co, B, and Si.
  • metal elements are mentioned.
  • metal elements other than these metal elements may be used.
  • X in the composition formula (1) indicates the content (molar ratio) of lithium (Li) with respect to the total amount of Ni, Co, M, B, and Si.
  • the lithium content x in the composition formula (1) is preferably in the range of 0.95 ⁇ x ⁇ 1.05 in that, for example, the charge / discharge capacity of the nonaqueous electrolyte secondary battery can be improved. 0.98 ⁇ x ⁇ 1 is more preferable.
  • ⁇ in the composition formula (1) indicates the content (molar ratio) of nickel (Ni) with respect to the total amount of Ni, Co, M, B, and Si.
  • the nickel content ⁇ in the composition formula (1) is preferably in the range of 0.80 ⁇ ⁇ ⁇ 1, for example, in that the charge / discharge capacity of the nonaqueous electrolyte secondary battery can be improved. More preferably, 85 ⁇ ⁇ 1.
  • P in the composition formula (1) indicates the content (molar ratio) of cobalt (Co) with respect to the total amount of Ni, Co, M, B, and Si.
  • the cobalt content p in the composition formula (1) is, for example, in the range of 0 ⁇ p ⁇ 0.15 in that the charge / discharge cycle characteristics and the charge / discharge capacity of the nonaqueous electrolyte secondary battery can be improved. Is more preferable, and 0.03 ⁇ p ⁇ 0.12 is more preferable.
  • Q in the composition formula (1) indicates the content (molar ratio) of M with respect to the total amount of Ni, Co, M, B, and Si.
  • the content q of M in the composition formula (1) is, for example, in the range of 0 ⁇ q ⁇ 0.15 in that the charge / discharge cycle characteristics and charge / discharge capacity of the nonaqueous electrolyte secondary battery can be improved. It is preferable that the range is 0.005 ⁇ q ⁇ 0.1.
  • ⁇ and ⁇ in the composition formula (1) indicate the content (molar ratio) of boron (B) and the content (molar ratio) of silicon (Si) with respect to the total amount of Ni, Co, M, B, and Si.
  • the boron content ⁇ and the silicon content ⁇ in the composition formula (1) are 0 ⁇ ⁇ 0.005 in that the charge / discharge cycle and the initial charge / discharge efficiency of the nonaqueous electrolyte secondary battery can be improved.
  • lithium borate may produce
  • silicon oxide when there is too much content of silicon, a large amount of lithium silicon oxide will produce
  • “2-y” in the composition formula (1) indicates the content (molar ratio) of oxygen atoms (O) with respect to the total amount of Ni, Co, M, B, and Si.
  • y represents the amount of oxygen deficiency, and when the value of y increases, the amount of divalent Ni increases accordingly, so-called “rock chloride” in which the layered structure becomes a rock salt structure occurs, and the charge / discharge capacity May decrease.
  • y which is an acceleration factor of rock chloride, be in the range of 0 ⁇ y ⁇ 0.05, for example.
  • ICP-AES inductively coupled plasma optical emission spectrometer
  • EPMA electron microanalyzer
  • EDX energy dispersive X-ray analyzer
  • the lattice constant a indicating the a-axis length of the crystal structure obtained from the result of the X-ray diffraction pattern by X-ray diffraction is in the range of 2.866 ⁇ ⁇ a ⁇ 2.873 ⁇
  • the c-axis The lattice constant c indicating the length is preferably in the range of 14.1714 ⁇ c ⁇ 14.20 ⁇ .
  • the lattice constant a is 2.873 ⁇ or more
  • the interatomic distance in the crystal structure is wide and unstable, and the output of the nonaqueous electrolyte secondary battery is higher than that in the case where the above range is satisfied.
  • the characteristics may deteriorate.
  • the lattice constant c is 14.17 mm or less
  • the interatomic distance in the crystal structure is narrow and unstable, and the nonaqueous electrolyte secondary battery is charged as compared with the case where the above range is satisfied. Discharge cycle characteristics may deteriorate.
  • the lattice constant c is 14.20 mm or more
  • the interatomic distance in the crystal structure is wide and unstable, and the nonaqueous electrolyte secondary battery is charged as compared with the case where the above range is satisfied. Discharge cycle characteristics may deteriorate.
  • the X-ray diffraction pattern of the Ni-containing lithium transition metal oxide was determined by using a powder X-ray diffractometer (trade name “RINT-TTR”, source Cu-K ⁇ , manufactured by Rigaku Corporation) with the following conditions: Obtained by diffraction method.
  • the Ni-containing lithium transition metal oxide has a transition metal amount m present at the 3a site (lithium site) in the crystal structure obtained from the Rietveld analysis result of the X-ray diffraction pattern by X-ray diffraction. It is preferably included in the range of 0 mol ⁇ m ⁇ 2 mol% with respect to the total molar amount.
  • the amount of transition metal m present at the 3a site (lithium site) in the crystal structure exceeds 2 mol% with respect to the total molar amount of the transition metal, the crystal structure is distorted and lithium in the Ni-containing lithium transition metal oxide Ion diffusivity may be reduced.
  • the Rietveld analysis result of the X-ray diffraction pattern can be obtained by using PDXL2 (Rigaku Corporation) which is Rietveld analysis software.
  • the Ni-containing lithium transition metal oxide has a crystallite size s calculated from Scherrer's equation (Scherrer equation) from the half-value width of the diffraction peak of the (104) plane of the X-ray diffraction pattern by X-ray diffraction is 300 ⁇ ⁇ s ⁇ . It is preferably 800cm.
  • the crystallite size s of the Ni-containing lithium transition metal oxide is smaller than 300 mm, the crystallinity is lowered, and the charge / discharge cycle characteristics of the nonaqueous electrolyte secondary battery are lowered as compared with the case where the above range is satisfied. There is a case.
  • Equation (2) s is the crystallite size, ⁇ is the X-ray wavelength, B is the half width of the diffraction peak of the (104) plane, ⁇ is the diffraction angle (rad), and K is the Scherrer constant. In this embodiment, K is 0.9.
  • the content of the Ni-containing lithium transition metal oxide is, for example, 90% with respect to the total mass of the positive electrode active material for a non-aqueous electrolyte secondary battery in that the charge / discharge capacity of the non-aqueous electrolyte secondary battery can be improved. It is preferable that it is mass% or more, and it is preferable that it is 99 mass% or more.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery of the present embodiment may contain other lithium transition metal oxides in addition to the Ni-containing lithium transition metal oxide.
  • other lithium transition metal oxides include lithium transition metal oxides having a Ni content of 0 mol% to less than 80 mol%, and the lithium transition metal oxides include B, Si, and other metal elements. And lithium transition metal oxides.
  • Li-containing compound hereinafter sometimes referred to as Li raw material
  • Ni-containing metal raw material a metal-containing compound containing Ni
  • B-containing compound a B-containing compound
  • Si-containing compound a Si-containing compound at a target mixing ratio and firing the mixture.
  • the mixture is fired, for example, in the air or in an oxygen stream.
  • the firing temperature is, for example, about 650 ° C. to 800 ° C.
  • the firing time is, for example, about 1 to 10 hours.
  • Each parameter such as the lattice constant a, the lattice constant c, the amount of transition metal m present at the 3a site (lithium site) in the crystal structure, and the crystallite size s in the Ni-containing lithium transition metal oxide is, for example, It adjusts by controlling the molar ratio of each metal element in the mixture which mixed each raw material, baking temperature, baking time, etc. In particular, it is preferable to control the molar ratio of each metal element in the mixture in terms of easy adjustment of the above parameters.
  • the Li raw material so that the molar ratio L of Li to the gold element excluding Li in the mixture is in the range of 1.03 ⁇ L ⁇ 1.3, and 1.04 ⁇ L It is more preferable to add the Li raw material so as to be in the range of ⁇ 1.2.
  • the molar ratio L of Li to the gold element other than Li in the mixture is 1.03 or less, or 1.3 or more, it may be difficult to adjust each of the parameters to the specified range.
  • a method for synthesizing a Ni-containing lithium transition metal oxide for example, after firing a mixture A in which a Li raw material and a metal raw material containing Ni are fired, the obtained fired product, B raw material, and Si raw material are used.
  • the method of mixing and baking the said mixture B is mentioned.
  • a nonaqueous electrolyte secondary battery includes, for example, an electrode body in which a positive electrode and a negative electrode are wound or stacked with a separator interposed therebetween, a nonaqueous electrolyte, and an exterior body in which the electrode body and the nonaqueous electrolyte are accommodated.
  • the form of the nonaqueous electrolyte secondary battery is not particularly limited, and examples thereof include a cylindrical shape, a square shape, a coin shape, a button shape, and a laminate shape.
  • the positive electrode includes a positive electrode current collector such as a metal foil and a positive electrode active material layer formed on the positive electrode current collector.
  • a positive electrode current collector such as a metal foil and a positive electrode active material layer formed on the positive electrode current collector.
  • a metal foil that is stable in the potential range of the positive electrode such as aluminum, a film in which the metal is disposed on the surface layer, or the like can be used.
  • the positive electrode active material layer includes, for example, a positive electrode active material for a non-aqueous electrolyte secondary battery including the aforementioned Ni-containing lithium transition metal oxide, a conductive material, and a binder.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery containing the Ni-containing lithium transition metal oxide is as described above, and the description thereof is omitted.
  • the conductive material examples include carbon materials such as carbon black, acetylene black, ketjen black, and graphite.
  • the content of the conductive material is preferably 0.1 to 30% by mass, and preferably 0.1 to 20% by mass with respect to the total mass of the positive electrode active material layer in terms of improving the conductivity of the positive electrode active material layer. More preferred is 0.1 to 10% by mass.
  • binder for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyvinyl acetate, polymethacrylate, polyacrylate, polyacrylonitrile, polyvinyl alcohol, or the like is used.
  • the binder may be used in combination with a thickener such as carboxymethyl cellulose (CMC) or polyethylene oxide (PEO).
  • CMC carboxymethyl cellulose
  • PEO polyethylene oxide
  • the content of the binder is preferably 0.1 to 30% by mass with respect to the total mass of the positive electrode active material layer, for example, in terms of improving the adhesion between the positive electrode active material layer and the positive electrode current collector. More preferably, it is 1 to 20% by mass, and particularly preferably 0.1 to 10% by mass.
  • the negative electrode includes, for example, a negative electrode current collector such as a metal foil, and a negative electrode active material layer formed on the surface of the negative electrode current collector.
  • a negative electrode current collector such as a metal foil
  • a negative electrode active material layer formed on the surface of the negative electrode current collector.
  • the negative electrode active material layer preferably contains a binder in addition to the negative electrode active material capable of inserting and extracting lithium ions. Further, a conductive material may be included as necessary.
  • the negative electrode active material examples include natural graphite, artificial graphite, lithium, silicon, carbon, tin, germanium, aluminum, lead, indium, gallium, lithium alloy, carbon in which lithium is occluded in advance, silicon, and alloys thereof. Is mentioned.
  • the binder the same material as in the case of the positive electrode may be used. However, it is preferable to use a styrene-butadiene copolymer (SBR) or a modified product thereof.
  • SBR styrene-butadiene copolymer
  • the binder may be used in combination with a thickener such as CMC.
  • the non-aqueous electrolyte includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the nonaqueous electrolyte is not limited to a liquid electrolyte (nonaqueous electrolyte solution), and may be a solid electrolyte using a gel polymer or the like.
  • 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.
  • esters include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, acetic acid
  • carboxylic acid esters such as methyl, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and ⁇ -butyrolactone.
  • ethers include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 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-cineol, crown ether, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, Dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether
  • the non-aqueous solvent preferably contains a halogen substitution product obtained by substituting hydrogen of the above various solvents with a halogen atom such as fluorine.
  • a fluorinated cyclic carbonate and a fluorinated chain carbonate are preferable, and it is more preferable to use a mixture of both. Thereby, a good protective film is formed not only in the negative electrode but also in the positive electrode, and the cycle characteristics are improved.
  • Preferred examples of the fluorinated cyclic carbonate include 4-fluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,4,5-trifluoroethylene carbonate, 4,4,5 , 5-tetrafluoroethylene carbonate and the like.
  • Preferable examples of the fluorinated chain ester include ethyl 2,2,2-trifluoroacetate, methyl 3,3,3-trifluoropropionate, methyl pentafluoropropionate and the like.
  • the electrolyte salt is preferably a lithium salt.
  • lithium salts include LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 , LiN (C 1 F 2l + 1 SO 2 ) (C m F 2m + 1 SO 2 ) (l , m is an integer of 1 or more), LiC (C p F2 p + 1 SO 2) (C q F 2q + 1 SO 2) (C r F 2r + 1 SO 2) (p, q, r is an integer of 1 or more), Li [B (C 2 O 4 ) 2 ] (bis (oxalate) lithium borate (LiBOB)), Li [B (C 2 O 4 ) F 2 ], Li [P (C 2 O 4 ) F 4 ], Li [P (C 2 O 4 ) 2 F 2 ], LiPO 2 F 2 and the like.
  • a porous sheet having ion permeability and insulating properties is used.
  • the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
  • olefinic resins such as polyethylene and polypropylene, cellulose and the like are suitable.
  • the separator may be a laminate having a cellulose fiber layer and a thermoplastic resin fiber layer such as an olefin resin.
  • Example 1 [Preparation of positive electrode active material (Ni-containing lithium transition metal oxide)]
  • Ni 0.88 Co 0.09 Al 0.03 (OH) 2 was obtained by coprecipitation and then heat-treated at 500 ° C. to prepare a composite oxide.
  • LiOH, the composite oxide, H 3 BO 3 and SiO are combined with Li, the sum of transition metals (Ni, Co and Al), and the molar ratio of B and Si is 1.1: 1: 0.01: 0. Mixed in an amount of .01. Thereafter, the mixture was fired in an oxygen stream at 670 ° C. for 1 hour, and then subjected to two-stage firing at 710 ° C.
  • Ni-containing lithium transition metal oxide was measured using an ICP emission spectroscopic analyzer (manufactured by Thermo Fisher Scientific, trade name “iCAP6300”). As a result, the composition formula of the obtained Ni-containing lithium transition metal oxide was Li 0.98 Ni 0.88 Co 0.09 Al 0.03 B 0.001 Si 0.002 O 2 .
  • the ratio of B to the total molar amount of the metal elements excluding lithium in the Ni-containing lithium transition metal oxide (hereinafter simply referred to as B ratio) is 0.1 mol%, and the Ni-containing lithium transition metal oxide
  • the ratio of Si to the total molar amount of the metal elements excluding lithium therein (hereinafter simply referred to as Si ratio) was 0.2 mol%. This was used as the positive electrode active material of Example 1.
  • Ethylene carbonate (EC), methyl ethyl carbonate (MEC), and dimethyl carbonate (DMC) were mixed at a volume ratio of 3: 3: 4.
  • a nonaqueous electrolyte was prepared by dissolving lithium hexafluorophosphate (LiPF 6 ) in the mixed solvent so as to have a concentration of 1.2 mol / liter.
  • test cell The positive electrode and a negative electrode made of lithium metal foil were laminated so as to face each other with a separator interposed therebetween, and this was wound to produce an electrode body. Next, the electrode body and the non-aqueous electrolyte were inserted into an aluminum exterior body to produce a test cell.
  • Example 2 In the preparation of the positive electrode active material, LiOH, the above composite oxide, H 3 BO 3 and SiO were combined with Li, the sum of transition metals (Ni, Co and Al), and the molar ratio of B and Si was 1.15: 1: 0. 0.03: A Ni-containing lithium transition metal oxide was produced in the same manner as in Example 1 except that the amount was 0.01. The composition formula of the Ni-containing lithium transition metal oxide was Li 0.98 Ni 0.88 Co 0.09 Al 0.03 B 0.002 Si 0.003 O 2 . That is, the ratio of B was 0.2 mol%, and the ratio of Si was 0.3 mol%. Using this as the positive electrode active material of Example 2, a test cell was produced in the same manner as in Example 1.
  • Example 3 In the preparation of the positive electrode active material, LiOH, the above composite oxide, H 3 BO 3 and SiO are combined with Li, the sum of transition metals (Ni, Co and Al), and the molar ratio of B and Si is 1.13: 1: 0. 0.01: A Ni-containing lithium transition metal oxide was prepared in the same manner as in Example 1 except that it was mixed in an amount of 0.015.
  • the composition formula of the Ni-containing lithium transition metal oxide was Li 0.98 Ni 0.88 Co 0.09 Al 0.03 B 0.001 Si 0.007 O 2 . That is, the ratio of B was 0.1 mol%, and the ratio of Si was 0.7 mol%.
  • a test cell was produced in the same manner as in Example 1.
  • Example 4 In the preparation of the positive electrode active material, LiOH, the above composite oxide, H 3 BO 3 and SiO were combined with Li, the sum of transition metals (Ni, Co and Al), and the molar ratio of B and Si was 1.15: 1: 0. 0.02: A Ni-containing lithium transition metal oxide was prepared in the same manner as in Example 1 except that the amount of mixing was 0.015.
  • the composition formula of the Ni-containing lithium transition metal oxide was Li 0.98 Ni 0.88 Co 0.09 Al 0.03 B 0.002 Si 0.007 O 2 . That is, the ratio of B was 0.2 mol%, and the ratio of Si was 0.7 mol%.
  • a test cell was produced in the same manner as in Example 1.
  • Example 5 In the preparation of the positive electrode active material, LiOH, the above composite oxide, H 3 BO 3 and SiO are combined with Li, the sum of transition metals (Ni, Co and Al), and the molar ratio of B and Si is 1.18: 1: 0. 0.03: A Ni-containing lithium transition metal oxide was produced in the same manner as in Example 1 except that the amount of mixing was 0.015.
  • the composition formula of the Ni-containing lithium transition metal oxide was Li 0.98 Ni 0.88 Co 0.09 Al 0.03 B 0.003 Si 0.007 O 2 . That is, the ratio of B was 0.3 mol%, and the ratio of Si was 0.7 mol%.
  • a test cell was produced in the same manner as in Example 1.
  • ⁇ Comparative example 2> In the preparation of the positive electrode active material, SiO is not used, LiOH, the above composite oxide, and H 3 BO 3 are combined with Li, the total of transition metals (Ni, Co, and Al), and the molar ratio of B is 1.07: 1. : A Ni-containing lithium transition metal oxide was prepared in the same manner as in Example 1 except that it was mixed in an amount of 0.01. The composition formula of the Ni-containing lithium transition metal oxide was Li 0.98 Ni 0.88 Co 0.09 Al 0.03 B 0.001 O 2 . That is, the ratio of B was 0.1 mol% (the ratio of Si was 0 mol%). Using this as the positive electrode active material of Comparative Example 2, a test cell was produced in the same manner as in Example 1.
  • ⁇ Comparative Example 3> In the preparation of the positive electrode active material, SiO is not used, LiOH, the above composite oxide, and H 3 BO 3 are combined with Li, the total of transition metals (Ni, Co, and Al), and the molar ratio of B is 1.1: 1. : A Ni-containing lithium transition metal oxide was prepared in the same manner as in Example 1 except that it was mixed in an amount of 0.03. The composition formula of the Ni-containing lithium transition metal oxide was Li 0.98 Ni 0.88 Co 0.09 Al 0.03 B 0.003 O 2 . That is, the proportion of B was 0.3 mol% (the proportion of Si was 0 mol%). Using this as the positive electrode active material of Comparative Example 3, a test cell was produced in the same manner as in Example 1.
  • ⁇ Comparative example 4> In the preparation of the positive electrode active material, H 3 BO 3 is not used, LiOH, the above composite oxide, and SiO are combined with Li, transition metals (Ni, Co, and Al), and the molar ratio of Si is 1.03: 1. : A Ni-containing lithium transition metal oxide was prepared in the same manner as in Example 1 except that it was mixed in an amount of 0.01. The composition formula of the Ni-containing lithium transition metal oxide was Li 0.98 Ni 0.88 Co 0.09 Al 0.03 Si 0.002 O 2 . That is, the proportion of Si was 0.2 mol% (the proportion of B was 0 mol%). Using this as the positive electrode active material of Comparative Example 4, a test cell was produced in the same manner as in Example 1.
  • ⁇ Comparative Example 5> In the preparation of the positive electrode active material, H 3 BO 3 is not used, LiOH, the above composite oxide, and SiO are combined with Li, transition metals (Ni, Co, and Al), and the molar ratio of Si is 1.05: 1. : A Ni-containing lithium transition metal oxide was prepared in the same manner as in Example 1 except that it was mixed in an amount of 0.015. The composition formula of the Ni-containing lithium transition metal oxide was Li 0.98 Ni 0.88 Co 0.09 Al 0.03 B 0.001 Si 0.003 O 2 . That is, the proportion of Si was 0.3 mol% (the proportion of B was 0 mol%). Using this as the positive electrode active material of Comparative Example 5, a test cell was produced in the same manner as in Example 1.
  • test cells of Examples 1 to 5 and Comparative Examples 1 to 5 used for measuring the direct current resistance value are obtained by replacing the lithium metal foil of the negative electrode with a graphite electrode.
  • the battery was charged to SOC 10% at a constant current of 8 mA under a temperature condition of 25 ° C. Charging to SOC 10% means charging to 10% when the full charge of the test cell is 100%.
  • constant voltage charging was performed at 4.3 V until the current value reached 0.4 mA.
  • the battery was charged to 100% SOC at a constant current of 8 mA under a temperature condition of 25 ° C.
  • constant voltage charging was performed at 4.3 V until the current value reached 0.4 mA.
  • a current was passed at 20 mA for 10 seconds, and the difference ⁇ V between the voltage of the test cell before passing the current and the voltage of the test cell through which the current was passed for 10 seconds was measured.
  • ⁇ V was divided by the 20 mA current value, and the DC resistance value at SOC 100% was obtained.
  • Table 1 summarizes the ratios of B and Si in the Ni-containing transition metal oxides used in the examples and comparative examples. Table 1 summarizes the initial charge / discharge efficiency, capacity maintenance ratio, DC resistance values at SOC 10% and SOC 100% in the test cells of each Example and each Comparative Example.
  • FIG. 1 is a diagram showing X-ray diffraction patterns in each example and each comparative example. In all examples and comparative examples, diffraction lines showing a layered structure were confirmed.
  • Example 1 to 5 the initial charge / discharge efficiency and the capacity retention rate were both higher than those of Comparative Examples 1 to 5. From this result, B (boron) and Si (silicon) are present in the Ni (nickel) -containing lithium transition metal oxide having a layered structure, and the total molar amount of metal elements excluding lithium in the Ni-containing lithium transition metal oxide In contrast, the Ni ratio ⁇ is in the range of 80 mol% ⁇ ⁇ , the B ratio ⁇ is in the range of 0 mol% ⁇ ⁇ 0.5 mol%, and the Si ratio ⁇ is in the range of 0 mol% ⁇ ⁇ 1 mol%. Thus, it can be said that the initial charge / discharge efficiency and the charge / discharge cycle characteristics can be improved.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne un matériau actif d'électrode positive pour une cellule secondaire à électrolyte non aqueux contenant un oxyde métallique de transition de lithium contenant du Ni ayant une structure en couches, et l'oxyde métallique de transition de lithium contenant du Ni contient du B (bore) et du Si (silicium). Par rapport à la quantité molaire totale des éléments métalliques à l'exclusion du lithium dans l'oxyde métallique de transition de lithium, la proportion de Ni α est dans la plage de 80 % en moles ≤ α, la proportion de B β est dans la plage de 0 % en moles < β ≤ 0,5 % en moles, et la proportion de Si γ est dans la plage de 0 % en moles < γ ≤ 1 % en moles.
PCT/JP2017/044813 2016-12-27 2017-12-14 Matériau actif d'électrode positive pour cellule secondaire à électrolyte non aqueux WO2018123604A1 (fr)

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CN114792785A (zh) * 2021-01-25 2022-07-26 泰星能源解决方案有限公司 非水电解质二次电池
JP2025073089A (ja) * 2023-10-25 2025-05-12 エコプロ ビーエム カンパニー リミテッド 正極活物質、正極およびこれを含むリチウム二次電池

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JP2025014965A (ja) * 2023-07-20 2025-01-30 プライムプラネットエナジー＆ソリューションズ株式会社 正極およびこれを用いた二次電池

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JPH08213052A (ja) * 1994-08-04 1996-08-20 Seiko Instr Inc 非水電解質二次電池
JPH1140154A (ja) * 1997-07-18 1999-02-12 Hitachi Ltd 電極及びこれを用いた電池
JP2001196062A (ja) * 2000-01-12 2001-07-19 Mitsui Mining & Smelting Co Ltd マンガン酸リチウム混成体及びこれを用いたリチウム二次電池
JP2004303673A (ja) * 2003-04-01 2004-10-28 Hitachi Ltd リチウム二次電池用正極材料
WO2013008581A1 (fr) * 2011-07-13 2013-01-17 日本電気株式会社 Matériau actif destiné à des batteries rechargeables

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Publication number Priority date Publication date Assignee Title
JPH08213052A (ja) * 1994-08-04 1996-08-20 Seiko Instr Inc 非水電解質二次電池
JPH1140154A (ja) * 1997-07-18 1999-02-12 Hitachi Ltd 電極及びこれを用いた電池
JP2001196062A (ja) * 2000-01-12 2001-07-19 Mitsui Mining & Smelting Co Ltd マンガン酸リチウム混成体及びこれを用いたリチウム二次電池
JP2004303673A (ja) * 2003-04-01 2004-10-28 Hitachi Ltd リチウム二次電池用正極材料
WO2013008581A1 (fr) * 2011-07-13 2013-01-17 日本電気株式会社 Matériau actif destiné à des batteries rechargeables

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114792785A (zh) * 2021-01-25 2022-07-26 泰星能源解决方案有限公司 非水电解质二次电池
CN114792785B (zh) * 2021-01-25 2024-02-23 泰星能源解决方案有限公司 非水电解质二次电池
JP2025073089A (ja) * 2023-10-25 2025-05-12 エコプロ ビーエム カンパニー リミテッド 正極活物質、正極およびこれを含むリチウム二次電池

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