WO2014083848A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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WO2014083848A1
WO2014083848A1 PCT/JP2013/006978 JP2013006978W WO2014083848A1 WO 2014083848 A1 WO2014083848 A1 WO 2014083848A1 JP 2013006978 W JP2013006978 W JP 2013006978W WO 2014083848 A1 WO2014083848 A1 WO 2014083848A1
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secondary battery
electrolyte secondary
carbonate
lithium
positive electrode
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PCT/JP2013/006978
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English (en)
Japanese (ja)
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高橋　康文
明宏 前田
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三洋電機株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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

  • the present invention relates to a non-aqueous electrolyte secondary battery.
  • lithium-containing transition metal oxides produced by ion-exchange of sodium-containing transition metal oxides have been studied (see Non-Patent Document 1).
  • One kind of such lithium-containing transition metal oxides is different from a positive electrode active material (such as lithium cobaltate (LiCoO 2) having a crystal structure belonging to space group R-3m) that is currently in practical use, and is a crystal belonging to space group P6 3 mc. It has a structure.
  • the lithium-containing transition metal oxide having a crystal structure belonging to the space group P6 3 mc can be charged / discharged even when about 80% of the lithium in the oxide is extracted, and is a promising candidate for the next generation high capacity positive electrode active material. It is.
  • a non-aqueous electrolyte secondary battery using a lithium-containing transition metal oxide having a crystal structure belonging to the space group P6 3 mc as a positive electrode active material has a problem in charge / discharge cycle characteristics.
  • the non-aqueous electrolyte secondary battery according to the present invention is a non-aqueous electrolyte secondary battery including a positive electrode including a positive electrode active material, a negative electrode, and a non-aqueous electrolyte including a non-aqueous solvent.
  • the non-aqueous solvent contains a lithium-containing transition metal oxide having a crystal structure belonging to 3 mc, the non-aqueous solvent being 7% by volume or more and 70% by volume or less of a fluorinated cyclic carbonate and 30% as a chain carbonate And at least one of methyl ethyl carbonate and diethyl carbonate in an amount of not less than volume% and not more than 93 volume%.
  • a nonaqueous electrolyte secondary battery having a high energy density and excellent charge / discharge cycle characteristics can be provided.
  • a nonaqueous electrolyte secondary battery which is an example of an embodiment of the present invention includes a positive electrode including a positive electrode active material, a negative electrode, and a nonaqueous electrolyte including a nonaqueous solvent.
  • a separator between the positive electrode and the negative electrode.
  • the nonaqueous electrolyte secondary battery has, for example, a structure in which an electrode body in which a positive electrode and a negative electrode are wound via a separator and a nonaqueous electrolyte are accommodated in an exterior body.
  • the positive electrode includes, for example, 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.
  • the positive electrode active material layer preferably includes a conductive agent and a binder in addition to the positive electrode active material.
  • the positive electrode active material includes a lithium-containing transition metal oxide having a crystal structure belonging to the space group P6 3 mc.
  • a crystal structure belongs to the space group P6 3 mc and is defined by, for example, an O 2 structure.
  • the O2 structure is a structure in which lithium is present in the center of the oxygen octahedron and two types of overlapping of oxygen and transition metal oxide exist per unit cell.
  • the positive electrode active material may contain other oxides such as LiNi a Co b Mn c O 2 having an O3 structure belonging to the space group C2 / m, C2 / c, or R-3m within a range that does not impair the object of the present invention.
  • the O3 structure is common to the O2 structure in that lithium is present at the center of the oxygen octahedron, but differs from the O2 structure in that there are three types of overlapping of oxygen and transition metal oxide per unit lattice.
  • the lithium-containing transition metal oxide is Li x1 Na y1 Co ⁇ 1 M ⁇ 1 O ⁇ 1 (0.66 ⁇ x1 ⁇ 1.1, 0 ⁇ y1 ⁇ 0.05, 0.75 ⁇ ⁇ 1 ⁇ 1.0, 0 ⁇ Those represented by ⁇ 1 ⁇ 0.25, 1.8 ⁇ ⁇ 1 ⁇ 2.2) are preferable.
  • M is a metal element other than lithium (Li), sodium (Na), and cobalt (Co), and is preferably at least manganese (Mn).
  • x1 is less than the above range (0.66), the amount of lithium that can be involved in charge / discharge decreases, and the theoretical capacity decreases. On the other hand, when x1 is larger than the above range (1.1), lithium enters the transition metal site and the capacity density decreases.
  • y1 is larger than the above range (0.05), the crystal structure is likely to be broken when sodium is inserted and desorbed.
  • y1 is more preferably 0.02 or less, and the crystal structure is further stabilized by satisfying y1 ⁇ 0.02.
  • sodium may not be detected by powder X-ray diffraction measurement.
  • ⁇ 1 When ⁇ 1 is less than the above range (0.75), the discharge potential is lowered. If ⁇ 1 is larger than the above range (1.0), a positive crystal potential is high (eg, 4.6 V (vs. Li / Li + )), and a stable crystal structure cannot be obtained in the charging process. It is more preferable that ⁇ 1 is in the range of 0.80 to 0.95 because the energy density is further increased.
  • M is preferably at least Mn as described above.
  • M is only Mn, when ⁇ 1 is larger than the above range (0.25), the discharge capacity density of 3.2 V or less increases, and as a result, the average discharge potential is lowered.
  • M is a metal element other than Mn, such as magnesium (Mg), nickel (Ni), zirconium (Zr), molybdenum (Mo), tungsten (W), aluminum (Al), chromium (Cr), vanadium (V ), Cerium (Ce), titanium (Ti), iron (Fe), potassium (K), gallium (Ga), indium (In), and the like.
  • Mg magnesium
  • Ni nickel
  • Zr zirconium
  • Mo molybdenum
  • Al aluminum
  • Cr chromium
  • V vanadium
  • Cerium (Ce) Cerium
  • iron (Fe) iron
  • K gallium
  • Ga indium
  • In indium
  • at least one selected from the other metal elements in addition to Mn is added to the lithium-containing transition metal oxide.
  • Ti is particularly preferable.
  • the addition amount of these elements is preferably 10 mol% or less with respect to the total molar amount of Co and M
  • the surface of the lithium-containing transition metal oxide may be covered with fine particles of an oxide such as aluminum oxide (Al 2 O 3 ), an inorganic compound such as a phosphoric acid compound, or a boric acid compound.
  • an oxide such as aluminum oxide (Al 2 O 3 )
  • an inorganic compound such as a phosphoric acid compound, or a boric acid compound.
  • the lithium-containing transition metal oxide is preferably prepared by ion exchange of sodium in the sodium-containing transition metal oxide with lithium.
  • Sodium-containing transition metal oxides include, for example, sodium and lithium that does not exceed the molar amount of sodium. Specifically, Li x2 Na y2 Co ⁇ 2 M ⁇ 2 O ⁇ 2 (0 ⁇ x2 ⁇ 0.1, 0.66 ⁇ y2 ⁇ 0.75, 0.75 ⁇ ⁇ 2 ⁇ 1, 0 ⁇ ⁇ 2 ⁇ 0.25, Those represented by 1.9 ⁇ ⁇ 2 ⁇ 2.1) are preferred.
  • Examples of the method for ion-exchanging sodium to lithium include at least one selected from the group consisting of lithium nitrate, lithium sulfate, lithium chloride, lithium carbonate, lithium hydroxide, lithium iodide, lithium bromide, and lithium chloride.
  • a method of adding a molten salt bed of lithium salt to a sodium-containing transition metal oxide is mentioned.
  • a method of immersing a sodium-containing transition metal oxide in a solution containing at least one lithium salt can be given.
  • the conductive agent is used to increase the electrical conductivity of the positive electrode active material layer.
  • the conductive agent include carbon materials such as carbon black, acetylene black, ketjen black, and graphite. These may be used alone or in combination of two or more.
  • the above binder is used for maintaining a good contact state between the positive electrode active material and the conductive agent and enhancing the binding property of the positive electrode active material and the like to the surface of the positive electrode current collector.
  • the binder for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), or a modified product thereof is used.
  • the binder may be used in combination with a thickener such as carboxymethyl cellulose (CMC) or polyethylene oxide (PEO).
  • the positive electrode potential in a fully charged state of the positive electrode having the above structure can be set to a high potential of 4.0 V (vs. Li / Li + ) or higher.
  • End-of-charge potential of the positive electrode in view of high capacity, preferably 4.5V (vs.Li/Li +) or more, 4.55V (vs.Li/Li +) or more preferred.
  • the upper limit of the charge termination potential of the positive electrode is not particularly limited, but is preferably 5.0 V (vs. Li / Li + ) or less from the viewpoint of suppressing decomposition of the nonaqueous electrolyte.
  • 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 negative electrode current collector.
  • a negative electrode current collector such as a metal foil
  • a negative electrode active material layer formed on the negative electrode current collector.
  • a metal foil that is stable in the potential range of the negative electrode such as copper a film in which a metal that is stable in the potential range of the negative electrode such as copper is arranged on the surface layer, or the like can be used.
  • 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.
  • PTFE styrene-butadiene copolymer
  • the binder may be used in combination with a thickener such as CMC.
  • Examples of the negative electrode active material include natural graphite, artificial graphite, lithium, silicon, carbon, tin, germanium, aluminum, lead, indium, gallium, lithium alloy, carbon and silicon in which lithium is previously occluded, and alloys and mixtures thereof. Etc. can be used.
  • 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 contains a fluorinated cyclic carbonate and a specific chain carbonate in a blending ratio described later.
  • a good protective film is formed on the positive electrode. , Approximately 100%), the crystal structure is stable. That is, application of the non-aqueous solvent improves the cycle characteristics of the non-aqueous electrolyte secondary battery.
  • the fluorinated cyclic carbonate is preferably a fluorinated cyclic carbonate having a fluorine atom directly bonded to the carbonate ring.
  • fluoroethylene carbonate examples include 4-fluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,4,5-trifluoroethylene carbonate, 4,4,5,5- Tetrafluoroethylene carbonate is mentioned. Of these, monofluoroethylene carbonate and difluoroethylene carbonate having a relatively low viscosity are preferable from the viewpoint of achieving both storage characteristics and cycle characteristics, among which 4-fluoroethylene carbonate and 4,5-difluoroethylene carbonate are particularly preferable.
  • 4-fluoroethylene carbonate or the like it is assumed that a good protective film is formed not only on the negative electrode but also on the positive electrode, thereby improving cycle characteristics and the like.
  • the content of the fluorinated cyclic carbonate is preferably 7% by volume or more and 70% by volume or less, and 25% by volume or more and 70% by volume or less based on the total volume of the nonaqueous solvent in the nonaqueous electrolyte from the viewpoint of improving cycle characteristics. Is more preferable, and 50 volume% or more and 70 volume% or less are especially preferable.
  • various characteristics such as storage characteristics and load characteristics, and from the viewpoint of optimization of battery design including manufacturing costs, for example, 7% by volume to 50% by volume, or 7% by volume. More than 25 volume% may be suitable.
  • the specific chain carbonates are methyl ethyl carbonate (hereinafter referred to as MEC) and diethyl carbonate (hereinafter referred to as DEC).
  • MEC and DEC may be used in a range of 30 to 90% by volume with respect to the total volume of the nonaqueous solvent. However, from the viewpoint of improving cycle characteristics, it is preferable that the ratio of DEC is higher than that of MEC. More preferably, only DEC is used as the carbonic acid ester.
  • the content of the specific chain carbonate is preferably from 30 to 93% by volume, more preferably from 30% to 75% by volume, based on the total volume of the nonaqueous solvent in the nonaqueous electrolyte, from the viewpoint of improving cycle characteristics. It is preferably 30% by volume or more and 50% by volume or less.
  • various characteristics such as storage characteristics and load characteristics, and from the viewpoint of optimization of battery design including manufacturing cost, for example, 50 volume% or more and 93 volume% or less, or 75 volume% More than 93 volume% may be suitable.
  • the non-aqueous solvent preferably does not contain a fluorinated chain ester such as 2,2,2-trifluoroethyl methyl carbonate or methyl 3,3,3-trifluoropropionate. Since the fluorinated chain ester is more expensive than the fluorinated cyclic carbonate and is inferior in mass productivity, it is useful to improve the cycle characteristics without using it.
  • “not containing a fluorinated chain ester” means substantially not containing a fluorinated chain ester. Specifically, it means that 0.5% by volume or more of the fluorinated chain ester is not contained with respect to the total volume of the nonaqueous solvent in the nonaqueous electrolyte.
  • non-aqueous solvent in addition to the fluorinated cyclic carbonate and the specific chain carbonate, a non-fluorine solvent generally used as a non-aqueous solvent can be used in combination.
  • a non-fluorine solvent generally used as a non-aqueous solvent can be used in combination.
  • Specific examples include cyclic carbonates, chain carbonates (excluding MEC and DEC), carboxylic acid esters, cyclic ethers, chain ethers, nitriles, amides, and mixed solvents thereof. .
  • cyclic carbonate examples include ethylene carbonate, propylene carbonate, butylene carbonate and the like.
  • chain carbonate examples include diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate and the like.
  • carboxylic acid esters examples include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and ⁇ -butyrolactone.
  • cyclic ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1, 4-Dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineol, crown ether and the like can be mentioned.
  • chain ethers examples include 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.
  • Pentylphenyl ether methoxytoluene, benzylethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1,1-dimethoxymethane, 1,1-diethoxyethane, triethylene glycol dimethyl ether, Examples include traethylene glycol dimethyl.
  • nitriles examples include acetonitrile, and examples of the amides include dimethylformamide.
  • a cyclic carbonate and a chain ester are preferably used.
  • the nonaqueous electrolyte does not contain a solvent other than the fluorinated cyclic carbonate and the specific chain carbonate.
  • does not contain a solvent other than the fluorinated cyclic carbonate and the fluorinated chain ester means that it contains substantially no other solvent. Specifically, it means that no other solvent is contained in an amount of 0.5% by volume or more based on the total volume of the nonaqueous solvent in the nonaqueous electrolyte.
  • the electrolyte salt is preferably a lithium salt.
  • the lithium salt those generally used as a supporting salt in a conventional nonaqueous electrolyte secondary battery can be used. Specific examples 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 ).
  • These lithium salts may be used alone or in combination of two or more.
  • separator 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.
  • material of the separator polyolefin such as polyethylene and polypropylene is suitable.
  • Example 1 [Production of positive electrode] To obtain Na 0.8 Co 8/9 Mn 1/9 O 2 (prepared composition), sodium nitrate (NaNO 3 ), cobalt oxide (II III) (Co 3 O 4 ), and manganese (III) oxide (Mn 2 O 3 ) was mixed. Then, the said mixture was hold
  • a molten salt bed in which lithium nitrate (LiNO 3 ) and lithium hydroxide (LiOH) were mixed at a molar ratio of 61:39 was equivalent to 5 times equivalent (5 g) to 5 g of the obtained sodium-containing transition metal oxide. )added. Then, a part of sodium of the sodium-containing transition metal oxide was ion-exchanged into lithium by holding the mixture at 200 ° C. for 10 hours. Further, the ion-exchanged material was washed with water to obtain a lithium-containing transition metal oxide.
  • the obtained lithium-containing transition metal oxide was analyzed by a powder X-ray diffraction method (manufactured by Rigaku Corporation, using a powder XRD measuring device RINT2200 (radiation source Cu-K ⁇ ); the same applies hereinafter) to identify the crystal structure. It was.
  • the obtained crystal structure was assigned to the O2 structure of the space group P6 3 mc.
  • the composition of the lithium-containing transition metal oxide was calculated by ICP emission analysis (Thermo Fisher Scientific, using ICP emission spectroscopic analyzer iCAP6300. The same applies hereinafter).
  • ICP emission analysis Thermo Fisher Scientific, using ICP emission spectroscopic analyzer iCAP6300. The same applies hereinafter).
  • the obtained lithium-containing transition metal oxide is used as a positive electrode active material
  • the positive electrode active material is 95% by mass
  • the conductive agent is 2.5% by mass of acetylene black
  • the binder is 2.5% by mass of polyvinylidene fluoride.
  • non-aqueous electrolyte 4-Fluoroethylene carbonate (hereinafter referred to as FEC) as a fluorinated cyclic carbonate and MEC were mixed at a volume ratio of 25:75 to obtain a nonaqueous solvent.
  • a nonaqueous electrolyte was prepared by dissolving lithium hexafluorophosphate (hereinafter referred to as LiPF 6 ) as an electrolyte salt in the nonaqueous solvent so as to have a concentration of 1.0 mol / l.
  • LiPF 6 lithium hexafluorophosphate
  • test cell A1 which is a 363562-type square nonaqueous electrolyte secondary battery with a rated capacity of 900 mAh was produced.
  • Example 2 In order to obtain Na 0.8 Co 8/9 Mn 2/27 Ti 1/27 O 2 (prepared composition), sodium nitrate (NaNO 3 ), cobalt oxide (II III) (Co 3 O 4 ), manganese oxide (III ) (Mn 2 O 3 ) and titanium dioxide (TiO 2 ). Then, the sodium containing transition metal oxide was obtained by hold
  • a molten salt bed in which lithium nitrate (LiNO 3 ) and lithium hydroxide (LiOH) were mixed at a molar ratio of 61:39 was equivalent to 5 times equivalent (5 g) to 5 g of the obtained sodium-containing transition metal oxide. )added. Then, a part of sodium of the sodium-containing transition metal oxide was ion-exchanged into lithium by holding the mixture at 200 ° C. for 10 hours. Further, the ion-exchanged material was washed with water to obtain a lithium-containing transition metal oxide.
  • the obtained lithium-containing transition metal oxide was analyzed by a powder X-ray diffraction method, and the crystal structure was identified. The obtained crystal structure was assigned to the O2 structure of the space group P6 3 mc. Further, the composition of the lithium-containing transition metal oxides, the result calculated by ICP emission analysis was Li 0.86 Na 0.022 Co 0.89 Mn 0.07 Ti 0.04 O 2. Test cell A2 was produced in the same manner as in Example 1 except that the lithium-containing transition metal oxide thus obtained was used as the positive electrode active material.
  • Example 3 As the nonaqueous solvent for the nonaqueous electrolyte, a nonaqueous solvent in which 4,5-difluoroethylene carbonate (hereinafter referred to as DFEC) and MEC were mixed at a volume ratio of 25:75 was used. Test cell A3 was produced in the same manner as in Example 2.
  • Example 4 A test cell A4 was produced in the same manner as in Example 1 except that a nonaqueous solvent in which FEC and DEC were mixed at a volume ratio of 25:75 was used as a nonaqueous solvent for the nonaqueous electrolyte. .
  • Example 5 A test cell A5 was produced in the same manner as in Example 1 except that a nonaqueous solvent in which FEC and MEC were mixed at a volume ratio of 10:90 was used as the nonaqueous electrolyte nonaqueous solvent. .
  • Test cell A6 was produced in the same manner as in Example 1 except that a nonaqueous solvent in which FEC and MEC were mixed at a volume ratio of 50:50 was used as the nonaqueous solvent for the nonaqueous electrolyte. .
  • Test cell A7 was produced in the same manner as in Example 1 except that a nonaqueous solvent in which FEC and MEC were mixed at a volume ratio of 70:30 was used as the nonaqueous solvent for the nonaqueous electrolyte. .
  • Example 8> A test cell A8 was produced in the same manner as in Example 2 except that a nonaqueous solvent in which DFEC and MEC were mixed at a volume ratio of 50:50 was used as a nonaqueous electrolyte nonaqueous electrolyte. .
  • Test cell A9 was produced in the same manner as in Example 1 except that a nonaqueous solvent in which FEC and MEC were mixed at a volume ratio of 7:93 was used as a nonaqueous electrolyte nonaqueous electrolyte. .
  • the crystal structure was assigned to the O3 structure of the space group R-3m.
  • the composition of the lithium-containing transition metal oxide was calculated by ICP emission analysis, and was Li 1.01 CoO 2 .
  • Comparative Example 2 The same as Comparative Example 1 except that a nonaqueous solvent in which ethylene carbonate (hereinafter referred to as EC) and MEC were mixed at a volume ratio of 25:75 was used as the nonaqueous solvent for the nonaqueous electrolyte. Thus, a test cell X2 was produced.
  • EC ethylene carbonate
  • MEC ethylene carbonate
  • Example 3 A test cell X3 was produced in the same manner as in Example 1 except that a nonaqueous solvent in which EC and MEC were mixed at a volume ratio of 25:75 was used as the nonaqueous electrolyte nonaqueous solvent. .
  • test cell X4 was produced in the same manner as in Example 1 except that a nonaqueous solvent in which FEC and MEC were mixed at a volume ratio of 5:95 was used as a nonaqueous solvent for the nonaqueous electrolyte. .
  • Test cell X5 was produced in the same manner as in Example 1 except that a nonaqueous solvent in which FEC and MEC were mixed at a volume ratio of 90:10 was used as the nonaqueous solvent for the nonaqueous electrolyte. .
  • Table 1 shows a summary of the composition and crystal structure (space group) of the positive electrode active material and the composition of the nonaqueous electrolyte in Examples 1 to 9 and Comparative Examples 1 to 5.
  • Table 2 shows capacity retention rates after 15, 30, and 50 cycles for test cells A1 to A9 of Examples 1 to 9 and test cells X1 to X5 of Comparative Examples 1 to 5.
  • test cells A1 to A8 of the example all show excellent cycle characteristics as compared with the test cells X1 to X5 of the comparative example. That is, a lithium-containing transition metal oxide having a crystal structure belonging to the space group P6 3 mc is used as a positive electrode active material, and mixed in a predetermined volume ratio with a fluorinated cyclic carbonate (FEC, DFEC) and a specific chain carbonate (MEC). , DEC) is applied to the non-aqueous electrolyte, it is considered that capacity reduction due to decomposition of the non-aqueous electrolyte accompanying charge / discharge is suppressed, and good cycle characteristics are obtained.
  • FEC fluorinated cyclic carbonate
  • MEC specific chain carbonate
  • test cells X1 and X2 of Comparative Examples 1 and 2 of Comparative Examples 1 and 2 a fluorinated cyclic carbonate and a specific chain carbonate mixed with a predetermined volume ratio of lithium cobaltate having a crystal structure belonging to space group R-3m as a positive electrode active material.
  • a non-aqueous solvent containing an ester was applied to the non-aqueous electrolyte, but good cycle characteristics were not obtained. That is, with respect to lithium cobaltate having a crystal structure belonging to the space group R-3m that is currently in practical use, the non-aqueous solvent containing a fluorinated cyclic carbonate and a specific chain carbonate did not show an effect of improving cycle characteristics. .
  • the fluorinated cyclic carbonate mixed at a predetermined volume ratio and Good cycle characteristics were obtained by applying a non-aqueous solvent containing a specific chain carbonate. That is, the non-aqueous solvent which has no effect on the positive electrode active material currently in practical use has a large cycle characteristic when the positive electrode active material is a lithium-containing transition metal oxide having a crystal structure belonging to the space group P6 3 mc. Improve.
  • the active material is easily cleaved with charge and discharge, and a coating that smoothly inserts and desorbs lithium on the newly generated active material surface is provided. Although it is thought that it was formed, the evaluation result was extremely good than expected.
  • the fluorinated cyclic carbonate is 7% by volume or more and 70% by volume or less with respect to the total volume of the nonaqueous solvent, and at least one of the specific chain carbonates MEC and DEC is 30% by volume. It is obtained only when the content is 93% by volume or less, and cannot be obtained when the amount is outside this range.
  • the ratio of the fluorinated cyclic carbonate exceeds 70% by volume, the cycle characteristics are remarkably deteriorated, and charge / discharge cannot be performed with a low number of cycles as in the test cell X5 of Comparative Example 5.
  • the ratio of the fluorinated cyclic carbonate is less than 7% by volume, good cycle characteristics cannot be obtained as in the test cell X4 of Comparative Example 4.
  • cycling characteristics can be improved, so that the ratio of the fluorinated cyclic carbonate in a non-aqueous solvent is made high in the range of 7 volume% or more and 70 volume% or less.
  • the non-aqueous electrolyte is substantially free of fluorinated cyclic carbonate and other solvents other than MEC and DEC, and the volume ratio of the two is 7:93 to 70:30, and 25:75 More preferably, it is ⁇ 70: 30, and particularly preferably 50:50 to 70:30.
  • DEFC fluorinated cyclic ester carbonate
  • FEC fluorinated cyclic ester carbonate
  • specific chain carbonate it is preferable to use a larger amount of DEC than MEC or to use only DEC. Thereby, cycle characteristics can be further improved (see Examples 1 and 4).
  • the positive electrode active material it is preferable to use a lithium-containing transition metal oxide containing Ti in addition to Co and Mn as transition metal elements.
  • the contents of Co, Mn, and Ti are preferably Co>Mn> Ti.
  • cycle characteristics can be further improved (see Examples 1 and 2).
  • the effect of improving cycle characteristics due to the addition of Ti is remarkable, and the capacity retention ratio after 50 cycles of test cell A1 (Example 1) using Li 0.84 Na 0.028 Co 0.89 Mn 0.11 O 2 as the positive electrode active material is 79.9%.
  • the same capacity retention rate of Test Cell A2 (Example 2) using Li 0.86 Na 0.022 Co 0.89 Mn 0.07 Ti 0.04 O 2 as the positive electrode active material was 96.6%.
  • Example 10 A three-electrode cell B1 was produced using the positive electrode produced in Example 1 as a working electrode and metal lithium as a counter electrode and a reference electrode. The battery was charged at a constant current rate of 0.2 C until the positive electrode potential reached 4.6 V, and further charged at a constant potential of 4.6 V until the current value reached 1/20 C. Then, the charge / discharge capacity (mAh) of the battery was measured by discharging until the positive electrode potential reached 3.2 V at a constant current of 0.2 C. This charge / discharge was repeated, and the charge / discharge efficiency was evaluated by multiplying the value obtained by dividing the discharge capacity at the 10th cycle by the charge capacity.
  • mAh charge / discharge capacity
  • Example 6 A test cell Y1 was prepared in the same manner as in Example 10 except that a nonaqueous solvent in which EC and MEC were mixed at a volume ratio of 25:75 was used as the nonaqueous electrolyte nonaqueous electrolyte. The charge / discharge efficiency at the 10th cycle was evaluated.
  • Table 3 shows a summary of the composition of the positive electrode active material, the composition of the nonaqueous electrolyte, and the charge / discharge efficiency at the 10th cycle in Example 10 and Comparative Example 6.
  • the test cell B1 of Example 10 exhibits excellent charge / discharge efficiency as compared to the test cell Y1 of Comparative Example 6, and is considered to have good cycle characteristics.
  • a lithium-containing transition metal oxide having a crystal structure belonging to the space group P6 3 mc is used as a positive electrode active material, and a non-aqueous solvent containing a fluorinated cyclic carbonate and a chain carbonate mixed in a predetermined volume ratio is applied to a non-aqueous electrolyte. By doing so, a charge / discharge cycle involving charging to a high potential of 4.55V, 4.6V becomes possible.

Abstract

La présente invention concerne une batterie secondaire à électrolyte non aqueux qui est pourvue d'une électrode positive, qui comprend un matériau actif d'électrode positive, d'une électrode négative, et d'un électrolyte non aqueux qui contient un solvant non aqueux, le matériau actif d'électrode positive comprenant un oxyde de métal de transition qui contient du lithium, ledit oxyde de métal de transition qui contient du lithium possédant une structure cristalline qui appartient à un groupe spatial P63mc, et le solvant non aqueux contenant, par rapport au volume total, 7 à 70 % inclus en volume d'esters de carbonate cyclique fluoré, et 30 à 93 % inclus en volume de carbonate de méthyléthyle et/ou de carbonate de diéthyle en tant qu'esters de carbonate en chaîne.
PCT/JP2013/006978 2012-11-30 2013-11-27 Batterie secondaire à électrolyte non aqueux WO2014083848A1 (fr)

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EP4207379A4 (fr) * 2020-11-10 2024-03-13 Ningde Amperex Technology Ltd Matériau actif d'électrode positive et dispositif électrochimique

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