WO2012073747A1 - Électrode positive pour batteries secondaires à électrolyte non aqueux, procédé de production associé, et batterie secondaire à électrolyte non aqueux - Google Patents

Électrode positive pour batteries secondaires à électrolyte non aqueux, procédé de production associé, et batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2012073747A1
WO2012073747A1 PCT/JP2011/076850 JP2011076850W WO2012073747A1 WO 2012073747 A1 WO2012073747 A1 WO 2012073747A1 JP 2011076850 W JP2011076850 W JP 2011076850W WO 2012073747 A1 WO2012073747 A1 WO 2012073747A1
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positive electrode
electrolyte secondary
secondary battery
inorganic particle
nonaqueous electrolyte
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PCT/JP2011/076850
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English (en)
Japanese (ja)
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山本　諭
伸宏 鉾谷
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三洋電機株式会社
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Priority to JP2012546787A priority Critical patent/JP5888512B2/ja
Publication of WO2012073747A1 publication Critical patent/WO2012073747A1/fr

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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 positive electrode for a non-aqueous electrolyte secondary battery, a method for producing the same, and a non-aqueous electrolyte secondary battery, and particularly for a non-aqueous electrolyte secondary battery capable of improving storage characteristics and cycle characteristics in a high temperature and high voltage state.
  • the present invention relates to a positive electrode, a manufacturing method thereof, and a nonaqueous electrolyte secondary battery including the positive electrode.
  • non-aqueous electrolyte secondary batteries represented by high-capacity lithium ion secondary batteries are widely used.
  • the positive electrode active material of these nonaqueous electrolyte secondary batteries is represented by LiMO 2 (where M is at least one of Co, Ni, and Mn) capable of reversibly occluding and releasing lithium ions.
  • a carbon material such as graphite or a material alloyed with lithium such as Si or Sn is used as the negative electrode active material.
  • lithium-cobalt composite oxides and heterogeneous metal element-added lithium-cobalt composite oxides are often used because various battery characteristics are superior to others.
  • cobalt is expensive and has a small abundance as a resource. Therefore, in order to continue using these lithium cobalt composite oxides and lithium cobalt composite oxides containing different metal elements as positive electrode active materials for non-aqueous electrolyte secondary batteries, further enhancement of the performance of non-aqueous electrolyte secondary batteries is desired. ing.
  • non-aqueous electrolyte secondary batteries are required to have higher capacities due to demands for increased power consumption and long-term driving of HEVs and EVs with enhancement of entertainment functions such as video playback and game functions in recent mobile information terminals.
  • the end-of-charge voltage is 4.
  • a method of raising the voltage from 3V to about 4.6V is known.
  • the above side reaction is likely to occur, and battery performance such as cycle characteristics and storage characteristics is greatly impaired.
  • the oxidization reaction (dehydrogenation reaction) of the separator reduces the piercing strength and tensile strength of the separator, impairing the insulating function and shutdown function that the separator should originally perform, and lowering the reliability of the battery.
  • Patent Document 1 and Patent Document 2 below disclose a technique for suppressing these side reactions by forming a porous inorganic particle layer on the surface of the positive electrode mixture layer.
  • Patent Document 3 listed below discloses an invention of a lithium ion secondary battery in which high-temperature storage characteristics and cycle characteristics are improved by including an alkali metal phosphate in the positive electrode mixture layer. .
  • the porous inorganic particle layer is formed on the surface of the positive electrode mixture layer, so that the storage characteristics and cycle characteristics in a high voltage state are improved. Although improvement is achieved to some extent, the effect is still insufficient particularly in a high temperature environment, and there is room for further improvement.
  • no porous inorganic particle layer is formed on the surface of the positive electrode mixture layer.
  • An object of the present invention is to provide a positive electrode for a nonaqueous electrolyte secondary battery with improved capacity and charge / discharge cycle characteristics, a method for producing the same, and a nonaqueous electrolyte secondary battery including the positive electrode.
  • a positive electrode for a non-aqueous electrolyte secondary battery is formed on a surface of a positive electrode mixture layer including a positive electrode active material formed on the surface of a positive electrode core and the positive electrode mixture layer.
  • the porous inorganic particle layer is selected from sodium hexametaphosphate, sodium pyrophosphate, trisodium phosphate, and disodium hydrogen phosphate It contains at least one sodium phosphate salt.
  • an inorganic particle layer is formed on the surface of the positive electrode mixture layer. Therefore, the oxidative decomposition product of the non-aqueous electrolyte on the positive electrode surface is trapped by this inorganic particle layer. Therefore, deposition on the negative electrode can be suppressed.
  • At least one sodium phosphate selected from sodium hexametaphosphate, sodium pyrophosphate, trisodium phosphate, and disodium hydrogen phosphate in the inorganic particle layer. Contains salt.
  • the nonaqueous electrolyte secondary battery is inevitably mixed with a trace amount of water from the manufacturing process. Moreover, under high charging voltage, moisture is generated by the decomposition of the non-aqueous electrolyte.
  • the inorganic particle layer contains sodium phosphate salt, the reaction rate between these sodium phosphate salt and moisture is faster than the reaction rate between lithium salt as electrolyte and moisture.
  • the decomposition reaction of the lithium salt as the electrolyte can be suppressed.
  • the sodium phosphate salt is included in the inorganic particle layer, the sodium phosphate salt and the non-aqueous electrolyte solution are more contained in the positive electrode active material mixture layer than in the case of including the sodium phosphate salt as in the conventional example. It becomes easy to come into contact with moisture.
  • the charge end voltage is set to a high level of 4.4 V or more and 4.6 V or less on a lithium basis, and a high temperature environment. Even when placed underneath, both the storage characteristics and the cycle characteristics are much better than when the positive electrode for a nonaqueous electrolyte secondary battery of the conventional example is used.
  • the content of sodium phosphate contained in the porous inorganic particle layer is set to 0.03% by mass or more to 1% by mass of the positive electrode active material mixture. It is preferable to make it 0.0 mass% or less.
  • the content of sodium phosphate salt is less than 0.03% by mass, the above effect is hardly achieved, and when it exceeds 1.0% by mass, the positive electrode active material mixture that can be filled in the battery outer can by that much Since the amount decreases, the charge capacity per unit volume decreases, which is not preferable.
  • the inorganic particles contained in the porous inorganic particle layer are at least selected from titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), silicon oxide (SiO 2 ), and zirconium oxide (ZrO 2 ).
  • TiO 2 titanium oxide
  • Al 2 O 3 aluminum oxide
  • SiO 2 silicon oxide
  • ZrO 2 zirconium oxide
  • One kind can be used, and aluminum oxide and rutile type titanium oxide are particularly preferable in consideration of stability in the battery, reactivity with lithium, and cost.
  • the average particle diameter of the inorganic particles is preferably 1 ⁇ m or less, and more preferably in the range of 0.1 to 0.8 ⁇ m. Moreover, it is preferable that an average particle diameter is larger than the average hole diameter of the separator used for a nonaqueous electrolyte secondary battery.
  • the method for producing a positive electrode for a non-aqueous electrolyte secondary battery according to the present invention includes a step of forming a positive electrode mixture layer on the surface of the positive electrode core, and a porous material on the surface of the positive electrode mixture layer.
  • porous inorganic particle layer in the method for producing a positive electrode for a non-aqueous electrolyte secondary battery having a step of forming a porous inorganic particle layer, and the step of forming the porous inorganic particle layer includes: inorganic particles, sodium hexametaphosphate, sodium pyrophosphate, phosphoric acid A slurry containing at least one sodium phosphate selected from trisodium and disodium hydrogen phosphate is applied by a gravure coating method and then dried.
  • the surface of the positive electrode mixture layer contains inorganic particles and sodium phosphate salt.
  • the slurry is applied by a gravure coating method and then dried. When such a method is employed, a slurry containing inorganic particles and sodium phosphate salt is thinly formed on the surface of the positive electrode mixture layer, and can be continuously formed with a uniform thickness.
  • a positive electrode for a non-aqueous electrolyte secondary battery of the present invention it becomes possible to continuously manufacture a positive electrode for a non-aqueous electrolyte secondary battery having a uniform quality, and the end-of-charge voltage is 4 based on lithium.
  • the production efficiency of a nonaqueous electrolyte secondary battery having excellent storage characteristics and cycle characteristics is improved even when placed in a high temperature environment of .4 V or more and 4.6 V or less.
  • phosphorous comprising at least one selected from inorganic particles and sodium hexametaphosphate, sodium pyrophosphate, trisodium phosphate, and disodium hydrogen phosphate.
  • a solvent it is preferable to select a solvent according to the type of the binder contained in the positive electrode active material mixture layer.
  • the binder contained in the positive electrode mixture layer is a hydrophobic substance
  • the binder to be used is a hydrophilic substance
  • the above lithium cobaltate powder was mixed to 96 parts by mass, carbon powder as a conductive material to 2 parts by mass, and polyvinylidene fluoride (PVdF) powder as a binder to 2 parts by mass, and this was mixed with N-methylpyrrolidone.
  • a positive electrode active material mixture slurry was prepared by mixing with (NMP) solution. This slurry was applied to both surfaces of a positive electrode core made of aluminum having a thickness of 15 ⁇ m by a doctor blade method.
  • the coated portion on one surface of the positive electrode core was 277 mm, the uncoated portion was 57 mm, the coated portion on the other surface was 208 mm, After coating so that the coated portion was 126 mm, NMP was removed by drying by passing through a dryer.
  • the positive electrode mixture layer was formed on both surfaces of the positive electrode core body by compressing using a compression roller so that the thickness of the double-side coated portion was 132 ⁇ m.
  • inorganic particle slurry 30% by mass of aluminum oxide (Al 2 O 3 ) as inorganic particles, 0.15% by mass of carboxymethylcellulose (CMC), and 69.85% by mass of pure water are mixed, and a kneader (TK High-Pixics manufactured by PRIMIX) After kneading, the obtained slurry was dispersed with a bead mill (Nanomill dispersing device manufactured by Asada Tekko) to obtain an inorganic particle slurry containing no phosphate.
  • TK High-Pixics manufactured by PRIMIX a kneader
  • the dispersion conditions were as follows: internal volume: 0.3 L, bead diameter: 0.5 ⁇ , slit: 0.15 mm, bead filling amount: 90%, peripheral speed 40 Hz, treatment flow rate: 1.0 kg / min.
  • aluminum oxide AK3000 (trade name: manufactured by Sumitomo Chemical Co., Ltd.) was used.
  • CMC Daicel Chemical Industries 1380 was used.
  • binder (acrylic rubber-type binder) is added with respect to aluminum oxide to an inorganic particle slurry. Furthermore, sodium hexametaphosphate as a phosphate is added so that it may become 33 mass% of slurry solid content whole quantity. It was. Thereafter, by adding pure water so that the ratio of aluminum oxide to the total amount of the slurry is finally 30% by mass, and kneading again with the above kneader, the phosphate-containing inorganic particle slurry used in each example is obtained. Prepared.
  • the positive electrode mixture layer formed on both surfaces of the positive electrode core is coated and coated on the surface of the positive electrode mixture layer with the phosphate-containing inorganic particle slurry obtained as described above by the gravure coating method.
  • a porous inorganic particle layer was formed to obtain a positive electrode plate used in Example 1.
  • the coating amount of the phosphate-containing inorganic particle slurry was 1% by mass in terms of solid content of the phosphate-containing inorganic particle slurry with respect to the positive electrode active material mixture (solid content).
  • the sodium hexametaphosphate content of the positive electrode is 0.33% by mass with respect to the positive electrode active material mixture (solid content).
  • the coating amount of the negative electrode active material mixture was the mass per unit area after drying, and the coating mass on one side was 11.3 mg / cm 2 . Then, the negative electrode active material layer was formed on both surfaces of the negative electrode core by passing through a dryer and drying. Subsequently, it was set as the negative electrode plate used by each Example and a comparative example by compressing so that the thickness of a double-sided application part might be 155 micrometers using a compression roller.
  • the potential of graphite at the time of charging is about 0.1 V with respect to Li.
  • the positive electrode and negative electrode active material filling amount is such that the charge capacity ratio of the positive electrode to the negative electrode (negative electrode charge capacity / positive electrode charge capacity) is 1.0 to 1.1 at the potential of the positive electrode active material as a design standard. Adjusted.
  • Lithium hexafluorophosphate LiPF 6
  • MEC methyl ethyl carbonate
  • VC vinylene carbonate
  • Electrode body An aluminum lead wire is welded and fixed to the obtained positive electrode plate, and a nickel lead wire is welded and fixed to the obtained negative electrode plate, and then the positive electrode plate and the negative electrode plate are made of a polyethylene microporous film.
  • a spiral electrode body was produced by winding it in a flat shape through a separator.
  • the obtained electrode body was sealed in a laminate container, and the obtained nonaqueous electrolytic solution was injected in a glove box filled with Ar. Thereafter, the injection hole was closed to produce a laminate battery, and a nonaqueous electrolyte secondary battery according to Example 1 was obtained.
  • the design capacity of the obtained non-aqueous electrolyte secondary battery is 800 mAh.
  • Example 2 and 3 A non-aqueous electrolyte secondary battery according to Examples 2 and 3 was prepared by producing a laminated battery in the same manner as in Example 1 except that the amount of sodium hexametaphosphate added to the inorganic particle slurry was changed in the inorganic particle slurry preparation step. It was.
  • a phosphate-containing inorganic particle slurry in which the content of sodium hexametaphosphate is 3.3% by mass (Example 2) and 50% by mass (Example 3) with respect to the total amount of slurry solids is mixed with the positive electrode mixture.
  • the nonaqueous electrolyte secondary battery which concerns on Example 2 and 3 was produced using the positive electrode plate obtained by apply
  • the sodium hexametaphosphate content of the positive electrode is 0.03% by mass (Example 2) and 0.5% by mass (Example 3) with respect to the positive electrode active material mixture (solid content).
  • Example 4 to 6 A non-aqueous electrolyte secondary battery according to Examples 4 to 6 was prepared in the same manner as in Example 1 except that the kind of phosphate contained in the inorganic particle slurry was changed in the preparation process of the inorganic particle slurry. did.
  • the positive electrode plates obtained by applying the slurry to the surface of the positive electrode mixture layer non-aqueous electrolyte secondary batteries according to Examples 4 to 6 were produced.
  • content of the phosphate in an inorganic particle slurry shall be 33 mass% similarly to Example 1, and the phosphate content in a positive electrode is 0.33 mass with respect to positive electrode active material mixture (solid content). %.
  • Example 1 A laminated battery was produced in the same manner as in Example 1 except that phosphate was not added to the inorganic particle slurry, and a nonaqueous electrolyte secondary battery according to Comparative Example 1 was obtained. That is, a comparative example using a positive electrode plate obtained by applying a slurry obtained by kneading after adding only a binder to an inorganic particle slurry not containing phosphate, on the surface of the positive electrode mixture layer A non-aqueous electrolyte secondary battery according to No. 1 was produced.
  • Example 2 A laminated battery was produced in the same manner as in Example 1 except that the porous inorganic particle layer was not formed on the positive electrode plate, and a nonaqueous electrolyte secondary battery according to Comparative Example 2 was obtained. That is, a non-aqueous electrolyte secondary battery according to Comparative Example 2 was manufactured using only a positive electrode mixture layer formed on the positive electrode core as a positive electrode plate.
  • the positive electrode plates in Comparative Examples 3 to 5 were obtained by adding sodium hexametaphosphate to the positive electrode active material mixture slurry in Example 1 and kneading them (phosphate-containing positive electrode active material mixture). Slurry) is applied to both surfaces of the positive electrode core to form a positive electrode mixture layer, and then the slurry obtained by kneading after adding only a binder to the inorganic particle slurry containing no phosphate is mixed with the positive electrode mixture.
  • a positive electrode plate used in Comparative Examples 3 to 5 was further produced using a positive electrode plate obtained by forming an inorganic particle layer by coating on the surface of the layer. The amount of sodium hexametaphosphate added was 0.05% by mass (Comparative Example 3), 0.5% by mass (Comparative Example 4), and 1.0% by mass (comparative) with respect to the positive electrode active material mixture (solid content). Example 5).
  • Remaining capacity ratio (%) (Remaining capacity after high temperature storage / Charging capacity before high temperature storage) x 100
  • Capacity maintenance rate (%) (Discharge capacity at 500th cycle / discharge capacity at the first cycle) x 100
  • Comparative Example 1 has improved high-temperature storage characteristics and high-temperature cycle characteristics as compared with Comparative Example 2.
  • Comparative Example 2 By forming an inorganic particle layer on the surface of the positive electrode mixture layer, high-temperature storage characteristics and high-temperature cycle characteristics are to some extent. It can be confirmed that there is an improvement. This indicates that the oxidation reaction of the separator is suppressed by the trap effect of the inorganic particle layer formed on the surface of the positive electrode mixture layer.
  • Example 1 the high-temperature storage characteristics and the high-temperature cycle characteristics are more significantly improved as compared with Comparative Example 1, and sodium hexametaphosphate is added to the inorganic particle layer formed on the surface of the positive electrode mixture layer.
  • a non-aqueous electrolyte secondary battery having significantly improved high-temperature storage characteristics and high-temperature cycle characteristics can be obtained.
  • the effect of improving the high-temperature storage characteristics and the high-temperature cycle characteristics by containing sodium hexametaphosphate in the inorganic particle layer is that the sodium hexametaphosphate content is positive electrode active material mixture (solid It can be seen that even a very small amount of 0.03% by mass with respect to (min) is sufficiently exerted.
  • the presence of moisture in the battery causes hydrolysis of a lithium salt such as LiPF 6 that is an electrolyte salt, and accordingly, hydrofluoric acid is generated. Since the positive electrode active material is corroded by this hydrofluoric acid and the original charge / discharge function cannot be exhibited, it is considered that the storage characteristics and the cycle characteristics particularly in a high temperature and high voltage state are deteriorated.
  • a lithium salt such as LiPF 6 that is an electrolyte salt
  • an inorganic particle layer is formed on the surface of the positive electrode mixture layer, and sodium hexametaphosphate, sodium pyrophosphate, and trisodium phosphate are further formed in the inorganic particle layer. Because it contains any phosphate of disodium hydrogen phosphate, hydrolysis of lithium salt due to moisture and oxidation of the separator are suppressed, improving storage characteristics and cycle characteristics at high temperature and high voltage it is conceivable that. This is because decomposition of the lithium salt can be suppressed because the reactivity of the phosphate with moisture is higher than that of the lithium salt.
  • Example 3 and Comparative Example 4 are compared, the amount of phosphate present in the battery is the same, but the effect is greatly different. This is thought to be because the contact efficiency between the phosphate and the electrolyte is high by mixing only the positive electrode inorganic particle layer rather than simply mixing the phosphate with the positive electrode mixture layer. In order to increase the filling of the positive electrode material for the purpose, it is necessary to contain only the positive electrode inorganic particle layer with the phosphate.
  • an inorganic particle layer is formed on the surface of the positive electrode mixture layer, and the phosphate is selected from sodium hexametaphosphate, sodium pyrophosphate, trisodium phosphate, and disodium hydrogen phosphate in the inorganic particle layer.
  • the phosphate is selected from sodium hexametaphosphate, sodium pyrophosphate, trisodium phosphate, and disodium hydrogen phosphate in the inorganic particle layer.
  • lithium cobaltate was used as the positive electrode active material.
  • the present invention is not limited to this, and lithium ions can be reversibly occluded / released.
  • graphite was used as the negative electrode active material.
  • carbonaceous materials such as natural graphite, artificial graphite, and coke capable of reversibly occluding and releasing lithium ions, silicon, tin, etc.
  • An alloy, an oxide, a mixture thereof, or the like can be used.
  • nonaqueous solvent organic solvent
  • carbonates lactones, ethers, esters and the like
  • two or more of these solvents can be used in combination.
  • carbonates are preferable.
  • EC EC
  • MEC propylene carbonate
  • BC butylene carbonate
  • FEC fluoroethylene carbonate
  • sulfolane 3-methylsulfolane, 2,4.
  • -Dimethylsulfolane 3-methyl-1,3-oxazolidine-2-one, dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl propyl carbonate, methyl butyl carbonate, ethyl propyl carbonate, ethyl butyl carbonate, dipropyl carbonate, ⁇ -Butyrolactone, ⁇ -valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, methyl acetate, ethyl acetate, 1,4-dioxane, etc. be able to.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • methyl propyl carbonate methyl butyl carbonate
  • ethyl propyl carbonate ethyl butyl carbonate
  • dipropyl carbonate ⁇ -Butyrolactone, ⁇
  • a lithium salt generally used as a solute in the nonaqueous electrolyte secondary battery can be used.
  • a lithium salt in addition to LiPF 6 used in the examples, LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2) (C 4 F 9 SO 2), LiC (CF 3 SO 2) 3, LiC (C 2 F 5 SO 2) 3, LiAsF 6, LiClO 4, Li 2 B 10 Cl 10, Li 2 B 12 Examples include Cl 12 and mixtures thereof.
  • the amount of solute dissolved in the non-aqueous solvent is preferably 0.5 to 2.0 mol / L.
  • an organic solvent such as N-methyl-pyrrolidone (NMP) as the slurry solvent when preparing the inorganic particle slurry, in which case the dispersion stability of the slurry is good.
  • NMP N-methyl-pyrrolidone
  • organic solvents such as MNP are easy to vaporize, the water content in the porous inorganic particle layer can be easily reduced by drying, so that the amount of water in the porous inorganic particle layer can be made extremely low.
  • a non-aqueous electrolyte secondary battery having excellent storage characteristics and cycle characteristics can be produced.
  • the solvent from which a binder is hard to elute to an inorganic particle layer can be selected.
  • a highly hydrophobic binder is used in preparing the positive electrode active material mixture slurry, such as PVdF used in the above examples, the binder (PVdF) is eluted into the inorganic particle layer.
  • PVdF highly hydrophobic binder
  • an inorganic particle slurry is used using a non-aqueous solvent. Is preferably prepared.
  • Examples of the method of applying the inorganic particle slurry on the surface of the positive electrode mixture layer include a die coating method, a gravure coating method, a dip coating method, a curtain coating method, and a spray coating method.
  • the inorganic particle slurry can be continuously formed in a thin and uniform thickness, so that a positive electrode for a non-aqueous electrolyte secondary battery of uniform quality can be continuously manufactured. Become.
  • the charging voltage of the battery is 4.4 V on the basis of lithium
  • the charging voltage of the positive electrode is 4.5 V on the basis of lithium
  • the charging voltage of the positive electrode is 4.4 V on the basis of lithium. If it is above, the same effect is produced. However, if the charging voltage of the positive electrode exceeds 4.6 V on the basis of lithium, the oxidative decomposition of the nonaqueous electrolyte becomes severe and the positive electrode active material tends to deteriorate, so the charging voltage is 4.4 V or more on the basis of lithium. It is preferable that it is 6V or less.

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Abstract

La présente invention a pour objectif de fournir : une électrode positive pour batteries secondaires à électrolyte non aqueux, capable d'améliorer les caractéristiques de stockage et les caractéristiques de cycle dans un état de haute tension et de température élevée ; un procédé de production de l'électrode positive pour batteries secondaires à électrolyte non aqueux ; et une batterie secondaire à électrolyte non aqueux comprenant l'électrode positive. Pour ce faire, une électrode positive pour batteries secondaires à électrolyte non aqueux comprend : une couche de mélange d'électrode positive qui contient un matériau actif d'électrode positive, un agent conducteur, et un liant ; et une couche de particule inorganique poreuse qui est formée sur la surface de la couche de mélange d'électrode positive. La couche de particule inorganique poreuse contient au moins une substance qui est choisie parmi l'hexamétaphosphate de sodium, le pyrophosphate de sodium, le triphosphate de sodium et le dihydrogénophosphate de sodium.
PCT/JP2011/076850 2010-11-30 2011-11-22 Électrode positive pour batteries secondaires à électrolyte non aqueux, procédé de production associé, et batterie secondaire à électrolyte non aqueux WO2012073747A1 (fr)

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Cited By (6)

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JP2015103471A (ja) * 2013-11-27 2015-06-04 株式会社豊田自動織機 蓄電装置の製造方法および蓄電装置
JP2017091698A (ja) * 2015-11-05 2017-05-25 トヨタ自動車株式会社 非水電解液二次電池
JP2018032649A (ja) * 2012-09-07 2018-03-01 旭化成株式会社 非水電解液二次電池用セパレータ及び非水電解液二次電池
JPWO2017018436A1 (ja) * 2015-07-28 2018-05-17 日本電気株式会社 リチウムイオン二次電池
WO2021084671A1 (fr) 2019-10-31 2021-05-06 Ｔｐｒ株式会社 Liant
CN117457856A (zh) * 2023-12-20 2024-01-26 清陶(昆山)能源发展股份有限公司 复合正极及其制备方法

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