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WO2012043733A1 - Procédé de fabrication de batterie secondaire à électrolyte non aqueux - Google Patents

Procédé de fabrication de batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2012043733A1
WO2012043733A1 PCT/JP2011/072413 JP2011072413W WO2012043733A1 WO 2012043733 A1 WO2012043733 A1 WO 2012043733A1 JP 2011072413 W JP2011072413 W JP 2011072413W WO 2012043733 A1 WO2012043733 A1 WO 2012043733A1
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WIPO (PCT)
Prior art keywords
negative electrode
secondary battery
aqueous electrolyte
electrolyte secondary
nonaqueous electrolyte
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Ceased
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PCT/JP2011/072413
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English (en)
Japanese (ja)
Inventor
篤史 貝塚
岩永　征人
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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Publication of WO2012043733A1 publication Critical patent/WO2012043733A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for producing a non-aqueous electrolyte secondary battery, and more particularly to a method for producing a non-aqueous electrolyte secondary battery in which gas generation during high-temperature charge storage is suppressed.
  • Non-aqueous electrolyte secondary batteries are light and have high energy density, and are therefore widely used as power sources for mobile electronic devices such as mobile phones and notebook computers.
  • a carbonaceous material such as graphite is used as the negative electrode active material of the nonaqueous electrolyte secondary battery, and a lithium metal composite oxide such as LiCoO 2 , LiNiO 2 , Li 2 MnO 4, or LiFePO 4 is used as the positive electrode active material.
  • a lithium metal composite oxide such as LiCoO 2 , LiNiO 2 , Li 2 MnO 4, or LiFePO 4 is used as the positive electrode active material.
  • LiCoO 2 LiCoO 2 , LiNiO 2 , Li 2 MnO 4, or LiFePO 4
  • Patent Documents 1 to 3 exemplify non-aqueous electrolytes to which a dinitrile compound is added, and it is described that cycle characteristics and storage characteristics are improved by the addition of a dinitrile compound.
  • non-aqueous electrolyte secondary batteries copper (Cu), iron (Fe), nickel (Ni), or the like is used for metal members such as outer cans, current collectors, and current collecting tabs constituting the batteries. .
  • these metals are eluted in the non-aqueous electrolyte solution, they are deposited on the electrode plate, causing deterioration of battery characteristics and micro short circuit.
  • the negative electrode potential is 3.2 to 3.3 V on the basis of lithium, which is higher than the dissolution potential of Cu, Fe, Ni, etc. used for metal members (noble potential). ).
  • Patent Document 4 discloses a method for manufacturing a non-aqueous electrolyte secondary battery that performs pre-charging within 24 hours after injection of an electrolyte. Discloses a method for producing a non-aqueous electrolyte secondary battery in which an electrolytic solution is injected with a potential applied between a positive electrode and a negative electrode.
  • Patent Documents 1 and 2 describe that a dinitrile compound has an effect of improving cycle characteristics and storage characteristics because it has a function of protecting the positive electrode.
  • dinitrile compounds having 4 or less carbon atoms in an alkylene group such as adiponitrile are described as examples.
  • a linear dinitrile compound having an alkylene group having 5 or more carbon atoms should be added to the electrolyte. Was found to be preferable.
  • Patent Document 2 describes that addition of a dinitrile compound to an electrolytic solution has an effect of reducing corrosion of metal members such as battery outer cans and electrodes. Further, in Patent Document 3, since the dinitrile compound increases the dissolution potential of Cu or Cu alloy constituting the negative electrode current collector, even when the non-aqueous electrolyte secondary battery reaches an overdischarged state, the negative electrode current collector is disclosed. It is described that there is no possibility that the electric conductor is dissolved. However, as a result of the inventor's confirmation, an experimental result suggesting that the linear dinitrile compound having 5 or more carbon atoms of the alkylene group may promote the dissolution of the metal member such as the negative electrode current collector was obtained. . Such action of the dinitrile compound is not described in the aforementioned patent document.
  • the present invention suppresses gas generation during storage at high temperature charge while suppressing generation of defective products due to voltage drop after charge / discharge even when a linear dinitrile compound having 5 or more carbon atoms in the alkylene group is added to the electrolyte.
  • the present invention provides a method for manufacturing a non-aqueous electrolyte secondary battery.
  • the present invention provides an electrode group comprising a negative electrode including an active material capable of reversibly occluding and releasing lithium ions, a positive electrode including an active material capable of reversibly occluding and releasing lithium ions, and a separator separating the negative electrode and the positive electrode.
  • Non-aqueous electrolyte solution comprising a non-aqueous electrolyte solution inserted into an outer can and containing at least one dinitrile compound represented by the general formula CN— (CH 2 ) n —CN (n is an integer of 5 or more and 12 or less)
  • a method for manufacturing a secondary battery the step of injecting a non-aqueous electrolyte after inserting the electrode group into the outer can, injecting the non-aqueous electrolyte not containing the dinitrile compound, and Step 2 of charging until the negative electrode potential is equal to or lower than the dissolution potential of the metal member equipotential with the negative electrode after Step 1, and a non-aqueous electrolyte containing at least one of the dinitrile compounds after Step 2
  • It is a manufacturing method of the non-aqueous-electrolyte secondary battery characterized by including the step 3 to inject.
  • a dinitrile compound represented by the general formula CN— (CH 2 ) n —CN (n is an integer of 5 or more and 12 or less) is used as the dinitrile compound added to the electrolytic solution. This is because when the carbon number of the alkylene group is 5 or more, the effect of suppressing gas generation during high-temperature storage of the nonaqueous electrolyte secondary battery is great, and when it is 12 or less, the low temperature characteristics are not hindered.
  • the metal member having the same potential as the negative electrode means a metal member electrically connected to the negative electrode plate, and includes a negative electrode current collector and a negative electrode current collecting tab. Furthermore, when the current collecting tab of the negative electrode is electrically connected to the outer can of the battery, the outer can is also included as a metal member having the same potential as the negative electrode.
  • Examples of the metal material of the metal member such as the negative electrode current collector and the negative electrode current collecting tab include Cu, Ni, Fe, and alloys containing these.
  • Examples of the metal material constituting the outer can include Fe, Ni, or an alloy containing these. Note that the dissolution potential of the metal refers to the equilibrium potential of the dissolution / precipitation reaction.
  • the total liquid injection amount of the non-aqueous electrolyte secondary battery according to the present invention is determined by the respective liquid injection amounts in step 1 and step 3.
  • the distribution of these liquid injection amounts is preferably such that the liquid injection amount in step 1 is 50% by mass or more of the total liquid injection amount. If it is less than 50% by mass, the electrolyte does not sufficiently penetrate into the electrode plate, and the charging reaction in Step 2 becomes non-uniform, which is not preferable.
  • step 2 the battery is charged until the negative electrode potential is equal to or lower than the dissolution potential of the metal member equipotential with the negative electrode.
  • the charge amount may be determined based on the metal material exhibiting the lowest dissolution potential among them. For example, when a metal member equipotential to the negative electrode is composed of Cu, Ni, and Fe, if the negative electrode potential is charged to 2.5 V or less with respect to lithium, the negative electrode potential is set to be equal to or lower than the dissolution potential of the metal member. can do. Thereby, it can suppress that the metal component of the metal member which is equipotential with a negative electrode after a battery assembly elutes in electrolyte solution.
  • the negative electrode potential near 2.5 V with respect to lithium greatly changes depending on the amount of charge, it is preferable to charge until the negative electrode potential becomes 1 V or less with respect to lithium in consideration of variations between batteries and voltage changes due to neglect.
  • the charging current can be set arbitrarily, but if it is too large, side reactions such as precipitation of metallic lithium and decomposition of the electrolytic solution are involved.
  • the electrolyte used in Step 3 is preferably a mixture of the electrolyte used in Step 1 and at least one dinitrile compound.
  • the concentration of the dinitrile compound in the electrolytic solution used in Step 3 is preferably adjusted to be 0.01 to 10% by mass in the electrolytic solution of the finished battery. This is because if it is less than 0.01% by mass, the effect of suppressing gas generation during high-temperature charge storage due to the addition of the dinitrile compound cannot be obtained, and if it exceeds 10% by mass, cycle characteristics are deteriorated.
  • Step 3 only the dinitrile compound can be used instead of the electrolytic solution containing the dinitrile compound.
  • the active material according to the nonaqueous electrolyte secondary battery of the present invention can be used without particular limitation as long as it can electrochemically occlude and release lithium ions.
  • the negative electrode active material carbonaceous materials such as natural graphite and artificial graphite, silicon, tin and the like can be used.
  • LiMn 2 O 4 or LiFePO 4 can be used singly or in combination.
  • a microporous film formed from a polyolefin material such as polypropylene or polyethylene can be used as the separator used in the non-aqueous electrolyte secondary battery of the present invention.
  • a laminate of a plurality of polyolefin materials and a structure in which inorganic particles are supported on the surface can also be used.
  • nonaqueous solvent used in the nonaqueous electrolytic solution of the present invention it is preferable to use a nonaqueous solvent containing a cyclic carbonate and a chain carbonate.
  • a cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and fluoroethylene carbonate (FEC).
  • the chain carbonate include dimethyl carbonate (DMC), methyl ethyl carbonate ( MEC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), methyl butyl carbonate (MBC) and the like.
  • a cyclic carbonate and a chain carbonate in a volume ratio of 5:95 to 40:60.
  • cyclic carboxylic acid esters such as ⁇ -butyrolactone (BL) and ⁇ -valerolactone (VL)
  • chain carboxylic acids such as methyl pivalate, ethyl pivalate, methyl isobutyrate, and methyl propionate. Esters can also be used.
  • Examples of the electrolyte salt used in the non-aqueous electrolyte of the present invention include LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 and the like. Can be used.
  • at least one of LiPF 6 or LiBF 4 is preferably an electrolyte salt, and the concentration in the electrolytic solution is preferably 0.5 to 2 mol / L.
  • VEC vinylene carbonate
  • VEC vinyl ethylene carbonate
  • Example 1 Preparation of positive electrode
  • a mixture of lithium cobaltate and nickel manganese lithium cobaltate was used as the positive electrode active material. All of these have a layered structure, and lithium cobaltate containing a different element was used.
  • the heterogeneous element-containing lithium cobalt oxide was produced as follows. As a starting material, lithium carbonate is used as a lithium source, and cobalt carbonate is co-precipitated from an aqueous solution containing cobalt, magnesium, aluminum and zirconium at the time of synthesis as a cobalt source, and then magnesium and aluminum obtained by a thermal decomposition reaction. And tricobalt tetroxide containing zirconium. These were weighed and mixed in a predetermined amount, then calcined at 850 ° C. for 24 hours in an air atmosphere, and a heterogeneous element-containing cobalt acid represented by LiCo 0.973 Mg 0.005 Al 0.02 Zr 0.002 O 2 Lithium was obtained. This was pulverized with a mortar to an average particle size of 14 ⁇ m to obtain a positive electrode active material A.
  • the nickel manganese lithium cobaltate was produced as follows. As starting materials, lithium carbonate was used for the lithium source, and coprecipitated hydroxide represented by Ni 0.33 Mn 0.33 Co 0.34 (OH) 2 was used for the transition metal source. A predetermined amount of these were weighed and mixed, and then fired at 1000 ° C. for 20 hours in an air atmosphere to obtain lithium nickel manganese cobaltate represented by LiNi 0.33 Mn 0.33 Co 0.34 O 2 . This was pulverized to an average particle size of 5 ⁇ m with a mortar to obtain a positive electrode active material B.
  • the positive electrode active material A and the positive electrode active material B obtained as described above were mixed so that the mass ratio was 9: 1.
  • the mixture was mixed to 94% by mass, carbon powder as a conductive agent to 3% by mass, and polyvinylidene fluoride powder as a binder to 3% by mass, and this was mixed with an N-methylpyrrolidone solution to obtain a slurry.
  • This slurry was applied to both sides of a 15 ⁇ m thick aluminum positive electrode current collector by a doctor blade method and dried to form an active material layer on both surfaces of the positive electrode current collector. Then, it compressed using the compression roller and cut
  • a slurry was prepared by dispersing in 95% by weight of graphite powder as the negative electrode active material, 2% by weight of carboxymethyl cellulose as the thickener, and 3% by weight of styrene butadiene rubber as the binder. This slurry was applied to both sides of a copper negative electrode current collector having a thickness of 10 ⁇ m by the doctor blade method and then dried to form an active material layer on both surfaces of the negative electrode current collector. Then, it compressed using the compression roller and cut
  • the filling amount of the active material of the positive electrode and the negative electrode was adjusted so that the charge capacity ratio of the positive electrode to the negative electrode (negative electrode charge capacity / positive electrode charge capacity) was 1.1 at the potential of the positive electrode active material which is a design standard.
  • the design capacity of the battery when the end-of-charge voltage is 4.3 V is 2700 mAh.
  • Fluoroethylene carbonate (FEC), propylene carbonate (PC), and methyl ethyl carbonate (MEC) were mixed at a volume ratio of 25: 5: 70 (25 ° C.) to obtain a nonaqueous solvent used for the nonaqueous electrolyte.
  • a nonaqueous electrolytic solution A was prepared by dissolving LiPF 6 as an electrolyte salt at 1.0 mol / L. Furthermore, it mixed so that vinylene carbonate (VC) might be 0.5 mass% as an electrode protective agent.
  • An electrolyte B was prepared so that the non-aqueous electrolyte A contained 4% by mass of pimelonitrile.
  • the positive electrode plate and the negative electrode plate were wound through a polypropylene separator to prepare an electrode group. After the electrode group was inserted into the outer can, the nonaqueous electrolyte solution was injected by the following method.
  • the outer can was made of nickel-plated iron and the total amount of electrolyte was 5 g.
  • a nonaqueous electrolyte solution A containing no pimelonitrile was injected (step 1).
  • Step 1 3.75 g of electrolyte solution, which is 75% by mass of the total injection amount, was injected.
  • charging was performed at a current of 1350 mA until the charging depth (SOC) of the negative electrode reached 5% (step 2).
  • SOC charging depth
  • step 2 the negative electrode potential was 0.4 V on the basis of lithium.
  • an electrolytic solution B containing pimelonitrile was injected (step 3).
  • Step 3 1.25 g of electrolytic solution B, which is 25% by mass of the total injection amount, was injected.
  • temporary sealing with a sealing body was performed to prevent evaporation of the electrolyte.
  • the opening of the outer can was sealed with a sealing body to produce a cylindrical non-aqueous electrolyte secondary battery having a height of 65 mm and a diameter of 18 mm.
  • the design capacity of the battery is 2700 mAh.
  • Example 2 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that sebacononitrile was used instead of pimelonitrile.
  • Example 1 A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that 5 g of the electrolyte A was injected without using steps 1 to 3 in the step of injecting the electrolyte.
  • Comparative Example 2 A non-aqueous electrolyte secondary battery was produced in the same manner as in Comparative Example 1 except that instead of the electrolytic solution A, an electrolytic solution in which 1% by mass of adiponitrile was added to the electrolytic solution A was used.
  • Comparative Example 3 A nonaqueous electrolyte secondary battery was produced in the same manner as in Comparative Example 2 except that pimelonitrile was used instead of adiponitrile in Comparative Example 2.
  • Comparing Comparative Examples 1 to 3 it can be seen that the addition of a dinitrile compound to the electrolyte suppresses gas generation during high-temperature storage of the non-aqueous electrolyte secondary battery. Especially, it turns out that the gas generation
  • Comparative Example 3 shows that a voltage failure occurs during high-temperature discharge storage, and that pimelonitrile is a cause of defective products due to a voltage drop after charge and discharge. The difference in behavior between adiponitrile and pimelonitrile is thought to be due to the difference in carbon number of the alkylene group of the linear dinitrile compound.
  • Example 1 On the other hand, no voltage failure occurred in Example 1. This indicates that when an electrolytic solution containing pimelonitrile is injected, the method according to steps 1 to 3 described above can be used to suppress the occurrence of voltage failure while maintaining the effect of suppressing the amount of gas generated. .
  • Example 2 the gas generation amount is suppressed as in Example 1. This indicates that a straight-chain dinitrile compound having 5 or more carbon atoms in the alkylene group has an effect of suppressing gas generation.
  • the carbon number of the alkylene group of the linear dinitrile compound is between 4 and 5, the change in the action effect in the non-aqueous electrolyte secondary battery is large, but when the carbon number is between 5 and 8, the action effect is not significant. There is almost no change. From this, it is considered that a linear dinitrile compound having an alkylene group having 5 to 12 carbon atoms has an equivalent effect as an additive to the electrolytic solution.

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  • Manufacturing & Machinery (AREA)
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Abstract

L'invention concerne un procédé de fabrication de batterie secondaire à électrolyte non aqueux dans lequel la génération de gaz peut être supprimée pendant que la batterie secondaire à électrolyte non aqueux est chargée ou stockée à des températures élevées. L'invention concerne un procédé de fabrication de batterie secondaire à électrolyte non aqueux dans lequel un groupe d'électrodes qui comprend une électrode négative contenant un matériau actif capable d'absorber et de désorber de manière réversible des ions lithium une électrode positive contenant un matériau actif capable d'absorber et de désorber de manière réversible des ions lithium et un séparateur qui sépare l'électrode négative et l'électrode positive l'une de l'autre, est inséré dans un boîtier dans lequel est introduite une solution d'électrolyte non aqueuse contenant au moins un composant représenté par la formule générale CN-(CH2)n-CN (où n est un nombre entier de 5 à 12 inclus). Le procédé de fabrication de batterie secondaire à électrolyte non aqueux est caractérisé en ce que le processus au cours duquel la solution d'électrolyte non aqueuse est versée dans le boîtier d'emballage comprend : une étape 1 dans laquelle une solution d'électrolyte non aqueuse ne comprenant pas le composé de dinitrile susmentionné est versée ; une étape 2 dans laquelle la batterie est chargée après l'étape 1 sans que le potentiel de l'électrode négative dépasse le potentiel de fusion d'un élément métallique qui est équipotentiel à l'électrode négative ; et une étape 3 dans laquelle une solution d'électrolyte non aqueuse contenant au moins un composé de dinitrile susmentionné est versée après l'étape 2.
PCT/JP2011/072413 2010-09-30 2011-09-29 Procédé de fabrication de batterie secondaire à électrolyte non aqueux Ceased WO2012043733A1 (fr)

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JP2010-220988 2010-09-30
JP2010220988 2010-09-30

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016021301A (ja) * 2014-07-14 2016-02-04 トヨタ自動車株式会社 非水系二次電池の製造方法
JP2016143536A (ja) * 2015-01-30 2016-08-08 三菱化学株式会社 非水系電解質、及びそれを用いた非水系電解質二次電池
JP2016143449A (ja) * 2015-01-29 2016-08-08 三菱化学株式会社 非水系電解液、及びそれを用いた非水系電解液二次電池
JP2016173948A (ja) * 2015-03-17 2016-09-29 株式会社Ｇｓユアサ 蓄電素子の製造方法、蓄電素子、および、蓄電素子の電圧低下抑制方法。

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003007339A (ja) * 2001-06-22 2003-01-10 Toyota Motor Corp 電池の製造方法および電池
JP2010135316A (ja) * 2008-11-10 2010-06-17 Equos Research Co Ltd 集電体及び電池

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003007339A (ja) * 2001-06-22 2003-01-10 Toyota Motor Corp 電池の製造方法および電池
JP2010135316A (ja) * 2008-11-10 2010-06-17 Equos Research Co Ltd 集電体及び電池

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016021301A (ja) * 2014-07-14 2016-02-04 トヨタ自動車株式会社 非水系二次電池の製造方法
CN106537677A (zh) * 2014-07-14 2017-03-22 丰田自动车株式会社 制造非水二次电池的方法
KR101930178B1 (ko) * 2014-07-14 2018-12-17 도요타지도샤가부시키가이샤 비수계 이차 전지의 제조 방법
US10249915B2 (en) 2014-07-14 2019-04-02 Toyota Jidosha Kabushiki Kaisha Method of manufacturing nonaqueous secondary battery
CN106537677B (zh) * 2014-07-14 2019-08-09 丰田自动车株式会社 制造非水二次电池的方法
JP2016143449A (ja) * 2015-01-29 2016-08-08 三菱化学株式会社 非水系電解液、及びそれを用いた非水系電解液二次電池
JP2016143536A (ja) * 2015-01-30 2016-08-08 三菱化学株式会社 非水系電解質、及びそれを用いた非水系電解質二次電池
JP2016173948A (ja) * 2015-03-17 2016-09-29 株式会社Ｇｓユアサ 蓄電素子の製造方法、蓄電素子、および、蓄電素子の電圧低下抑制方法。

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