WO2012043733A1 - Method for manufacturing nonaqueous electrolyte secondary battery - Google Patents

Method for manufacturing nonaqueous electrolyte secondary battery Download PDF

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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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negative electrode
secondary battery
aqueous electrolyte
electrolyte secondary
nonaqueous electrolyte
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PCT/JP2011/072413
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French (fr)
Japanese (ja)
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篤史 貝塚
岩永　征人
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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
    • 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.

Abstract

[Problem] To provide a method for manufacturing a nonaqueous electrolyte secondary battery wherein generation of a gas can be suppressed during when the nonaqueous electrolyte secondary battery is charged or stored at high temperatures. [Solution] A method for manufacturing a nonaqueous electrolyte secondary battery wherein an electrode group, which is composed of a negative electrode that contains an active material capable of reversibly absorbing and desorbing lithium ions, a positive electrode that contains an active material capable of reversibly absorbing and desorbing lithium ions and a separator that separates the negative electrode and the positive electrode from each other, is inserted into a package can and a nonaqueous electrolyte solution that contains at least one compound represented by general formula: CN-(CH2)n-CN (wherein n represents an integer from 5 to 12 (inclusive)) is contained. The method for manufacturing a nonaqueous electrolyte secondary battery is characterized in that the process wherein the nonaqueous electrolyte solution is poured after inserting the electrode group into the package can comprises: a step 1 wherein a nonaqueous electrolyte solution that does not contain the above-described dinitrile compound is poured; a step 2 wherein the battery is charged after the step 1 until the potential of the negative electrode becomes not more than the melting potential of a metal member that is equipotential to the negative electrode; and a step 3 wherein a nonaqueous electrolyte solution that contains at least one above-described dinitrile compound is poured after the step 2.

Description

非水電解液二次電池の製造方法Method for producing non-aqueous electrolyte secondary battery
　本発明は、非水電解液二次電池の製造方法に関し、さらに詳しくは高温充電保存時のガス発生が抑制された非水電解液二次電池の製造方法に関する。 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.
　非水電解液二次電池は、軽量で、高エネルギー密度を有するため、携帯電話、ノートパソコンといったモバイル電子機器の電源として広く利用されている。非水電解液二次電池の負極活物質として黒鉛等の炭素質材料が用いられ、正極活物質としてはＬｉＣｏＯ２、ＬｉＮｉＯ２、Ｌｉ２ＭｎＯ４やＬｉＦｅＰＯ４等のリチウム金属複合酸化物が用いられている。また、電解液には非水溶媒に、電解質塩としてＬｉ塩を溶解したものが用いられている。 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. ing. Moreover, what dissolved Li salt as electrolyte salt in the nonaqueous solvent is used for electrolyte solution.
　近年、上記電子機器の高機能化に伴い、電源となる非水電解液二次電池に対して、さらなる高容量化や、高温環境下での信頼性、耐久性等といった電池特性に対する要求が厳しくなっている。 In recent years, with the enhancement of functionality of the above electronic devices, demands for battery characteristics such as higher capacity, reliability in high temperature environments, durability, etc. have become stricter with respect to non-aqueous electrolyte secondary batteries as power sources. It has become.
　非水電解液二次電池は、高温環境下で充電状態のまま放置されると、正極活物質中の金属イオンの溶出による性能劣化や、電解液の酸化分解によるガス発生による電池の膨化といった問題が発生する。また、正極活物質の利用率を高めるため、充電電圧を高めに設定すると、正極がより高電位に曝されることになるため、電解液や活物質の酸化に起因する課題がより顕著に現れることになる。この課題を解決するため、極板表面を保護するための電解液への添加剤に関する技術開発が進められている。特許文献１～３には、ジニトリル化合物が添加された非水電解液が例示されており、ジニトリル化合物の添加により、サイクル特性や保存特性が改善されることが記載されている。 When non-aqueous electrolyte secondary batteries are left in a charged state in a high temperature environment, problems such as performance deterioration due to elution of metal ions in the positive electrode active material and expansion of the battery due to gas generation due to oxidative decomposition of the electrolyte Will occur. Moreover, since the positive electrode is exposed to a higher potential when the charging voltage is set higher in order to increase the utilization rate of the positive electrode active material, problems due to the oxidation of the electrolytic solution and the active material appear more remarkably. It will be. In order to solve this problem, technological development relating to an additive to the electrolyte solution for protecting the electrode plate surface is being advanced. 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.
　また、非水電解液二次電池は、電池を構成する外装缶、集電体や集電タブといった金属部材には銅（Ｃｕ）、鉄（Ｆｅ）又はニッケル（Ｎｉ）などが用いられている。ところが、これらの金属が非水電解液中に溶出すると、極板上に析出するなどして、電池特性の低下や微小短絡の原因となってしまう。非水電解液二次電池の組立直後の負極電位はリチウム基準で３．２～３．３Ｖと、金属部材に使用されるＣｕ、Ｆｅ又はＮｉなどの溶解電位に比べて高い電位（貴な電位）を示すことになる。そのため、組立後の非水電解液二次電池を未充電のまま放置した場合、負極と電気的に接続されている金属部材中の微量の金属成分が溶出する可能性がある。このような金属成分の溶出を防ぐための技術として、特許文献４には、電解液の注液後２４時間以内に予備充電を行う非水電解液二次電池の製造方法が、特許文献５には、正極と負極の間に電位を印加した状態で電解液を注液する非水電解液二次電池の製造方法が開示されている。 In addition, in 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. . However, when 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. Immediately after the assembly of the non-aqueous electrolyte secondary battery, 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). ). Therefore, when the non-aqueous electrolyte secondary battery after assembly is left uncharged, a trace amount of metal components in the metal member electrically connected to the negative electrode may be eluted. As a technique for preventing such elution of metal components, 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.
特開平７－１７６３２２号公報JP 7-176322 A 特開２００４－１７９１４６号公報JP 2004-179146 A 特開２００６－７３５１３号公報JP 2006-73513 A 特開平５－１６６５３５号公報JP-A-5-166535 特開２００３－７３３９号公報JP 2003-7339 A
　特許文献１及び２には、ジニトリル化合物は、正極を保護する作用を有するため、サイクル特性や保存特性を改善する効果を奏することが記載されている。これらの特許文献には、アジポニトリル等のアルキレン基の炭素数が４以下のジニトリル化合物が実施例として記載されている。しかし、発明者が確認したところ、非水電解液二次電池の高温充電保存時のガス発生を抑制するには、アルキレン基の炭素数が５以上の直鎖ジニトリル化合物を電解液に添加することが好ましいことが明らかとなった。 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. In these patent documents, dinitrile compounds having 4 or less carbon atoms in an alkylene group such as adiponitrile are described as examples. However, as the inventors have confirmed, in order to suppress gas generation during storage at high temperature of a non-aqueous electrolyte secondary battery, 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.
　ところが、アルキレン基の炭素数が５以上の直鎖ジニトリル化合物を非水電解液二次電池の電解液に添加した場合、充放電後の電圧低下による不良品の発生率が高くなるとの課題が判明した。 However, when a linear dinitrile compound having 5 or more carbon atoms in the alkylene group is added to the electrolyte of the non-aqueous electrolyte secondary battery, it has been found that the incidence of defective products due to voltage drop after charge / discharge increases. did.
　特許文献２には、ジニトリル化合物の電解液への添加は電池の外装缶や電極などの金属部材の腐食を低減する効果があることが記載されている。さらに、特許文献３には、ジニトリル化合物は、負極集電体を構成するＣｕ又はＣｕ合金の溶解電位を上昇させるため、非水電解液二次電池が過放電状態に至った場合でも、負極集電体が溶解するおそれがないことが記載されている。しかし、発明者が確認したところ、アルキレン基の炭素数が５以上の直鎖ジニトリル化合物が、負極集電体等の金属部材の溶解を促進させている可能性を示唆する実験結果が得られた。前記ジニトリル化合物のこのような作用は、前述の特許文献には記載されていない。 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.
　なお、特許文献４に記載されているように注液後２４時間以内に予備充電を行うだけでは、前記ジニトリル化合物による課題を解決することができなかった。また、特許文献５に記載されたような正極と負極に電位を印加した状態で非水電解液を注液する製造方法では、電解液が極板群に浸透する前に充電されることになるため、充電反応を均一なものとすることができない。 In addition, as described in Patent Document 4, the problem caused by the dinitrile compound could not be solved only by performing preliminary charging within 24 hours after injection. Moreover, in the manufacturing method which inject | pours a nonaqueous electrolyte solution in the state which applied the electric potential to the positive electrode and negative electrode which were described in patent document 5, it will charge before electrolyte solution osmose | permeates an electrode group. Therefore, the charging reaction cannot be made uniform.
　本発明は、アルキレン基の炭素数が５以上の直鎖ジニトリル化合物を電解液に添加しても充放電後の電圧低下による不良品の発生を抑制しつつ、高温充電保存時のガス発生を抑制することができる非水電解液二次電池の製造方法を提供するものである。 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.
　本発明は、リチウムイオンを可逆的に吸蔵放出できる活物質を含む負極と、リチウムイオンを可逆的に吸蔵放出できる活物質を含む正極と、前記負極と前記正極を隔離するセパレータからなる電極群が外装缶に挿入され、一般式ＣＮ－（ＣＨ２）ｎ－ＣＮ（ｎは５以上１２以下の整数）で表されるジニトリル化合物の少なくとも１種を含む非水電解液を備える非水電解液二次電池の製造方法であって、前記電極群を前記外装缶に挿入した後、非水電解液を注液する工程が、前記ジニトリル化合物を含まない非水電解液を注液するステップ１と、ステップ１の後に前記負極電位が前記負極と等電位にある金属部材の溶解電位以下になるまで充電するステップ２と、ステップ２の後に前記ジニトリル化合物の少なくとも１種を含む非水電解液を注液するステップ３を含むことを特徴とする非水電解液二次電池の製造方法である。 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.
　上記の構成によれば、電解液に前記ジニトリル化合物を添加した場合の電圧低下による不良品の発生を抑制しつつ、高温充電保存時のガス発生を効果的に抑制することが可能となる。 According to the above configuration, it is possible to effectively suppress the generation of gas during storage at high temperature while suppressing the generation of defective products due to the voltage drop when the dinitrile compound is added to the electrolytic solution.
　本発明では、電解液に添加するジニトリル化合物として、一般式ＣＮ－（ＣＨ２）ｎ－ＣＮ（ｎは５以上１２以下の整数）で表されるジニトリル化合物を採用した。これは、アルキレン基の炭素数が５以上では非水電解液二次電池の高温保存時のガス発生抑制効果が大きく、１２以下では低温特性等が阻害されることがないためである。 In the present invention, 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.
　本発明にいう、負極と等電位にある金属部材とは、負極極板と電気的に接続されている金属部材をいい、負極集電体、負極の集電タブが挙げられる。さらに、負極の集電タブが電池の外装缶と電気的に接続されている場合は、外装缶も負極と等電位の金属部材として含まれる。 In the present invention, 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.
　負極集電体や負極の集電タブといった金属部材の金属材料としては、Ｃｕ、Ｎｉ、Ｆｅ又はこれらを含む合金が挙げられる。外装缶を構成する金属材料としては、Ｆｅ、Ｎｉ又はこれらを含む合金が挙げられる。なお、金属の溶解電位とはその溶解・析出反応の平衡電位を指すものとする。 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.
　本発明に係る非水電解液二次電池の総注液量は、ステップ１及びステップ３のそれぞれの注液量で決定される。これらの注液量の配分は、ステップ１の注液量が総注液量の５０質量％以上とすることが好ましい。５０質量％未満だと、極板への電解液の浸透が十分でなく、ステ
ップ２の充電反応が不均一なものとなるため好ましくない。 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.
　ステップ２においては、前記負極電位が、前記負極と等電位にある金属部材の溶解電位以下になるまで充電する。複数の金属材料が前記金属部材に使用されている場合は、その中で最も低い溶解電位を示す金属材料を基準として充電量を決定すればよい。例えば、負極と等電位にある金属部材が、Ｃｕ、Ｎｉ及びＦｅで構成される場合、負極電位がリチウム基準で２．５Ｖ以下になるまで充電すれば、負極電位を金属部材の溶解電位以下とすることができる。これにより、電池組立後に負極と等電位にある金属部材の金属成分が電解液中に溶出することを抑制することができる。ただし、リチウム基準で２．５Ｖ付近の負極電位は充電量による変化が大きいため、電池間のバラツキや放置による電圧変化を考慮すると、負極電位がリチウム基準で１Ｖ以下になるまで充電することが好ましい。充電電流は任意に設定できるが、過大であると金属リチウムの析出や電解液の分解といった副反応を伴うため３Ｉｔ以下とすることが好ましい。 In 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. When a plurality of metal materials are used for the metal member, 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. However, since 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.
　ステップ３で使用する電解液は、ステップ１で使用する電解液に前記ジニトリル化合物の少なくとも１種を混合したものを使用するのが好ましい。ステップ３で使用する電解液中のジニトリル化合物の濃度は、完成電池の電解液中で０．０１～１０質量％となるように調整することが好ましい。０．０１質量％未満だと、前記ジニトリル化合物の添加による高温充電保存時のガス発生の抑制効果が得られず、１０質量％を超えるとサイクル特性の低下が見られるからである。また、ステップ３においては、前記ジニトリル化合物を含む電解液に代えて、前記ジニトリル化合物のみを使用することもできる。 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. In Step 3, only the dinitrile compound can be used instead of the electrolytic solution containing the dinitrile compound.
　本発明の非水電解液二次電池に係る活物質としては、リチウムイオンを電気化学的に吸蔵放出できるものなら特に限定されずに使用することができる。負極活物質としては、天然黒鉛、人造黒鉛などの炭素質材料やケイ素、スズなどを用いることができる。また、正極活物質としては、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＮｉｙＣｏ１－ｙＯ２（ｙ＝０．０１～０．９９）、ＬｉＭｎＯ２、ＬｉＮｉｘＭｎｙＣｏｚＯ２（ｘ＋ｙ＋ｚ＝１）や、ＬｉＭｎ２Ｏ４又はＬｉＦｅＰＯ４などを一種単独もしくは複数種を混合して用いることができる。 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. As the negative electrode active material, carbonaceous materials such as natural graphite and artificial graphite, silicon, tin and the like can be used. As the cathode active material, LiCoO 2, LiNiO 2, LiNi y Co 1-y O 2 (y = 0.01 ~ 0.99), LiMnO 2, LiNi x Mn y Co z O 2 (x + y + z = 1) Alternatively, LiMn 2 O 4 or LiFePO 4 can be used singly or in combination.
　本発明の非水電解液二次電池に使用するセパレータとしては、ポリプロピレンやポリエチレンなどのポリオレフィン材料から形成された微多孔膜を使用することができる。セパレータのシャットダウン応答性と、耐熱性や化学的安定性を両立させるために複数のポリオレフィン材料の積層体や表面に無機粒子を担持させた構成とすることもできる。 As the separator used in the non-aqueous electrolyte secondary battery of the present invention, a microporous film formed from a polyolefin material such as polypropylene or polyethylene can be used. In order to achieve both the shutdown response of the separator and the heat resistance and chemical stability, a laminate of a plurality of polyolefin materials and a structure in which inorganic particles are supported on the surface can also be used.
　本発明の非水電解液に用いる非水溶媒としては、環状カーボネート、鎖状カーボネートを含む非水溶媒を使用することが好ましい。環状カーボネートとしては、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート（ＢＣ）、フルオロエチレンカーボネート（ＦＥＣ）などが挙げられ、鎖状カーボネートとしては、ジメチルカーボネート（ＤＭＣ）、メチルエチルカーボネート（ＭＥＣ）、ジエチルカーボネート（ＤＥＣ）、メチルプロピルカーボネート（ＭＰＣ）、メチルブチルカーボネート（ＭＢＣ）などが挙げられる。溶媒の粘度、イオン伝導度の観点から、環状カーボネートと鎖状カーボネートを体積比５：９５～４０：６０の範囲で使用することが好ましい。さらに非水溶媒として、γ－ブチロラクトン（ＢＬ）、γ－バレロラクトン（ＶＬ）などの環状カルボン酸エステルやピバリン酸メチル、ピバリン酸エチル、メチルイソブチレート、メチルプロピオネートなどの鎖状カルボン酸エステルを使用することもできる。 As the 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. Examples of the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and fluoroethylene carbonate (FEC). Examples of 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. From the viewpoint of the viscosity of the solvent and the ionic conductivity, it is preferable to use a cyclic carbonate and a chain carbonate in a volume ratio of 5:95 to 40:60. Further, as non-aqueous solvents, cyclic carboxylic acid esters such as γ-butyrolactone (BL) and γ-valerolactone (VL), and chain carboxylic acids such as methyl pivalate, ethyl pivalate, methyl isobutyrate, and methyl propionate. Esters can also be used.
　本発明の非水電解液に用いる電解質塩としてはＬｉＰＦ６、ＬｉＢＦ４、ＬｉＡｓＦ６、ＬｉＣｌＯ４、ＬｉＣＦ３ＳＯ３、ＬｉＮ(ＣＦ３ＳＯ２)２、ＬｉＮ(Ｃ２Ｆ５ＳＯ２)２等を使用することができる。特に、ＬｉＰＦ６又はＬｉＢＦ４の少なくとも一方を電解質塩とし、電解液中の濃度を０．５～２ｍｏｌ／Ｌとすることが好ましい。 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. In particular, 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.
　さらに、本発明の非水電解液には、電極保護剤として、ビニレンカーボネート（ＶＣ）、ビニルエチレンカーボネート（ＶＥＣ）などを添加することもできる。 Furthermore, vinylene carbonate (VC), vinyl ethylene carbonate (VEC), etc. can be added to the non-aqueous electrolyte of the present invention as an electrode protective agent.
　以下、本発明を実施するための最良の形態を実施例及び比較例を用いて詳細に説明する。ただし、以下に示す実施例は、本発明の技術思想を具体化するための非水電解液二次電池の製造方法の一例を例示するものであって、本発明をこの実施例に限定することを意図するものではなく、本発明は特許請求の範囲に示した技術思想を逸脱することなく種々の変更を行ったものにも均しく適用し得るものである。 Hereinafter, the best mode for carrying out the present invention will be described in detail using examples and comparative examples. However, the following examples illustrate an example of a method for manufacturing a non-aqueous electrolyte secondary battery for embodying the technical idea of the present invention, and the present invention is limited to this example. However, the present invention can be equally applied to various modifications without departing from the technical idea shown in the claims.
　（実施例）
　（実施例１）
　（正極の作製）
　正極活物質には、コバルト酸リチウムとニッケルマンガンコバルト酸リチウムの混合物を用いた。これらはいずれも層状構造を有しており、コバルト酸リチウムは異種元素を含むものを用いた。 (Example)
Example 1
(Preparation of positive electrode)
As the positive electrode active material, a mixture of lithium cobaltate and nickel manganese lithium cobaltate was used. All of these have a layered structure, and lithium cobaltate containing a different element was used.
　異種元素含有コバルト酸リチウムは次のようにして作製した。出発原料としては、リチウム源には炭酸リチウムを用い、コバルト源には合成時にコバルト、マグネシウム、アルミニウム及びジルコニウムを含む水溶液から炭酸コバルトを共沈させ、その後、熱分解反応によって得られたマグネシウム、アルミニウム及びジルコニウムを含有する四酸化三コバルトを用いた。これらを所定量秤量して混合した後、空気雰囲気下において８５０℃で２４時間焼成し、ＬｉＣｏ０．９７３Ｍｇ０．００５Ａｌ０．０２Ｚｒ０．００２Ｏ２で表される異種元素含有コバルト酸リチウムを得た。これを乳鉢で平均粒径１４μｍまで粉砕し、正極活物質Ａとした。 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 μm to obtain a positive electrode active material A.
　ニッケルマンガンコバルト酸リチウムは次のようにして作製した。出発原料としては、リチウム源には炭酸リチウムを、遷移金属源にはＮｉ０．３３Ｍｎ０．３３Ｃｏ０．３４（ＯＨ）２で表される共沈水酸化物を用いた。これらを所定量秤量して混合した後、空気雰囲気下において１０００℃で２０時間焼成し、ＬｉＮｉ０．３３Ｍｎ０．３３Ｃｏ０．３４Ｏ２で表されるニッケルマンガンコバルト酸リチウムを得た。これを乳鉢で平均粒径５μｍまで粉砕し、正極活物質Ｂとした。 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 μm with a mortar to obtain a positive electrode active material B.
　以上のようにして得られた正極活物質Ａと正極活物質Ｂを質量比が９：１になるように混合した。この混合物が９４質量％、導電剤としての炭素粉末が３質量％、結着剤としてのポリフッ化ビニリデン粉末が３質量％となるよう混合し、これをＮ－メチルピロリドン溶液と混合してスラリーを調製した。このスラリーを厚さ１５μｍのアルミニウム製の正極集電体の両面にドクターブレード法により塗布、乾燥して、正極集電体の両面に活物質層を形成した。その後、圧縮ローラーを用いて圧縮し、所定寸法に切断して正極を作製した。 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. Prepared. This slurry was applied to both sides of a 15 μm 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 | disconnected to the predetermined dimension, and produced the positive electrode.
　（負極の作製）
　負極活物質としての黒鉛粉末が９５質量％、増粘剤としてのカルボキシメチルセルロースが２質量％、結着剤としてのスチレンブタジエンゴムが３質量％となるように水に分散させ、スラリーを調製した。このスラリーを厚さ１０μｍの銅製の負極集電体の両面にドクターブレード法により塗布後、乾燥して負極集電体の両面に活物質層を形成した。その後、圧縮ローラーを用いて圧縮し、所定寸法に切断して負極を作製した。 (Preparation of negative electrode)
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 μm 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 | disconnected to the predetermined dimension, and produced the negative electrode.
　正極及び負極の活物質の充填量は、設計基準となる正極活物質の電位において、正極と負極の充電容量比（負極充電容量／正極充電容量）が１．１となるように調整した。なお、充電終止電圧を４．３Ｖとした場合の電池の設計容量は２７００ｍＡｈである。 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.
　（非水電解液の調製）
　フルオロエチレンカーボネート（ＦＥＣ）、プロピレンカーボネート（ＰＣ）及びメチルエチルカーボネート（ＭＥＣ）を体積比で２５：５：７０（２５℃）となるように混合して非水電解液に用いる非水溶媒とした。電解質塩としてＬｉＰＦ６が１．０ｍｏｌ／Ｌとなるように溶解して非水電解液Ａを調製した。さらに、電極保護剤としてビニレンカーボネート（ＶＣ）が０．５質量％となるように混合した。非水電解液Ａが４質量％のピメロニトリルを含むように調製したものを電解液Ｂとした。 (Preparation of non-aqueous electrolyte)
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.
　（電池の作製）
　正極極板と負極極板をポリプロピレン製のセパレータを介して巻取り、電極群を作製した。当該電極群を外装缶へ挿入した後、以下の方法で非水電解液の注液を行った。なお、外装缶にはニッケルめっきをした鉄製のものを用い、電解液の総注液量は５ｇとした。 (Production of battery)
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.
　まず、ピメロニトリルを含まない非水電解液Ａの注液を行った（ステップ１）。ステップ１では、総注液量の７５質量％となる３．７５ｇの電解液を注液した。２４時間放置後に１３５０ｍＡの電流で、負極の充電深度（ＳＯＣ）が５％となるまで充電を行った（ステップ２）。このとき、負極電位はリチウム基準で０．４Ｖであった。その後、ピメロニトリルを含む電解液Ｂの注液を行った（ステップ３）。ステップ３においては、総注液量の２５質量％となる１．２５ｇの電解液Ｂを注液した。なお、ステップ１からステップ２への待機時間中は、電解液の蒸発を防ぐため封口体による仮封口を行った。 First, a nonaqueous electrolyte solution A containing no pimelonitrile was injected (step 1). In Step 1, 3.75 g of electrolyte solution, which is 75% by mass of the total injection amount, was injected. After being left for 24 hours, charging was performed at a current of 1350 mA until the charging depth (SOC) of the negative electrode reached 5% (step 2). At this time, the negative electrode potential was 0.4 V on the basis of lithium. Thereafter, an electrolytic solution B containing pimelonitrile was injected (step 3). In Step 3, 1.25 g of electrolytic solution B, which is 25% by mass of the total injection amount, was injected. During the waiting time from step 1 to step 2, temporary sealing with a sealing body was performed to prevent evaporation of the electrolyte.
　上記の注液の後、封口体により外装缶の開口部を密閉し、高さ６５ｍｍ、直径１８ｍｍの円筒形非水電解液二次電池を作製した。当該電池の設計容量は、２７００ｍＡｈである。 After the above injection, 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.
　（実施例２）
　ピメロニトリルに代えてセバコニトリルを使用したことを除き、実施例１と同様にして非水電解液二次電池を作製した。 (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.
　（比較例１）
　電解液を注液する工程において、ステップ１～３を用いることなく、５ｇの電解液Ａを注液したことを除き、実施例１と同様にして非水電解液二次電池を作製した。 (Comparative 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.
　（比較例２）
　比較例１において、電解液Ａに代えて、電解液Ａにアジポニトリルを１質量％添加した電解液を使用したことを除き、比較例１と同様にして非水電解液二次電池を作製した。 (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.
　（比較例３）
　比較例２において、アジポニトリルに代えてピメロニトリルを使用したことを除き、比較例２と同様にして非水電解液二次電池を作製した。 (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.
　（高温充電保存試験）
　実施例１、２及び比較例１～３の各電池を２５℃において、０．５Ｉｔ＝１３５０ｍＡの定電流で充電し、電池電圧が４．３Ｖに達した後は、４．３Ｖの定電圧で充電電流が（１／５０）Ｉｔ＝５４ｍＡとなるまで充電した。その後、充電状態のまま６０℃に維持された恒温槽中に２０日間保存した。その後、電池を２５℃になるまで冷却し、有機溶媒中で、封口体を取り外し、電池内部のガスを捕集してガス発生量を測定した。本試験の結果を比較例２のガス発生量を１００とした場合の相対的な指数で表１に示した。 (High temperature charge storage test)
The batteries of Examples 1 and 2 and Comparative Examples 1 to 3 were charged at a constant current of 0.5 It = 1350 mA at 25 ° C. After the battery voltage reached 4.3 V, the batteries were charged with a constant voltage of 4.3 V. The battery was charged until the charging current was (1/50) It = 54 mA. Then, it preserve | saved for 20 days in the thermostat maintained at 60 degreeC with the charge condition. Thereafter, the battery was cooled to 25 ° C., the sealing body was removed in an organic solvent, the gas inside the battery was collected, and the amount of gas generated was measured. The results of this test are shown in Table 1 as relative indices when the amount of gas generated in Comparative Example 2 is 100.
　（高温放電保存試験）
　実施例１、２及び比較例１～３の各電池を２５℃において、０．５Ｉｔ＝１３５０ｍＡの定電流で充電し、電池電圧が４．３Ｖに達した後は、４．３Ｖの定電圧で充電電流が（１／５０）Ｉｔ＝５４ｍＡとなるまで充電した。さらに１０分休止後、０．５Ｉｔの定電流で電池電圧が３．０Ｖになるまで放電した。その後、放電状態で６０℃に維持された恒温槽中に３０日間保存した。本試験は、各ロット３０セルを使用し、放電保存前後の電圧低下量が、平均値から３σ（σは標準偏差）以上のものを不良品とした。本試験は、充放電後の電圧不良の発生率を評価するための加速試験として行った。ここで、平均値、σは各ロット電圧低下量の上下の５セルを除いた２０セルの結果から算出した。本試験で発生した不良品数を表１に示した。 (High-temperature discharge storage test)
The batteries of Examples 1 and 2 and Comparative Examples 1 to 3 were charged at a constant current of 0.5 It = 1350 mA at 25 ° C. After the battery voltage reached 4.3 V, the batteries were charged with a constant voltage of 4.3 V. The battery was charged until the charging current was (1/50) It = 54 mA. After a further 10 minutes of rest, the battery was discharged at a constant current of 0.5 It until the battery voltage reached 3.0V. Then, it preserve | saved for 30 days in the thermostat maintained at 60 degreeC in the discharge state. In this test, 30 cells were used for each lot, and a voltage drop amount before and after discharge storage was 3σ (σ is a standard deviation) or more from the average value as a defective product. This test was performed as an accelerated test for evaluating the incidence of voltage failure after charge / discharge. Here, the average value, σ, was calculated from the results of 20 cells excluding the upper and lower 5 cells of each lot voltage drop amount. The number of defective products generated in this test is shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　比較例１～３を比較すると、電解液にジニトリル化合物を添加することで非水電解液二次電池の高温保存時のガス発生が抑制されることがわかる。中でも、ピメロニトリルによるガス発生抑制効果が大きいことがわかる。しかし、比較例３には高温放電保存時の電圧不良が発生しており、ピメロニトリルが充放電後の電圧低下による不良品の発生原因となっていることが示されている。アジポニトリルとピメロニトリルの挙動の相違は、直鎖ジニトリル化合物のアルキレン基の炭素数の相違に起因するものと考えられる。 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 | occurrence | production suppression effect by a pimelonitrile is large. However, 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.
　一方、実施例１には電圧不良は発生していない。これは、ピメロニトリルを含む電解液を注液する場合、前記ステップ１～３に準じた方法を用いることで、ガス発生量の抑制効果を維持しつつ、電圧不良の発生を抑制できることを示している。 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. .
　さらに、実施例２においても実施例１と同様にガス発生量が抑制されている。このことは、アルキレン基の炭素数が５以上の直鎖ジニトリル化合物がガス発生抑制効果を有することを示すものである。また、直鎖ジニトリル化合物のアルキレン基の炭素数が４と５の間では、非水電解液二次電池中における作用効果の変化は大きいが、その炭素数が５と８の間では作用効果の変化は殆ど見られない。このことから、アルキレン基の炭素数が５～１２の範囲にある直鎖ジニトリル化合物は、電解液への添加剤として同等の効果を奏するものと考えられる。 Furthermore, in 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. In addition, when 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.
　以上より、本発明によれば、アルキレン基の炭素数の多い直鎖ジニトリル化合物を電解液に添加することで、高温保存時のガス発生が効果的に抑制されるとともに、充放電後の電圧低下による不良品が増加するという課題を解決しうることが明らかとなった。 As described above, according to the present invention, by adding a linear dinitrile compound having a large number of carbon atoms of an alkylene group to the electrolytic solution, gas generation during high-temperature storage is effectively suppressed, and voltage drop after charge / discharge is achieved. It became clear that the problem that the number of defective products due to the increase could be solved.
従来から製造されている円筒形の非水電解液二次電池を縦方向に切断して示す斜視図である。It is a perspective view which cuts the cylindrical nonaqueous electrolyte secondary battery manufactured conventionally from the lengthwise direction.
１０：非水電解液二次電池、１１：正極、１１ａ：正極の集電タブ、１２：負極、１２ａ：負極の集電タブ、１３：セパレータ、１４：巻回電極群、１７：外装缶　１８：封口体  10: nonaqueous electrolyte secondary battery, 11: positive electrode, 11a: current collector tab of positive electrode, 12: negative electrode, 12a: current collector tab of negative electrode, 13: separator, 14: wound electrode group, 17: outer can 18 : Sealed body

Claims (3)

  1. 　リチウムイオンを可逆的に吸蔵放出できる活物質を含む負極と、リチウムイオンを可逆的に吸蔵放出できる活物質を含む正極と、前記負極と前記正極を隔離するセパレータからなる電極群が外装缶に挿入され、一般式ＣＮ－（ＣＨ２）ｎ－ＣＮ（ｎは５以上１２以下の整数）で表されるジニトリル化合物の少なくとも１種を含む非水電解液を備える非水電解液二次電池の製造方法であって、
    　前記電極群を前記外装缶に挿入した後、非水電解液を注液する工程が、
    　前記ジニトリル化合物を含まない非水電解液を注液するステップ１と、
    　ステップ１の後、前記負極電位が、前記負極と等電位にある金属部材の溶解電位以下になるまで充電するステップ２と、
    　ステップ２の後、前記ジニトリル化合物の少なくとも１種を含む非水電解液を注液するステップ３を含むことを特徴とする、
    　非水電解液二次電池の製造方法。     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 an electrode group including a separator separating the negative electrode and the positive electrode are inserted into an outer can. And a non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte 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,
    After inserting the electrode group into the outer can, the step of injecting a non-aqueous electrolyte solution,
    Injecting a non-aqueous electrolyte containing no dinitrile compound; and
    After step 1, 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 2, the method includes a step 3 of injecting a non-aqueous electrolyte containing at least one of the dinitrile compounds.
    A method for producing a non-aqueous electrolyte secondary battery.
  2. 　請求項１記載のステップ３において、前記ジニトリル化合物の少なくとも１種を含む非水電解液に代えて、前記ジニトリル化合物の少なくとも１種を使用する非水電解液二次電池の製造方法。 The method for manufacturing a non-aqueous electrolyte secondary battery according to claim 3, wherein at least one of the dinitrile compounds is used in place of the non-aqueous electrolyte containing at least one of the dinitrile compounds.
  3. 　前記金属部材がＣｕ、Ｎｉ及びＦｅの少なくとも１種を含む請求項１又は２に記載の非水電解液二次電池の製造方法。
     
          The method for manufacturing a non-aqueous electrolyte secondary battery according to claim 1, wherein the metal member includes at least one of Cu, Ni, and Fe.

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JP2016143449A (en) * 2015-01-29 2016-08-08 三菱化学株式会社 Nonaqueous type electrolytic solution and nonaqueous type electrolytic solution secondary battery using the same
JP2016143536A (en) * 2015-01-30 2016-08-08 三菱化学株式会社 Nonaqueous type electrolyte and nonaqueous electrolyte secondary battery using the same
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