JPH11185804A - Non-aqueous electrolyte solution for a secondary battery - Google Patents

Non-aqueous electrolyte solution for a secondary battery

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Publication number
JPH11185804A
JPH11185804A JP36389597A JP36389597A JPH11185804A JP H11185804 A JPH11185804 A JP H11185804A JP 36389597 A JP36389597 A JP 36389597A JP 36389597 A JP36389597 A JP 36389597A JP H11185804 A JPH11185804 A JP H11185804A
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non
example
secondary battery
group
electrolyte
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Japanese (ja)
Inventor
Takashi Fujino
Tetsuo Kojima
Minoru Nakano
Takahiro Rokkaku
Sadao Ueda
Yusuke Watanuki
定夫 上田
稔 中野
隆広 六角
哲雄 小島
祐介 綿貫
高志 藤野
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Toyama Yakuhin Kogyo Kk
富山薬品工業株式会社
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Abstract

PROBLEM TO BE SOLVED: To enhance battery characteristics such as charging/discharging cycle characteristic, a low temperature discharge characteristic, or a storage characteristic by adding a silicon series anti-foaming agent represented by a specific formula to an electrolyte having concentration of the specified weight percent. SOLUTION: A silicone series anti-foaming agent represented by the formula [in the formula, R represents an organic group or a hydrogen atom, which may be the same or different] is used as a silicone series anti-foaming agent to be added. As the organic group, an alkyl group and an aryl group are listed, and the alkyl group having a low molecular weight is used to increase the conductivity of an electrolyte. As the example of the alkyl group, a methyl group and an ethyl group are listed, and as the example of the aryl group, a phenyl group is listed. The concentration of the anti-foaming agent in the nonaqueous electrolyte is preferable to be 10 ppm to 10 wt.% since too low concentration does not show sufficient effect and too high concentration tends to decrease the capacity of a battery.

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【発明の属する技術分野】本発明は、リチウム化合物を電解質として含有する二次電池用非水電解液に関し、特に、負極と非水電解液中の溶媒との反応に起因する、低温放電特性の低下の防止、インピ−ダンス特性の改善を目的とした当該非水電解液の改良技術に関する。 BACKGROUND OF THE INVENTION The present invention provides a lithium compound relates non-aqueous electrolyte secondary battery containing as an electrolyte, in particular, due to the reaction with the solvent of the negative electrode and the nonaqueous electrolyte solution, the low-temperature discharge characteristics prevention of reduction, Inpi - an improvement technology of the non-aqueous electrolyte for the purpose of improving the dance characteristics.

【0002】 [0002]

【従来の技術】近年、カメラ一体型VTR、携帯電話、 In recent years, camera-integrated VTR, mobile phone,
ラップトップコンピュータ等の新しいポータブル電源として、特に、従来のニッケルーカドミニウム(Ni−C As a new portable power source such as a laptop computer, in particular, the conventional nickel-cadmium (Ni-C
d)二次電池や鉛二次電池に比べ軽量で高容量且つ高エネルギー密度のリチウム二次電池が注目されている。 d) a high capacity and a lithium secondary battery of high energy density lighter than the secondary battery and a lead battery is attracting attention.

【0003】従来より、リチウム二次電池の非水電解液の電解質としては、LiPF 6 、LiBF 4等が、また、 Conventionally, as the electrolyte of the non-aqueous electrolyte lithium secondary battery, LiPF 6, LiBF 4 or the like, also,
非水溶媒としては、炭酸プロピレン(PC)、炭酸エチレン(EC)、γーブチロラクトン(GBL)、炭酸ジメチル(DMC)、炭酸エチルメチル(MEC)、炭酸ジエチル(DEC)、酢酸エチル(EA)、プロピオン酸メチル(MPR)、1,2−ジメトキシエタン(DM As the non-aqueous solvent, propylene carbonate (PC), ethylene carbonate (EC), gamma-butyrolactone (GBL), dimethyl carbonate (DMC), ethyl methyl carbonate (MEC), diethyl carbonate (DEC), ethyl acetate (EA), propionate (MPR), 1,2-dimethoxyethane (DM
E)、2−メチルテトラヒドロフラン(2−MeTH E), 2-methyltetrahydrofuran (2-metH
F)等が用いられている。 F) or the like is used.

【0004】しかしながら、負極活物質であるリチウムは反応性に富み、上記電解質と反応し、その反応生成物が電極表面に被膜となって付着し、その被膜が電池特性に大きく影響を与える。 However, lithium as the negative electrode active material highly reactive, reacts with the electrolyte, the reaction product is deposited a coating on the electrode surface, the coating will greatly affect the battery characteristics. そこで、電池特性に悪影響を及ぼさないよう電解液組成が工夫されており、一般に、上記PCあるいはEC等の炭酸エステル類は、リチウムと反応してイオン伝導性を有する炭酸塩の被膜を生成する為、電池内部抵抗の増加等の電池特性に及ぼす悪影響は少なく、さらに、この被膜が負極表面の保護膜となり、 Therefore, and the electrolyte composition not to adversely affect the battery characteristics is devised, in general, carbonic acid esters such as the PC or EC is to generate a film of reacting with lithium carbonate having ionic conductivity less adverse effect on the battery characteristics, such as increased battery internal resistance, furthermore, the coating is a protective layer of the negative electrode surface,
電池の保存特性等を良好にしているので、従来よりリチウム二次電池用非水電解液の主成分となっている。 Since the improving the storage characteristics of the battery, it is conventionally made mainly of the non-aqueous electrolyte for lithium secondary batteries. しかし、当該炭酸エステル類は、比較的融点が高く、また、 However, the carbonic acid esters is relatively high melting point, also,
当該PCあるいはEC等の環状のものは、粘性率が高く、さらに、上記DMCあるいはDEC等の直鎖状のものは、誘電率が低い為、上記GBLあるいはEA等のカルボン酸エステルと比較すると、電解液溶媒とした時の電解液の導電率が小さいという欠点がある。 Of the cyclic such as the PC or EC has a high viscosity, furthermore, is a straight-chain such as the DMC or DEC, since the dielectric constant is low, when compared with carboxylic acid esters such as the GBL or EA, there is a disadvantage that the conductivity of the electrolyte when the electrolyte solvent is small. 従って、高出力な二次電池として要求される充分な急速充電特性あるいは低温放電特性が得られなかった。 Therefore, sufficient rapid charge characteristics or low-temperature discharge characteristics are required as a high-output rechargeable battery is not obtained. さらに、炭酸エステル類は、二次電池の充電放電時あるいは高温下での保存中に、分解により炭酸ガスやオレフィンガスを生成する為、内圧が上昇し、電池が膨れるという問題があった。 Furthermore, such ester carbonate, during storage at the time of charge and discharge, or high temperature of the secondary battery, for generating a carbon dioxide gas or an olefin gas by decomposition, the internal pressure is increased, there is a problem that battery swelling.

【0005】 [0005]

【発明が解決しようとする課題】本発明は、かかる従来技術の有する欠点を解消できる技術を提供することを目的としたものであって、特に、二次電池の充電放電サイクル特性、低温放電特性、保存特性等の電池特性を向上させることができる技術を提供することを目的とする。 [0008] The present invention has been intended to provide a technique capable of eliminating the drawbacks possessed by the prior art, in particular, the charge-discharge cycle characteristics of the secondary battery, low-temperature discharge characteristics , and an object thereof is to provide a technique capable of improving the battery characteristics such as storage characteristics.
本発明の前記ならびにそのほかの目的と新規な特徴は、 The above and other objects and novel features of the present invention,
本明細書の記述および添付図面からもあきらかになるであろう。 It will become apparent from the description of this specification and the accompanying drawings.

【0006】 [0006]

【課題を解決するための手段】本発明者らは、上述の目的を達成する為に、鋭意検討した結果、非水電解液二次電池の非水電解液へシリコ−ン系消泡剤を添加することにより、充放電における非水電解液の分解によるガス発生を抑制し、また、放電容量の向上、並びに、インピ− Means for Solving the Problems The present inventors have found that in order to achieve the above object, a result of intensive studies, silicone to non-aqueous electrolyte of the non-aqueous electrolyte secondary battery - the emissions antifoam the addition, to suppress gas generation due to decomposition of the nonaqueous electrolytic solution in charge and discharge, also, improvement of the discharge capacity, as well, Inpi -
ダンス特性が改善できることを見出し、これに基づき、 It found that dance characteristics can be improved, based on this,
上述問題を解決する電解液を発明するに至った。 This has led to the invention the electrolyte to solve the above problems. すなわち、本発明は、非水溶媒と、電解質としてリチウム化合物を含む二次電池用非水電解液において、シリコ−ン系消泡剤を添加してなることを特徴とする二次電池用非水電解液に係るものである。 That is, the present invention provides a non-aqueous solvent, non-aqueous electrolyte solution for a secondary battery comprising a lithium compound as the electrolyte, silicone - characterized by comprising the addition of down antifoam nonaqueous secondary battery it relates to the electrolytic solution.

【0007】 [0007]

【発明の実施の形態】以下、本発明を詳細に説明する。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
本発明において使用されるシリコ−ン系消泡剤の例としては、次の式1で表されるシリコ−ン系消泡剤が挙げられる。 Silicone used in the present invention - Examples of emissions based defoaming agents, silicone represented by the following formula 1 - emissions based antifoaming agents.

【0008】 [0008]

【式1】 [Formula 1]

【0009】但し、上記式中のR [0009] However, R in the above formula は、有機基もしくは水素原子であり、同一でも、異なっていてもよい。 Is an organic group or a hydrogen atom may be identical or different. 有機基であることが、本発明の目的から好ましい。 It is preferred object of the present invention is an organic group. 有機基の例としては、アルキル基、アリ−ル基が挙げられる。 Examples of the organic group, an alkyl group, ant - Le group. 当該アルキル基における炭素数には特に上限はないが、電解液の導電性を良好にするには、できるだけ低分子のアルキル基が好ましく、当該アルキル基の例には、メチル基、エチル基が挙げられる。 Although no particular upper limit to the number of carbon atoms in the alkyl group, to improve the conductivity of the electrolyte is preferably an alkyl group of possible small molecules, examples of the alkyl group, and methyl group, an ethyl group It is. アリ−ル基の例としては、 Ali - Examples of group,
フェニル基が挙げられる。 And a phenyl group. シリコ−ン系消泡剤として、 As emissions based anti-foaming agent, - silico
上記のようなシリコ−ンオイルを溶剤に溶かした溶液型や各種添加剤を配合したもの等の二次製品的なものを使用できる。 Silicone as described above - N'oiru can be used a secondary product ones such as those obtained by blending a solution-type and various additives dissolved in a solvent. シリコ−ン系消泡剤は、市販のものを使用することができ、具体例としては、サンノプコ株式会社製ダッポ−SN−357(以下、SN−357と称する。)、信越化学工業株式会社製KS603(以下、K Silico - (. Which hereinafter referred to as SN-357) down antifoams may be used a commercially available, specific examples, Dappo -SN-357 manufactured by San Nopco Co., Shin-Etsu Chemical Co., Ltd. KS603 (below, K
S603と称する。 S603 referred to as. )等が挙げられる。 ), And the like.

【0010】シリコ−ン系消泡剤の非水電解液中での濃度は、低過ぎると添加した効果が充分でなく、高過ぎると電池容量が低下する傾向にあるので、10ppm〜1 [0010] silicone - concentration in emissions antifoam nonaqueous electrolytic solution was added too low effect is not sufficient, since too high battery capacity tends to decrease, 10Ppm~1
0重量%とすることが好ましい。 It is preferably 0% by weight.

【0011】本発明において使用される非水溶媒としては特に限定されるものではなく、従来より二次電池用非水電解液において用いられているような溶媒を使用することができる。 [0011] The non-aqueous solvent used in the present invention is not particularly limited, a solvent may be used, such as used in conventionally non-aqueous electrolyte secondary battery. 例えば、炭酸プロピレン(PC)、炭酸エチレン(EC)、炭酸ジメチル(DMC)、炭酸エチルメチル(MEC)、炭酸ジエチル(DEC)、γーブチロラクトン(GBL)、酢酸エチル(EA)、プロピオン酸メチル(MPR)、プロピオン酸エチル(EP For example, propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (MEC), diethyl carbonate (DEC), gamma-butyrolactone (GBL), ethyl acetate (EA), methyl propionate ( MPR), ethyl propionate (EP
R)、1,2−ジメトキシエタン(DME)、1,2− R), 1,2-dimethoxyethane (DME), 1,2-
ジエトキシエタン(DEE)、2−メチルテトラヒドロフラン(2−MeTHF)、テトラヒドロフラン(TH Diethoxyethane (DEE), 2-methyltetrahydrofuran (2-MeTHF), tetrahydrofuran (TH
F)、スルホラン(SL)、メチルスルホラン(MeS F), sulfolane (SL), methyl sulfolane (MeS
L)等を使用することができ、これらは二種以上を混合してもよい。 L) or the like can be used, it may be a mixture of two or more kinds thereof.

【0012】本発明の二次電池用非水電解液においては、電解質としてリチウム化合物を使用する。 [0012] In the non-aqueous electrolyte solution for a secondary battery of the present invention uses a lithium compound as an electrolyte. これにより、本電解質はリチウム二次電池の電解液として特に有用となる。 Thus, the electrolyte is particularly useful as an electrolytic solution for a lithium secondary battery. このようなリチウム化合物としては、従来のリチウム二次電池において用いられているものを使用することができる。 Such lithium compounds can be used those used in conventional lithium secondary batteries. 例えば、LiClO 4 、LiAsF 6 For example, LiClO 4, LiAsF 6,
LiPF 6 、LiBF 4 、LiCF 3 SO 3 、LiN(CF LiPF 6, LiBF 4, LiCF 3 SO 3, LiN (CF
3 SO 22 、LiC(CF 3 SO 23等を使用できる。 3 SO 2) 2, LiC ( CF 3 SO 2) 3 and the like can be used.
尚、電解質であるリチウム化合物の二次電池用非水電解液中での濃度は、導電率の点から0.1〜3.0mol The concentration in a non-aqueous electrolyte secondary battery of the lithium compound as the electrolyte is, 0.1~3.0Mol terms of conductivity
/リットル、好ましくは0.3〜2.0mol/リットルとするとよい。 / Liter, may preferably be a 0.3~2.0Mol / liter.

【0013】本発明の二次電池用非水電解液は、例えば、非水溶媒を撹拌しながら、その中に電解質としてリチウム化合物を添加して溶解させ、シリコ−ン系消泡剤を添加して溶解させることにより製造することができる。 [0013] The non-aqueous electrolyte secondary battery of the present invention, for example, stirring a nonaqueous solvent, and dissolved by addition of a lithium compound as an electrolyte therein, silicone - added down antifoam it can be prepared by dissolving Te.

【0014】本発明の二次電池用非水電解液は、リチウム化合物を電解質とする、種々の構成の二次電池に適用することができる。 [0014] secondary battery nonaqueous electrolytic solution of the present invention, the lithium compound and the electrolyte may be applied to secondary batteries of various configurations. 例えば、リチウム金属、リチウム合金またはリチウムをドープ・脱ドープすることができる材料からなる負極を有するリチウム二次電池に好ましく適用することができる。 For example, it is possible to lithium metal, is preferably applied to a lithium secondary battery having a negative electrode comprising a material capable of lithium alloy or doping and dedoping lithium. ここで、リチウム合金としては、リチウムーアルミニウム合金を例示することができる。 Here, the lithium alloy may be exemplified lithium-aluminum alloy. また、リチウムをドープ・脱ドープすることができる材料としては、例えば、熱分解炭素類、コークス類(ピッチコークス、ニードルコークス、石油コークス等)、グラファイト類、有機高分子化合物焼成体(フェノール樹脂、フラン樹脂等を適当な温度で焼成し炭素化したもの)、炭素繊維、活性炭等の炭素材料等を使用することができる。 As a material capable of doping and dedoping lithium, for example, pyrolytic carbons, cokes (pitch coke, needle coke, petroleum coke), graphite, organic polymer compound fired body (phenol resin, furan resins such as those obtained by firing and carbonizing at an appropriate temperature), it is possible to use carbon fibers, and activated carbon.

【0015】一方、正極は、充放電が可能な種々の材料から形成することができる。 Meanwhile, the positive electrode may be formed from a variety of materials that can be charged and discharged. 例えば、LiCoO 2 、L For example, LiCoO 2, L
iNiO 2 、LiMn 24 、LiMnO 2などのLi x iNiO 2, Li x M, such as LiMn 2 O 4, LiMnO 2
2 (ここで、Mは一種以上の遷移金属であり、xは電池の充放電状態によって異なり、通常0.05≦x≦ O 2 (where, M is one or more transition metals, x is different according to the charge and discharge state of the battery, usually 0.05 ≦ x ≦
1.20である)で表される、リチウムと一種以上の遷移金属との複合酸化物や、FeS 2 、TiS 2 、V 25 Represented by a is) 1.20, or a composite oxide of lithium and one or more transition metals, FeS 2, TiS 2, V 2 O 5,
MoO 3 、MoS 2などの遷移元素のカルコゲナイトあるいはポリアセチレン、ポリピロール等のポリマー等を使用することができる。 MoO 3, of the transition elements such as MoS 2 chalcogenide or polyacetylene, a polymer of polypyrrole and the like can be used.

【0016】本発明の二次電池用非水電解液を使用した二次電池の形状については特に限定されることはなく、 [0016] is not particularly limited for the shape of the secondary battery using the non-aqueous electrolyte secondary battery of the present invention,
ボタン型、円筒型、角型、コイン型等の種々の形状にすることができる。 Button, cylindrical, prismatic, may be of various shapes of a coin type.

【0017】 [0017]

【作用】本発明の二次電池用非水電解液において、非水電解液にシリコ−ン系消泡剤を含有させると、充電放電において、非水電解液の分解による炭酸ガス、オレフィンガス等の発生を抑制し、低温放電特性が向上され、インピ−ダンス特性を改善できる。 [Action] In the non-aqueous electrolyte solution for a secondary battery of the present invention, a non-aqueous electrolyte solution in silico - the inclusion of emissions based defoamer, the charge and discharge, the carbon dioxide gas due to the decomposition of the nonaqueous electrolyte solution, an olefin gas such as the generation suppression is improved low-temperature discharge characteristics, Inpi - can improve the dance performance.

【0018】 [0018]

【実施例】以下、本発明を実施例に基づいて更に説明する。 EXAMPLES The following further describes the present invention based on examples.

【0019】実施例1. [0019] Example 1. 当該実施例で用いた非水電解液二次電池につき、図1に基づいて説明する。 Per nonaqueous electrolyte secondary battery used in the embodiment will be described with reference to FIG. 図1に示すごとく、本例の非水電解液二次電池1は、正極2と負極3とセパレータ4と非水電解液5とボタン型電池容器6 As shown in FIG. 1, the non-aqueous electrolyte secondary battery 1 of this embodiment, the positive electrode 2 and the negative electrode 3 and the separator 4 and the non-aqueous electrolyte solution 5 and button-type battery container 6
と正極側集電体7と負極側集電体8とガスケット9とを有してなる。 Become and a positive electrode side current collector 7 and the negative collector 8 Gasket 9. 上記正極2としては、LiCoO 2を正極活物質とする合剤をペレット状に加圧成形した成形品を使用した。 As the positive electrode 2 was used a molded product having a mixture of a LiCoO 2 positive active material was pressed into pellets. また、負極3としては、コークスを負極活物質担体とした合剤をペレット状に加圧成形した成形品を使用した。 As the negative electrode 3, a mixture in which the coke as a negative electrode active substance carriers using molded article pressed into pellets. 非水電解液5には、炭酸エチレン(EC)と炭酸ジエチル(DEC)との混合溶媒(容量比2:3) The non-aqueous electrolyte solution 5, a mixed solvent of ethylene carbonate and (EC) and diethyl carbonate (DEC) (volume ratio 2: 3)
に、LiPF 6からなる電解質を濃度1mol/リットルにて含有させ、さらに、シリコ−ン系消泡剤SN−3 In an electrolyte consisting of LiPF 6 is contained at a concentration 1mol / l, further silicone - down antifoaming agent SN-3
57を0.05wt%含有してなる溶液を使用した。 57 was used a solution comprising 0.05 wt%. 上記セパレータ4にはポリプロピレン製の不織布よりなるセパレータを用いた。 The above separator 4 was used a separator made of polypropylene nonwoven fabric. また、正極側集電体7はステンレス鋼により構成し、一方、負極側集電体8はニッケルエキスパンドメタルにより構成した。 Also, the positive electrode side current collector 7 constructed of stainless steel, while the negative electrode side current collector 8 is constituted by a nickel expanded metal. さらに、前記電池容器6はステンレス鋼より構成し、その正極缶と負極缶をポリプロピレンのガスケット9により固定した。 Furthermore, the battery container 6 is composed of stainless steel and the cathode can and the negative electrode can be fixed by a polypropylene gasket 9. 以上のようにして作製した電池について、電池容量、低温放電時の電池容量、電池インピ−ダンスを調べた。 The battery fabricated in the manner described above, the battery capacity, the battery capacity at the time of low-temperature discharge, battery Inpi - were examined dance. 尚、充電は定電流法とし、上限電圧を4.2V、定電流での電流密度を0.60(0.2C)mA/cm 2 The charging is a constant current method, 4.2 V upper limit voltage, the current density at a constant current 0.60 (0.2C) mA / cm 2 に設定し、放電は、電流密度を0.60(0.2C)mA/cm 2または3(1C)mA/cm 2下定電流で行ない、終止電圧は2.7Vとした。 Set, discharge, the current density carried by 0.60 (0.2C) mA / cm 2 or 3 (1C) mA / cm 2 under a constant current, final voltage was set to 2.7V. 通常充放電は20℃で実施した。 Usually charging and discharging were carried out at 20 ° C..
低温放電時の電池容量は、通常充電した電池を−10℃ Battery capacity at low temperature discharge, -10 ° C. The battery normally charged
に放置し、電流密度3(1C)mA/cm 2で放電を実施し、通常放電した電池容量の比較から評価した。 Was left in the discharge was performed at a current density 3 (1C) mA / cm 2 , it was evaluated from a comparison of the battery capacity that typically discharged. また、電池を温度90℃の環境下に100時間放置した後、電池を分解し、電解液を赤外分光光度計を使用して炭酸ガス濃度を測定して評価した。 Further, after standing for 100 hours in an environment temperature of 90 ° C. The battery, the battery was disassembled, an electrolyte solution was evaluated by measuring the carbon dioxide concentration using an infrared spectrophotometer.

【0020】実施例2. [0020] Example 2. 実施例1におけるシリコ−ン系消泡剤をKS603に変えた以外は、上記実施例1と同様にしてボタン型電池を作製し、実施例1と同様の条件下で、電池容量、低温放電時の電池容量、インピ−ダンス、電解液の炭酸ガス濃度を調べた。 Silico in Example 1 - except for changing the emission-based antifoaming agent KS603, to produce a button-type battery in the same manner as in Example 1, under the same conditions as in Example 1, the battery capacity, the low temperature discharge battery capacity, Inpi - examined dancing, the carbon dioxide concentration of the electrolyte solution.

【0021】実施例3. [0021] Example 3. 実施例1におけるシリコ−ン系消泡剤SN−357の含有量を0.1%に変えた以外は、実施例1と同様にしてボタン型電池を作製し、実施例1と同様の条件下で、電池容量、低温放電時の電池容量、インピ−ダンス、電解液の炭酸ガス濃度を調べた。 Silico in Example 1 - a except for changing 0.1% content of emissions antifoaming agent SN-357, to produce a button-type battery in the same manner as in Example 1, the same conditions as in Example 1 in the battery capacity, the battery capacity at the time of low-temperature discharge, Inpi - examined dancing, the carbon dioxide concentration of the electrolyte solution.

【0022】実施例4. [0022] Example 4. 実施例2におけるシリコ−ン系消泡剤KS603の含有量を0.1%とした以外は、実施例1と同様にしてボタン型電池を作製し、上述の同様の条件下で、電池容量、低温放電時の電池容量、インピ−ダンス、電解液の炭酸ガス濃度を調べた。 Silico in Example 2 - except for using 0.1% content of emissions antifoaming agent KS603, to produce a button-type battery in the same manner as in Example 1, under the same conditions described above, the battery capacity, battery capacity at low temperature discharge, Inpi - examined dancing, the carbon dioxide concentration of the electrolyte solution.

【0023】実施例5. [0023] Example 5. 上記実施例3における非水電解液を、炭酸エチレン(EC)と炭酸ジメチル(DMC) The non-aqueous electrolytic solution in Example 3, ethylene carbonate (EC) and dimethyl carbonate (DMC)
との混合溶媒(容量比1:1)とした以外は、実施例3 Mixed solvent (volume ratio 1: 1) and except that, in Example 3
と同様にしてボタン型電池を作製し、実施例1と同様の条件下で、電池容量、低温放電時の電池容量、インピ− To produce a button-type battery in the same manner as, under the same conditions as in Example 1, the battery capacity, the battery capacity at the time of low-temperature discharge, Inpi -
ダンスを調べた。 We examined the dance.

【0024】実施例6. [0024] Example 6. 上記実施例4における非水電解液を、炭酸エチレン(EC)と炭酸ジメチル(DMC) The non-aqueous electrolytic solution in Example 4, ethylene carbonate (EC) and dimethyl carbonate (DMC)
との混合溶媒(容量比1:1)とした以外は、実施例4 Mixed solvent (volume ratio 1: 1) and then addition was the Example 4
と同様にしてボタン型電池を作製し、実施例1と同様の条件下で、電池容量、低温放電時の電池容量、インピ− To produce a button-type battery in the same manner as, under the same conditions as in Example 1, the battery capacity, the battery capacity at the time of low-temperature discharge, Inpi -
ダンスを調べた。 We examined the dance.

【0025】比較例1. [0025] Comparative Example 1. 実施例1においてシリコ−ン系消泡剤を添加しなかった以外は、実施例1と同様にしてボタン型電池を作製し、実施例1と同様の条件下で、電池容量、低温放電時の電池容量、インピ−ダンス、電解液の炭酸ガス濃度を調べた。 Silico in Example 1 - except for adding no emissions antifoaming agent, to produce a button-type battery in the same manner as in Example 1, under the same conditions as in Example 1, the battery capacity, the time of low-temperature discharge battery capacity, Inpi - examined dancing, the carbon dioxide concentration of the electrolyte solution.

【0026】比較例2. [0026] Comparative Example 2. 実施例5において、シリコ−ン系消泡剤を添加しなかった以外は、実施例5と同様にしてボタン型電池を作製し、実施例1と同様の条件下で、 In Example 5, silico - except for adding no emissions antifoaming agent, to produce a button-type battery in the same manner as in Example 5, under the same conditions as in Example 1,
電池容量、低温放電時の電池容量、インピ−ダンス、電解液の炭酸ガス濃度を調べた。 Battery capacity, the battery capacity at the time of low-temperature discharge, Inpi - examined dancing, the carbon dioxide concentration of the electrolyte solution.

【0027】以上の結果を、表1、図2(A)及び図2 The above results are shown in Table 1, FIG. 2 (A) and 2
(B)に示す。 It is shown in (B). 尚、図2(A)は、実施例3および実施例4と比較例1の低温放電後のインピ−ダンス曲線を示す。 Incidentally, FIG. 2 (A), Inpi after low-temperature discharge of Comparative Example 1 and Example 3 and Example 4 - shows a dancing curve. また、図2(B)は、実施例5および実施例6と比較例2の低温放電後のインピ−ダンス曲線を示す。 Also, FIG. 2 (B), Inpi after low-temperature discharge of Examples 5 and 6 and Comparative Example 2 - shows a dancing curve.

【0028】 [0028]

【表1】 [Table 1]

【0029】表1に示すように、本発明のシリコ−ン系消泡剤を添加した電解液(実施例1〜6)は、初期放電容量、低温放電時の電池容量の全てにおいて、当該シリコ−ン系消泡剤を加えていない電解液(比較例1、比較例2)に比較して、増加が見られ、効果があることが判る。 As shown in Table 1, silicone of the present invention - electrolytic liquid containing emissions defoaming agent (Examples 1-6), the initial discharge capacity, in all of the battery capacity at the time of low-temperature discharge, the silicone - electrolyte without added emissions based defoaming agent (Comparative example 1, Comparative example 2) compared to an increase was observed, it is found to be effective. 図2(A)は、実施例3および実施例4と比較例1 2 (A) is, Comparative Example 3 and Example 4 Example 1
の低温放電後のインピ−ダンス曲線を示すが、当該図2 Inpi after low-temperature discharge of - show dance curve, the Figure 2
(A)に示すように、実施例3、実施例4とも比較例1 (A), the Example 3, Example 4 Both Comparative Example 1
に比べインピ−ダンスが下がり優れていることが判る。 Inpi compared to - it can be seen that is better fall dance.
また、図2(B)は、実施例5および実施例6と比較例2の低温放電後のインピ−ダンス曲線を示すが、当該図2(B)に示すように、実施例5、実施例6とも比較例2に比べインピ−ダンスが下がり優れていることが判る。 Also, FIG. 2 (B), Inpi after low-temperature discharge of Examples 5 and 6 and Comparative Example 2 - As shown in show dance curve, the Figure 2 (B), Example 5, Example 6 both Inpi compared with Comparative example 2 - it is understood that the superior edge dance. さらに、シリコ−ン系消泡剤を添加した電解液(実施例1〜4)は、90℃、100時間放置後の炭酸ガス濃度において、当該シリコ−ン系消泡剤を加えていない電解液(比較例1、比較例2)に比較して、低下が見られ、効果があることが判る。 Furthermore, silicone - electrolytic liquid containing emissions defoaming agent (Examples 1-4) is, 90 ° C., the carbon dioxide concentration after 100 hours, the silicone - electrolyte without added emissions antifoam (Comparative example 1, Comparative example 2) compared to a decrease was observed, it is found to be effective.

【0030】以上本発明者によってなされた発明を実施例にもとずき具体的に説明したが、本発明は上記実施例に限定されるものではなく、その要旨を逸脱しない範囲で種々変更可能であることはいうまでもない。 [0030] Although the present invention made by the inventor has been described also preparative not a Ki specific embodiment, the present invention is not limited to the above embodiments, various modifications possible without departing from the scope of the invention it is needless to say. 例えば、 For example,
上記実施例では、電池の形状はボタン型で説明を行なったが、これに限定されるものではなく、他の角型、円筒型、コイン型等であっても同様の効果を得ることが出来る。 In the above embodiment, the shape of the battery is been explained in button-type, but the invention is not limited to this, other rectangular, cylindrical, it is possible to obtain the same effect even coin-like .

【0031】 [0031]

【発明の効果】本願において開示される発明のうち代表的なものによって得られる効果を簡単に説明すれば、下記のとおりである。 To briefly explain advantageous effects obtained by typical ones of the inventions disclosed in the present application, according to the present invention, it is as follows. すなわち、本発明によれば、二次電池用非水電解液において、シリコ−ン系消泡剤を添加することにより、その電解液を用いた二次電池の放電特性、低温放電特性、および分解ガスの抑制を向上させることができる。 That is, according to the present invention, the non-aqueous electrolyte secondary battery, silico - by adding emission antifoaming agent, discharge characteristics of the secondary battery using the electrolytic solution, low-temperature discharge characteristics, and degradation it is possible to improve the suppression of gas.

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS

【図1】図1は、本発明の実施例に係る非水電解液二次電池の一例断面図である。 FIG. 1 is a sectional view of an example of a non-aqueous electrolyte secondary battery in accordance with an embodiment of the present invention.

【図2】図2(A)および(B)は、それぞれ、本発明の作用効果を説明する低温放電後のインピ−ダンス曲線によるグラフである。 [2] Figure 2 (A) and (B), respectively, Inpi after low-temperature discharge explaining the effects of the present invention - is a graph according to dance curve.

【符号の説明】 DESCRIPTION OF SYMBOLS

1…非水電解液二次電池 2…正極 3…負極 4…セパレータ 5…非水電解液 6…ボタン型電池容器 7…正極側集電体 8…負極側集電体 9…ガスケット 1 ... non-aqueous electrolyte secondary battery 2 ... positive electrode 3 ... negative electrode 4 ... separator 5 ... non-aqueous electrolyte 6 ... button-type battery case 7 ... positive side current collector 8 ... negative electrode current collector 9 ... Gasket

フロントページの続き (72)発明者 小島 哲雄 埼玉県富士見市水谷東3−11−1 富山薬 品工業株式会社志木工場内 (72)発明者 上田 定夫 埼玉県富士見市水谷東3−11−1 富山薬 品工業株式会社志木工場内 (72)発明者 中野 稔 埼玉県富士見市水谷東3−11−1 富山薬 品工業株式会社志木工場内 Of the front page Continued (72) inventor Tetsuo Kojima Saitama Prefecture Fujimi Mizutanihigashi 3-11-1 Toyama medicine goods Industrial Co., Ltd. Shiki in the factory (72), Saitama Prefecture Fujimi inventor Sadao Ueda Mizutanihigashi 3-11-1 Toyama medicine goods industrial Co., Ltd. Shiki in the factory (72) inventor Minoru Nakano Saitama Prefecture Fujimi Mizutanihigashi 3-11-1 Toyama medicine goods industrial Co., Ltd. Shiki in the factory

Claims (3)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 非水溶媒と、電解質としてリチウム化合物を含む二次電池用非水電解液において、シリコ−ン系消泡剤を添加してなることを特徴とする二次電池用非水電解液。 1. A non-aqueous solvent, non-aqueous electrolyte solution for a secondary battery comprising a lithium compound as the electrolyte, silicone - emission system nonaqueous secondary battery, characterized by comprising an antifoaming agent liquid.
  2. 【請求項2】 シリコ−ン系消泡剤の二次電池用非水電解液中の濃度が、10ppm〜10重量%であることを特徴とする、請求項1に記載の二次電池用非水電解液。 2. A silico - concentration in the non-aqueous electrolyte secondary battery of emissions based defoaming agent, characterized in that it is a 10ppm~10 wt%, the non-secondary battery of claim 1 aqueous electrolyte.
  3. 【請求項3】 シリコ−ン系消泡剤が、次の式1で表されるシリコ−ン系消泡剤であることを特徴とする、請求項1または2に記載の二次電池用非水電解液。 3. A silicone - down type defoaming agent, silicone represented by the following formula 1 - characterized in that it is a down defoamers, non for a secondary battery according to claim 1 or 2 aqueous electrolyte. 【式1】 [Formula 1] 但し、上記式中のR However, R in the above formula は、有機基もしくは水素原子であり、同一でも、異なっていてもよい。 Is an organic group or a hydrogen atom may be identical or different.
JP36389597A 1997-12-18 1997-12-18 Non-aqueous electrolyte solution for a secondary battery Granted JPH11185804A (en)

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US7226702B2 (en) 2002-03-22 2007-06-05 Quallion Llc Solid polymer electrolyte and method of preparation
US8076031B1 (en) 2003-09-10 2011-12-13 West Robert C Electrochemical device having electrolyte including disiloxane
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US8076032B1 (en) 2004-02-04 2011-12-13 West Robert C Electrolyte including silane for use in electrochemical devices
US9786954B2 (en) 2004-02-04 2017-10-10 Robert C. West Electrolyte including silane for use in electrochemical devices
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