JP2963898B1 - Electrolyte for non-aqueous battery and secondary battery using this electrolyte - Google Patents
Electrolyte for non-aqueous battery and secondary battery using this electrolyteInfo
- Publication number
- JP2963898B1 JP2963898B1 JP10217953A JP21795398A JP2963898B1 JP 2963898 B1 JP2963898 B1 JP 2963898B1 JP 10217953 A JP10217953 A JP 10217953A JP 21795398 A JP21795398 A JP 21795398A JP 2963898 B1 JP2963898 B1 JP 2963898B1
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- battery
- biphenylyl
- weight
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
Abstract
【要約】
【課題】 電解液に添加しても低温特性や保存特性など
の電池特性に悪影響を及ぼさなく、かつ過充電に対して
は有効に作用する添加剤を用いて電池の安全性を確保で
きるようにする。
【解決手段】 有機溶媒に溶質としてリチウム塩を溶解
した電解液に下記の化１０の一般式で表されるエステル
誘導体が含有されている。ただし、化１０に示したＲ1
はフェニル基、ビフェニリル基を示し、Ｒ2は炭素数１
〜６のアルキル基、フェニル基を示す。
【化１０】
Abstract: PROBLEM TO BE SOLVED: To ensure the safety of a battery by using an additive that does not adversely affect battery characteristics such as low-temperature characteristics and storage characteristics even when added to an electrolyte solution and that effectively acts against overcharging. It can be so. SOLUTION: An electrolytic solution obtained by dissolving a lithium salt as a solute in an organic solvent contains an ester derivative represented by the following general formula. However, R 1 shown in Chemical formula 10
Represents a phenyl group or a biphenylyl group, and R 2 has 1 carbon atom.
To 6 alkyl groups and phenyl groups. Embedded image
Description
【０００１】[0001]
【発明の属する技術分野】本発明は有機溶媒に溶質とし
てリチウム塩を溶解した非水系電池用電解液およびこの
電解液を用いた非水系二次電池に係り、特に、過充電し
ても安全性が確保できる電解液およびこの電解液を用い
た非水系二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolyte for a non-aqueous battery in which a lithium salt is dissolved as a solute in an organic solvent and a non-aqueous secondary battery using the electrolyte. And a non-aqueous secondary battery using the electrolyte.
【０００２】[0002]
【従来の技術】近年、電子機器の小型化、軽量化はめざ
ましく、それに伴い、電源となる電池に対しても小型軽
量化の要望が非常に大きい。一次電池の分野では既にリ
チウム電池等の小型軽量電池が実用化されているが、こ
れらは一次電池であるが故に繰り返し使用できず、その
用途は限られたものであった。一方、二次電池の分野で
は従来より鉛蓄電池、ニッケル−カドミウム蓄電池、ニ
ッケル−水素蓄電池等が用いられてきたが、これらは小
型軽量化という点で大きな問題点を有している。2. Description of the Related Art In recent years, there has been a remarkable reduction in the size and weight of electronic devices, and accordingly, there has been a great demand for smaller and lighter batteries that serve as power supplies. In the field of primary batteries, small and lightweight batteries such as lithium batteries have already been put to practical use, but since these are primary batteries, they cannot be used repeatedly, and their uses have been limited. On the other hand, in the field of secondary batteries, lead storage batteries, nickel-cadmium storage batteries, nickel-hydrogen storage batteries, and the like have been conventionally used, but these have major problems in terms of size and weight reduction.
【０００３】そこで、小型軽量でかつ高容量で充放電可
能な電池としてリチウムイオン電池が実用化されるよう
になり、小型ビデオカメラ、携帯電話、ノートパソコン
等の携帯用電子・通信機器等に用いられるようになっ
た。この種のリチウムイオン電池は、負極活物質として
リチウムイオンを吸蔵・脱離し得るカーボン系材料を用
い、正極活物質として、ＬｉＣｏＯ2，ＬｉＮｉＯ2，Ｌ
ｉＭｎ2Ｏ4，ＬｉＦｅＯ2等のリチウム含有遷移金属酸
化物を用い、有機溶媒に溶質としてリチウム塩を溶解し
た電解液を用い、電池として組み立てた後、初回の充電
により正極活物質から出たリチウムイオンがカーボン粒
子内に入って充放電可能となる電池である。Therefore, lithium-ion batteries have come into practical use as small, lightweight, high-capacity, chargeable / dischargeable batteries, and are used in portable electronic and communication devices such as small video cameras, mobile phones, and notebook personal computers. Is now available. This type of lithium ion battery uses a carbon-based material capable of inserting and extracting lithium ions as a negative electrode active material, and uses LiCoO 2 , LiNiO 2 , L as a positive electrode active material.
using IMN 2 O 4, LiFeO lithium-containing transition metal oxides such as 2, lithium using an electrolyte prepared by dissolving lithium salt as a solute in an organic solvent, after assembling a battery, exiting from the positive electrode active material by the first charging This is a battery in which ions can be charged and discharged by entering carbon particles.
【０００４】このようなリチウムイオン電池にあって
は、過充電を行うと、過充電状態になるに伴い、正極か
らは過剰なリチウムが抽出され、負極ではリチウムの過
剰な挿入が生じて、正・負極の両極が熱的に不安定化す
る。正・負極の両極が熱的に不安定になると、やがては
電解液の有機溶媒を分解するように作用し、急激な発熱
反応が生じて、電池が異常に発熱するという事態を生
じ、電池の安全性が損なわれるという問題を生じた。こ
のような状況は、リチウムイオン電池のエネルギー密度
が増加するほど重要な問題となる。[0004] In such a lithium ion battery, when overcharging is performed, excess lithium is extracted from the positive electrode as the overcharged state occurs, and excessive insertion of lithium occurs in the negative electrode, resulting in a positive charge. -Both electrodes of the negative electrode become thermally unstable. If both the positive and negative electrodes become thermally unstable, they will eventually act to decompose the organic solvent in the electrolytic solution, causing a rapid exothermic reaction and causing the battery to generate abnormal heat. There was a problem that safety was impaired. Such a situation becomes more important as the energy density of the lithium ion battery increases.
【０００５】このような問題を解決するため、電解液中
に添加剤として少量の芳香族化合物を添加することによ
って、過充電に対して安全性を確保できるようにしたも
のが、例えば、特開平７−３０２６１４号公報、特開平
９−５０８２２号公報において提案された。この特開平
７−３０２６１４号公報、特開平９−５０８２２号公報
において提案されたものにあっては、負極に炭素材料を
用い、電解液の添加剤として、分子量５００以下で満充
電時の正極電位よりも貴な電位に可逆性酸化還元電位を
有するようなπ電子軌道をもつアニソール誘導体などの
芳香族化合物を使用するようにしている。このような芳
香族化合物は、過充電時に過充電を消費することで電池
が保護される。In order to solve such a problem, a technique has been proposed in which a small amount of an aromatic compound is added as an additive to an electrolytic solution to ensure safety against overcharging. It has been proposed in JP-A-7-302614 and JP-A-9-50822. In those proposed in JP-A-7-302614 and JP-A-9-50822, a carbon material is used for a negative electrode, and as an additive of an electrolytic solution, a positive electrode potential at full charge with a molecular weight of 500 or less is used. An aromatic compound such as an anisole derivative having a π-electron orbit that has a reversible oxidation-reduction potential at a more noble potential is used. Such an aromatic compound protects the battery by consuming the overcharge at the time of overcharge.
【０００６】また、電解液中に添加剤を添加することに
よって、過充電に対して安全性を確保できるようにした
ものが、例えば、特開平９−１０６８３５号公報におい
て提案された。この特開平９−１０６８３５号公報にお
いて提案されたものにあっては、負極に炭素材料を用
い、電解液の添加剤として、電池の最大動作電圧以上の
電池電圧で重合することによって、電池の内部電圧を高
くし、過充電時に電池を保護することができるようにし
ている。[0006] In addition, Japanese Patent Application Laid-Open No. 9-106835 has proposed a device capable of ensuring safety against overcharging by adding an additive to an electrolytic solution. In the method proposed in Japanese Patent Application Laid-Open No. 9-106835, a carbon material is used for a negative electrode, and as an additive for an electrolytic solution, polymerization is performed at a battery voltage equal to or higher than the maximum operating voltage of the battery. The voltage is increased so that the battery can be protected during overcharge.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、特開平
７−３０２６１４号公報、特開平９−５０８２２号公報
において提案されたものにあっては、アニソール誘導体
は過充電に対しては有効に作用するのに対して、サイク
ル特性や保存特性などの電池特性に悪影響を及ぼすとい
う問題を生じた。また、芳香族化合物は４．５Ｖ程度の
電位で酸化分解されて、ガスを発生するとともに、重合
物を形成することにより、過充電を消費して電池を保護
する反面、電解液組成によっては、その重合物が溶解し
て過充電を消費できない場合も生じる。結局、π電子軌
道をもつアニソール誘導体などの芳香族化合物は必ずし
も過充電を抑制するとはいえないものである。However, in those proposed in Japanese Patent Application Laid-Open Nos. 7-302614 and 9-50822, the anisole derivative effectively acts on overcharging. However, there is a problem that the battery characteristics such as cycle characteristics and storage characteristics are adversely affected. Further, the aromatic compound is oxidatively decomposed at a potential of about 4.5 V to generate gas and form a polymer, thereby consuming the overcharge and protecting the battery, but depending on the electrolyte composition, In some cases, the polymer dissolves and the overcharge cannot be consumed. As a result, aromatic compounds such as anisole derivatives having a π-electron orbit cannot always be said to suppress overcharge.
【０００８】一方、特開平９−１０６８３５号公報にお
いて提案されたものにあっては、電解液の添加剤として
使用するビフェニルは、極性が低く、かつ電解液に対す
る溶解性が低いため、低温作動時に添加剤が一部析出し
て電池特性の低下を惹起するという問題を生じた。ま
た、３−クロロ−チオフェンは刺激性があり、しかも悪
臭が強くて取り扱いが難しく、さらに酸化分解されやす
いという問題点があり、フランも酸化分解されやすく、
いずれの化合物も電池特性に悪影響を及ぼすという問題
点がある。On the other hand, in the method proposed in Japanese Patent Application Laid-Open No. 9-106835, biphenyl used as an additive for the electrolyte has low polarity and low solubility in the electrolyte. There has been a problem that the additives are partially deposited to cause deterioration of battery characteristics. In addition, 3-chloro-thiophene is irritating, has a strong odor, is difficult to handle, and has a problem that it is easily decomposed by oxidation. Furan is also easily decomposed by oxidation,
All of these compounds have a problem that they adversely affect battery characteristics.
【０００９】そこで、本発明は上記問題点に鑑みてなさ
れたものであり、電解液に添加しても低温特性や保存特
性などの電池特性に悪影響を及ぼさなく、かつ過充電に
対しては有効に作用する添加剤を用いて電池の安全性を
確保できるようにすることを目的とするものである。Accordingly, the present invention has been made in view of the above problems, and does not adversely affect battery characteristics such as low-temperature characteristics and storage characteristics even when added to an electrolytic solution, and is effective against overcharging. It is an object of the present invention to ensure the safety of a battery by using an additive that acts on the battery.
【００１０】[0010]
【課題を解決するための手段およびその作用・効果】こ
のため、本発明の非水系電池用電解液においては、有機
溶媒に下記の化３の一般式で表されるエステル誘導体が
含有されていることを特徴とする。ただし、化３に示し
たＲ1 はビフェニリル基を示し、Ｒ2は炭素数１〜６のア
ルキル基、フェニル基、ベンジル基を示す。Means for Solving the Problems and Actions and Effects Therefor, in the electrolyte for a non-aqueous battery of the present invention, the organic solvent contains an ester derivative represented by the following general formula (3). It is characterized by the following. However, R 1 indicated in Chemical Formula 3 represents a bi Feniriru group, R 2 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group.
【００１１】[0011]
【化３】 Embedded image
【００１２】上記化３の一般式で表されるエステル誘導
体は、電解液中の有機溶媒との親和性が良いため、低温
特性や保存特性などの電池特性に悪影響を及ぼすことは
ない。このため、上記化３の一般式で表されるエステル
誘導体が含有された電解液は電池性能を劣化させること
がない。また、エステル誘導体が重合反応して生成され
た重合物は、電解液中で再溶解が起こりにくい物質であ
るため、過充電に対しても有効に作用する。このため、
上記化３の一般式で表されるエステル誘導体が含有され
た電解液を用いることにより、電池の安全性が確保でき
るようになる。Since the ester derivative represented by the general formula (3) has a good affinity for an organic solvent in an electrolytic solution, it does not adversely affect battery characteristics such as low-temperature characteristics and storage characteristics. For this reason, the electrolytic solution containing the ester derivative represented by the general formula 3 does not deteriorate the battery performance. Further, a polymer produced by the polymerization reaction of the ester derivative is a substance that is unlikely to be redissolved in the electrolytic solution, and thus effectively acts on overcharging. For this reason,
The use of the electrolytic solution containing the ester derivative represented by the general formula (3) above can ensure the safety of the battery.
【００１３】そして、上記のエステル誘導体としては、
４−ビフェニリルアセテート、４−ビフェニリルベンゾ
エート、４−ビフェニリルベンジルカルボキシレートあ
るいは２−ビフェニリルプロピオネートから選択した少
なくとも１種を備えるようにすることが好ましい。[0013] The above ester derivatives include:
4- biphenylyl acetate tape bets, 4 - biphenylyl benzoate, 4-biphenylyl benzylcarboxy it is preferable to include a rate or at least one selected from 2-biphenylyl propionate.
【００１４】また、本発明は、リチウム含有金属酸化物
を正極活物質とする正極と炭素を負極活物質とする負極
とをセパレータを介して積層して構成した電極体を電池
容器内に備えるとともに、有機溶媒に溶質としてリチウ
ム塩を溶解した電解液を備えた非水系二次電池であっ
て、電解液に下記の化４の一般式で表されるエステル誘
導体が含有されていることを特徴とする。ただし、化４
に示したＲ1 はビフェニリル基を示し、Ｒ2は炭素数１〜
６のアルキル基、フェニル基、ベンジル基を示す。Further, according to the present invention, a battery container is provided with an electrode body formed by laminating a positive electrode using a lithium-containing metal oxide as a positive electrode active material and a negative electrode using carbon as a negative electrode active material via a separator. A non-aqueous secondary battery provided with an electrolyte in which a lithium salt is dissolved as a solute in an organic solvent, wherein the electrolyte contains an ester derivative represented by the following general formula (4). I do. However,
R 1 shown in represents a bi Feniriru group, R 2 is 1 to the number of carbon atoms
6 represents an alkyl group, a phenyl group, and a benzyl group.
【００１５】[0015]
【化４】 Embedded image
【００１６】上記化４の一般式で表されるエステル誘導
体は電解液中の有機溶媒との親和性が良いため、このよ
うなエステル誘導体をリチウム塩とともに有機溶媒中に
添加された電解液を用いると、低温特性や保存特性など
の電池特性に悪影響を及ぼすことはない。Since the ester derivative represented by the general formula (4) has a good affinity for the organic solvent in the electrolytic solution, an electrolytic solution in which such an ester derivative is added to the organic solvent together with the lithium salt is used. It does not adversely affect battery characteristics such as low-temperature characteristics and storage characteristics.
【００１７】また、これらの添加剤は電池電圧が過充電
状態の電圧に達すると、分解反応を開始してガスを発生
するようになるとともに重合反応を開始して重合物が生
成される。この重合物は抵抗体として作用するととも
に、この重合物は電解液中で再溶解が起こりにくい物質
であるため、過充電に対しては有効に作用する。結局、
このようなエステル誘導体をリチウム塩とともに有機溶
媒中に添加された電解液を用いると、低温特性や保存特
性などの電池特性に悪影響を及ぼすことなく、即ち、電
池性能を劣化させることなく電池の安全性を確保できる
ようになる。When the battery voltage reaches an overcharged voltage, these additives start a decomposition reaction to generate gas and start a polymerization reaction to produce a polymer. This polymer acts as a resistor, and since this polymer is a substance that is unlikely to be redissolved in the electrolytic solution, it effectively acts on overcharging. After all,
The use of an electrolyte solution in which such an ester derivative is added to an organic solvent together with a lithium salt does not adversely affect battery characteristics such as low-temperature characteristics and storage characteristics, that is, does not degrade battery performance, and thus, the safety of batteries can be improved. Nature can be secured.
【００１８】[0018]
【発明の実施の形態】以下に、本発明のリチウムイオン
電池の一実施形態を図１および図２に基づいて説明す
る。なお、図１は本発明の電解液を備えた一実施形態の
リチウムイオン電池のセパレータを介して重ね合わせた
正・負極板を卷回して外装缶内に収納した状態を示す断
面図であり、図２は外装缶の開口部に装着される電流遮
断封口体を示す一部破断図である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the lithium ion battery of the present invention will be described below with reference to FIGS. FIG. 1 is a cross-sectional view showing a state in which positive and negative electrodes stacked on each other via a separator of the lithium ion battery of one embodiment including the electrolytic solution of the present invention are wound and housed in an outer can. FIG. 2 is a partially cutaway view showing the current blocking sealing body attached to the opening of the outer can.
【００１９】１．負極板の作製 天然黒鉛（ｄ＝３．３６ ）よりなる負極活物質とポリ
ビニリデンフルオライド（ＰＶＤＦ）よりなる結着剤等
とを、Ｎ−メチルピロリドンからなる有機溶剤等に溶解
したものを混合して、スラリーあるいはペーストとす
る。これらのスラリーあるいはペーストを、スラリーの
場合はダイコーター、ドクターブレード等を用いて、ペ
ーストの場合はローラコーティング法等により金属芯体
（例えば、厚みが２０μｍの銅箔）の両面の全面にわた
って均一に塗布して、活物質層を塗布した負極板を形成
する。1. Preparation of Negative Electrode Plate A negative active material made of natural graphite (d = 3.36) and a binder made of polyvinylidene fluoride (PVDF) dissolved in an organic solvent made of N-methylpyrrolidone are mixed. Then, a slurry or a paste is obtained. These slurries or pastes are uniformly spread over both surfaces of a metal core (for example, a copper foil having a thickness of 20 μm) by a die coater, a doctor blade or the like in the case of a slurry, or by a roller coating method in the case of a paste. By coating, a negative electrode plate coated with the active material layer is formed.
【００２０】この後、活物質層を塗布した負極板を乾燥
機中を通過させて、スラリーあるいはペースト作製に必
要であった有機溶剤を除去して乾燥させる。この後、こ
の乾燥負極板をロールプレス機により圧延して、厚みが
０．１４ｍｍの負極板１０とする。Thereafter, the negative electrode plate coated with the active material layer is passed through a drier to remove an organic solvent necessary for preparing a slurry or a paste, followed by drying. Thereafter, the dried negative electrode plate is rolled by a roll press to obtain a negative electrode plate 10 having a thickness of 0.14 mm.
【００２１】２．正極板の作製 一方、ＬｉＣｏＯ2からなる正極活物質と、アセチレン
ブラック、グラファイト等の炭素系導電剤と、ポリビニ
リデンフルオライド（ＰＶＤＦ）よりなる結着剤等と
を、Ｎ−メチルピロリドンからなる有機溶剤等に溶解し
たものを混合して、スラリーあるいはペーストとする。2. Preparation of Positive Electrode On the other hand, a positive electrode active material made of LiCoO 2 , a carbon-based conductive agent such as acetylene black and graphite, a binder made of polyvinylidene fluoride (PVDF), and the like are combined with an organic material made of N-methylpyrrolidone. A solution dissolved in a solvent or the like is mixed to form a slurry or paste.
【００２２】これらのスラリーあるいはペーストを、ス
ラリーの場合はダイコーター、ドクターブレード等を用
いて、ペーストの場合はローラコーティング法等により
金属芯体（例えば、厚みが２０μｍのアルミニウム箔）
の両面に均一に塗布して、活物質層を塗布した正極板を
形成する。この後、活物質層を塗布した正極板を乾燥機
中を通過させて、スラリーあるいはペースト作製に必要
であった有機溶剤を除去して乾燥させる。乾燥後、この
乾燥正極板をロールプレス機により圧延して、厚みが
０．１７ｍｍの正極板２０とする。A metal core (for example, an aluminum foil having a thickness of 20 μm) is prepared by using a slurry such as a die coater or a doctor blade in the case of a slurry, or a roller coating method in the case of a paste.
To form a positive electrode plate coated with an active material layer. Thereafter, the positive electrode plate coated with the active material layer is passed through a drier to remove an organic solvent necessary for preparing a slurry or a paste, followed by drying. After drying, the dried positive electrode plate is rolled by a roll press to form a positive electrode plate 20 having a thickness of 0.17 mm.
【００２３】３．電極体の作製 上述のようにして作製した負極板１０と正極板２０と
を、有機溶媒との反応性が低く、かつ安価なポリオレフ
ィン系樹脂からなる微多孔膜、好適にはポリエチレン製
微多孔膜（例えば、厚みが０．０２５ｍｍ）３０を間に
し、かつ、各極板１０，２０の幅方向の中心線を一致さ
せて重ね合わせる。この後、図示しない巻き取り機によ
り卷回する。この後、最外周をテープ止めして渦巻状電
極体とする。角形電池の場合は、プレス機で角形外装缶
に挿入できるような形に成形して電極体とする。3. Production of Electrode Body The negative electrode plate 10 and the positive electrode plate 20 produced as described above were prepared by forming a microporous film made of an inexpensive polyolefin resin having low reactivity with an organic solvent, preferably a polyethylene microporous film. (For example, the thickness is 0.025 mm), and the electrode plates 10 and 20 are overlapped with their center lines in the width direction coincided with each other. Thereafter, it is wound by a winder (not shown). Thereafter, the outermost periphery is taped to form a spiral electrode body. In the case of a prismatic battery, it is formed into a shape that can be inserted into a prismatic outer can with a press machine to form an electrode body.
【００２４】４．電解液の調整 実施例１ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに下
記の化５の構造式で表される４−ビフェニリルアセテー
トを２重量％添加混合して作製した電解液ａを実施例１
の電解液とする。4. Preparation of Electrolyte Example 1 A mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC)
Example 1 was prepared by adding and mixing 1M LiPF 6 as an electrolyte salt and further adding and mixing 2% by weight of 4-biphenylyl acetate represented by the following structural formula.
Electrolyte solution.
【００２５】[0025]
【化５】 Embedded image
【００２６】参考例１ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに下
記の化６の構造式で表されるフェニルプロピオネートを
２重量％添加混合して作製した電解液ｂを参考例１の電
解液とする。 Reference Example 1 A mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC)
An electrolyte b prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 2% by weight of phenylpropionate represented by the following structural formula 6 is used as an electrolyte of Reference Example 1 .
【００２７】[0027]
【化６】 Embedded image
【００２８】実施例２ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに下
記の化７の構造式で表される４−ビフェニリルベンゾエ
ートを２重量％添加混合して作製した電解液ｃを実施例
２の電解液とする。 Example 2 In a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC),
Example 1 was prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt, and further adding and mixing 2 wt% of 4-biphenylylbenzoate represented by the following structural formula.
2 electrolyte solution.
【００２９】[0029]
【化７】 Embedded image
【００３０】実施例３ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに下
記の化８の構造式で表される４−ビフェニリルベンジル
カルボキシレートを２重量％添加混合して作製した電解
液ｄを実施例３の電解液とする。 Example 3 In a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC),
An electrolyte d prepared by adding and mixing 1M LiPF 6 as an electrolyte salt and further adding and mixing 2% by weight of 4-biphenylylbenzylcarboxylate represented by the following structural formula was mixed with the electrolyte of Example 3. I do.
【００３１】[0031]
【化８】 Embedded image
【００３２】実施例４ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに下
記の化９の構造式で表される２−ビフェニリルプロピオ
ネートを２重量％添加混合して作製した電解液ｅを実施
例４の電解液とする。 Example 4 In a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC),
Adding and mixing 1M LiPF 6 as an electrolyte salt, further implementing the electrolyte e a 2-biphenylyl propionate represented by the structural formula was prepared by adding and mixing 2 weight% of the formula 9 below
The electrolyte of Example 4 was used.
【００３３】[0033]
【化９】 Embedded image
【００３４】実施例５ エチレンカーボネート（ＥＣ）４０重量部とジメチルカ
ーボネート（ＤＭＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに上
記化５の構造式で表される４−ビフェニリルアセテート
を２重量％添加混合して作製した電解液ｆを実施例５の
電解液とする。 Example 5 In a mixed solvent comprising 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of dimethyl carbonate (DMC),
An electrolyte f prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt, and further adding and mixing 2 wt% of 4-biphenylyl acetate represented by the structural formula of the above formula (5) is used as an electrolyte of Example 5 .
【００３５】実施例６ エチレンカーボネート（ＥＣ）４０重量部とメチルエチ
ルカーボネート（ＭＥＣ）６０重量部よりなる混合溶媒
に、電解質塩として１ＭＬｉＰＦ6を添加混合し、さら
に上記化５の構造式で表される４−ビフェニリルアセテ
ートを２重量％添加混合して作製した電解液ｇを実施例
６の電解液とする。 Example 6 1 M LiPF 6 as an electrolyte salt was added to a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of methyl ethyl carbonate (MEC), and the mixture was further mixed. An electrolyte g prepared by adding and mixing 2% by weight of 4-biphenylyl acetate was used as an example.
6 as the electrolytic solution.
【００３６】実施例７ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）３０重量部とジメチルカーボネー
ト（ＤＭＣ）３０重量部よりなる混合溶媒に、電解質塩
として１ＭＬｉＰＦ6を添加混合し、さらに上記化５の
構造式で表される４−ビフェニリルアセテートを２重量
％添加混合して作製した電解液ｈを実施例７の電解液と
する。 Example 7 1 M LiPF 6 as an electrolyte salt was added to a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC), 30 parts by weight of diethyl carbonate (DEC) and 30 parts by weight of dimethyl carbonate (DMC) and mixed. An electrolytic solution h prepared by adding and mixing 2 wt% of 4-biphenylyl acetate represented by the structural formula of Chemical Formula 5 is used as an electrolytic solution of Example 7 .
【００３７】実施例８ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として０．５ＭＬｉＰＦ6と０．５ＭＬｉＢＦ4
を添加混合し、さらに上記化５の構造式で表される４−
ビフェニリルアセテートを２重量％添加混合して作製し
た電解液ｉを実施例８の電解液とする。 Example 8 A mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC) was
0.5 M LiPF 6 and 0.5 M LiBF 4 as electrolyte salts
Is added and mixed, and furthermore, 4-
An electrolyte i prepared by adding and mixing 2% by weight of biphenylyl acetate is used as an electrolyte of Example 8 .
【００３８】比較例１ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合して作製した
電解液ｊを比較例１の電解液とする。Comparative Example 1 A mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC) was
An electrolyte j prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt is used as an electrolyte of Comparative Example 1.
【００３９】比較例２ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらにビ
フェニルを２重量％添加混合して作製した電解液ｋを比
較例２の電解液とする。Comparative Example 2 A mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC) was
An electrolyte k prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 2% by weight of biphenyl is used as an electrolyte of Comparative Example 2.
【００４０】比較例３ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに４
−クロロアニソールを２重量％添加混合して作製した電
解液ｌを比較例３の電解液とする。Comparative Example 3 A mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC)
1M LiPF 6 was added and mixed as an electrolyte salt.
-An electrolyte 1 prepared by adding and mixing 2% by weight of chloroanisole is used as an electrolyte of Comparative Example 3.
【００４１】５．リチウムイオン電池の作製 ついで、図１に示すように、上述のようにして作製した
電極体の上下にそれぞれ絶縁板４１を配置した後、１枚
板からプレス加工により円筒状に成形した負極端子を兼
ねるスチール製の外装缶４０の開口部より、この電極体
を挿入する。ついで、電極体の負極板１０より延出する
負極集電タブ１０ａを外装缶４０の内底部に溶接すると
ともに、電極体の正極板２０より延出する正極集電タブ
２０ａを電流遮断封口体５０の底板５４の底部に溶接す
る。5. Production of Lithium Ion Battery Next, as shown in FIG. 1, insulating plates 41 were arranged above and below the electrode body produced as described above, and then a negative electrode terminal formed into a cylindrical shape by pressing from one sheet was formed. This electrode body is inserted through the opening of the steel outer can 40 also serving as the outer case. Next, the negative electrode current collecting tab 10a extending from the negative electrode plate 10 of the electrode body is welded to the inner bottom portion of the outer can 40, and the positive current collecting tab 20a extending from the positive electrode plate 20 of the electrode body is connected to the current blocking sealing body 50. Is welded to the bottom of the bottom plate 54.
【００４２】なお、電流遮断封口体５０は、図２に示す
ように、逆皿状（キャップ状）に形成されたステンレス
製の正極キャップ５１と、皿状に形成されたステンレス
製の底板５４とから構成される。正極キャップ５１は、
電池外部に向けて膨出する凸部５２と、この凸部５２の
底辺部を構成する平板状のフランジ部５３とからなり、
凸部５２の角部には複数のガス抜き孔５２ａを設けてい
る。一方、底板５４は、電池内部に向けて膨出する凹部
５５と、この凹部５５の底辺部を構成する平板状のフラ
ンジ部５６とからなる。凹部５５の角部にはガス抜き孔
５５ａが設けられている。As shown in FIG. 2, the current blocking sealing body 50 includes a stainless steel positive electrode cap 51 formed in an inverted dish shape (cap shape) and a stainless steel bottom plate 54 formed in a dish shape. Consists of The positive electrode cap 51
A convex portion 52 swelling toward the outside of the battery, and a flat flange portion 53 forming a bottom portion of the convex portion 52;
A plurality of gas vent holes 52a are provided at the corners of the convex portion 52. On the other hand, the bottom plate 54 includes a concave portion 55 that swells toward the inside of the battery, and a flat flange portion 56 that forms the bottom of the concave portion 55. A gas vent hole 55a is provided at a corner of the concave portion 55.
【００４３】これらの正極キャップ５１と底板５４との
内部には、電池内部のガス圧が上昇して所定の圧力以上
になると変形する電力導出板５７が収容されている。こ
の電力導出板５７は凹部５７ａとフランジ部５７ｂとか
らなり、例えば、厚みが０．２ｍｍで表面の凹凸が０．
００５ｍｍのアルミニウム箔から構成される。凹部５７
ａの最低部は底板５４の凹部５５の上表面に接触して配
設されており、フランジ部５７ｂは正極キャップ５１の
フランジ部５３と底板５４のフランジ部５６との間に狭
持される。なお、正極キャップ５１と底板５４とはポリ
プロピレン（ＰＰ）製の封口体用絶縁ガスケット５９に
より液密に封口されている。Inside the positive electrode cap 51 and the bottom plate 54, an electric power lead-out plate 57 which is deformed when the gas pressure inside the battery rises and exceeds a predetermined pressure is accommodated. The power lead-out plate 57 is composed of a concave portion 57a and a flange portion 57b.
It is composed of 005 mm aluminum foil. Recess 57
The lowest portion of a is disposed in contact with the upper surface of the concave portion 55 of the bottom plate 54, and the flange portion 57b is sandwiched between the flange portion 53 of the positive electrode cap 51 and the flange portion 56 of the bottom plate 54. In addition, the positive electrode cap 51 and the bottom plate 54 are liquid-tightly sealed by a sealing body insulating gasket 59 made of polypropylene (PP).
【００４４】フランジ部５７ｂの上部の一部には、ＰＴ
Ｃ（Positive Temperature Coefficient）サーミスタ素
子５８が配設され、電池内に過電流が流れて異常な発熱
現象を生じると、このＰＴＣサーミスタ素子５８の抵抗
値が増大して過電流を減少させる。そして、電池内部の
ガス圧が上昇して所定の圧力以上になると電力導出板５
７の凹部５７ａは変形するため、電力導出板５７と底板
５４の凹部５５との接触が遮断されて過電流あるいは短
絡電流が遮断されるようになる。The upper part of the flange portion 57b has a PT
A C (Positive Temperature Coefficient) thermistor element 58 is provided, and when an overcurrent flows in the battery and an abnormal heat generation phenomenon occurs, the resistance value of the PTC thermistor element 58 increases to reduce the overcurrent. When the gas pressure inside the battery rises to a predetermined pressure or more, the power outlet plate 5
Since the concave portion 57a of the base 7 is deformed, the contact between the power lead-out plate 57 and the concave portion 55 of the bottom plate 54 is cut off, so that overcurrent or short-circuit current is cut off.
【００４５】ついで、外装缶４０の開口部に上述した電
解液ａ〜ｌをそれぞれ注入した後、外装缶４０の開口部
にポリプロピレン（ＰＰ）製の外装缶用絶縁ガスケット
４２を介して電流遮断封口体５０を載置し、外装缶４０
の開口部の上端部を電流遮断封口体５０側にカシメて液
密に封口して、１２種類の円筒形のリチウムイオン電池
をそれぞれ作成する。このようにして作製した各リチウ
ムイオン電池Ａ〜Ｌの公称容量は１３５０ｍＡｈとな
る。Then, after the above-mentioned electrolyte solutions a to l are respectively injected into the opening of the outer can 40, the current interrupting sealing is carried out through the outer can insulating gasket 42 made of polypropylene (PP) into the opening of the outer can 40. The body 50 is placed and the outer can 40
The upper end of the opening is crimped to the current blocking sealing body 50 side and sealed in a liquid-tight manner to produce 12 types of cylindrical lithium ion batteries. The nominal capacity of each of the lithium ion batteries A to L thus produced is 1350 mAh.
【００４６】なお、電池Ａは実施例１の電解液ａを注入
したものであり、電池Ｂは実施例２の電解液ｂを注入し
たものであり、電池Ｃは実施例３の電解液ｃを注入した
ものであり、電池Ｄは実施例４の電解液ｄを注入したも
のであり、電池Ｅは実施例５の電解液ｅを注入したもの
であり、電池Ｆは実施例６の電解液ｆを注入したもので
あり、電池Ｇは実施例７の電解液ｇを注入したものであ
り、電池Ｈは実施例８の電解液ｈを注入したものであ
り、電池Ｉは実施例９の電解液ｉを注入したものであ
り、電池Ｊは比較例１の電解液ｊを注入したものであ
り、電池Ｋは比較例２の電解液ｋを注入したものであ
り、電池Ｌは比較例３の電解液ｌを注入したものであ
る。The battery A was prepared by injecting the electrolyte a of Example 1, the battery B was obtained by injecting the electrolyte b of Example 2, and the battery C was prepared by injecting the electrolyte c of Example 3. The battery D was the one injected with the electrolyte d of the fourth embodiment, the battery E was the one injected with the electrolyte e of the fifth embodiment, and the battery F was the electrolyte f of the sixth embodiment. , The battery G was injected with the electrolyte g of Example 7, the battery H was injected with the electrolyte h of Example 8, and the battery I was injected with the electrolyte h of Example 9. i, the battery J was injected with the electrolyte j of Comparative Example 1, the battery K was injected with the electrolyte k of Comparative Example 2, and the battery L was the electrolyte of Comparative Example 3. Liquid 1 was injected.
【００４７】６．試験 ａ．過充電試験 上述のように作製した１２種類の各リチウムイオン電池
Ａ〜Ｌを１３５０ｍＡ（１Ｃ）の充電々流で電池電圧が
４．１Ｖになるまで充電し、その後、４．１Ｖの定電圧
で３時間充電して満充電状態とする。このように満充電
された１２種類の各リチウムイオン電池Ａ〜Ｌの各正・
負極端子間に２７００ｍＡ（２Ｃ）の充電電流を流して
過充電を行い、過充電開始から電流遮断封口体５０が作
動するまでの時間と、そのときの各電池Ａ〜Ｌの最高温
度を測定すると、下記の表１に示すような結果となっ
た。6 Test a. Overcharge test Each of the 12 types of lithium ion batteries A to L produced as described above was charged at a charge current of 1350 mA (1 C) until the battery voltage reached 4.1 V, and then at a constant voltage of 4.1 V. The battery is charged for 3 hours to be fully charged. The positive and negative of each of the 12 types of lithium ion batteries A to L fully charged in this way
When a charging current of 2700 mA (2C) is passed between the negative electrodes to perform overcharging, the time from the start of overcharging to the activation of the current cutoff sealing body 50 and the maximum temperature of each of the batteries A to L at that time are measured. The results were as shown in Table 1 below.
【００４８】ｂ．低温特性 上述のように作製した１２種類の各リチウムイオン電池
Ａ〜Ｌを、室温（２５℃）で１３５０ｍＡ（１Ｃ）の充
電々流で電池電圧が４．１Ｖになるまで充電し、その
後、４．１Ｖの定電圧で３時間充電して満充電状態とす
る。その後、室温で３時間休止させた後、室温で１３５
０ｍＡ（１Ｃ）の放電々流で終止電圧が２．７５Ｖにな
るまで放電させ、放電時間から室温での放電容量（ｍＡ
ｈ）を求めた。B. Low temperature characteristics The 12 kinds of lithium ion batteries A to L produced as described above were charged at room temperature (25 ° C.) at a charge current of 1350 mA (1 C) until the battery voltage reached 4.1 V. The battery is charged at a constant voltage of 0.1 V for 3 hours to reach a fully charged state. Then, after suspending for 3 hours at room temperature, 135 hours at room temperature.
Discharge was performed at a discharge current of 0 mA (1 C) until the final voltage reached 2.75 V, and the discharge capacity at room temperature (mA
h) was determined.
【００４９】一方、上述のように作製した１２種類の各
リチウムイオン電池Ａ〜Ｌを、室温（２５℃）で１３５
０ｍＡ（１Ｃ）の充電々流で電池電圧が４．１Ｖになる
まで充電し、その後、４．１Ｖの定電圧で３時間充電し
て満充電状態とする。その後、０℃の温度で３時間休止
させた後、０℃の温度で１３５０ｍＡ（１Ｃ）の放電々
流で終止電圧が２．７５Ｖになるまで放電させ、放電時
間から低温での放電容量（ｍＡｈ）を求めた。On the other hand, each of the 12 kinds of lithium ion batteries A to L produced as described above was subjected to 135 at room temperature (25 ° C.).
The battery is charged at a charge current of 0 mA (1 C) until the battery voltage reaches 4.1 V, and then charged at a constant voltage of 4.1 V for 3 hours to be fully charged. Thereafter, the battery was suspended at a temperature of 0 ° C. for 3 hours, and then discharged at a temperature of 0 ° C. with a discharge current of 1350 mA (1 C) until the final voltage reached 2.75 V. From the discharge time, the discharge capacity at a low temperature (mAh) ).
【００５０】ついで、上述のようにして求めた各容量に
基づいて、室温での放電容量（ｍＡｈ）に対する低温で
の放電容量（ｍＡｈ）の割合を低温特性として下記の数
１の数式により算出すると、下記の表１に示すような結
果となった。Next, based on the respective capacities obtained as described above, the ratio of the discharge capacity at low temperature (mAh) to the discharge capacity at room temperature (mAh) is calculated as a low temperature characteristic by the following equation (1). The results were as shown in Table 1 below.
【００５１】[0051]
【数１】低温特性＝（低温での放電容量／室温での放電
容量）×１００％（１） ｃ．保存特性 上述のように作製した１２種類の各リチウムイオン電池
Ａ〜Ｌを室温（２５℃）で１３５０ｍＡ（１Ｃ）の充電
々流で電池電圧が４．１Ｖになるまで充電し、その後、
４．１Ｖの定電圧で３時間充電して満充電状態とする。
その後、６０℃の雰囲気中に２０日間保存した後、１３
５０ｍＡ（１Ｃ）の放電々流で電池電圧が２．７５Ｖに
なるまで放電させ、放電時間から高温保存後の放電容量
を求めた。ついで、上記で求めた室温での放電容量に対
する高温保存後の放電容量の割合を保存特性として下記
の数２の数式により算出すると、下記の表１に示すよう
な結果となった。(1) Low temperature characteristic = (discharge capacity at low temperature / discharge capacity at room temperature) × 100% (1) c. Storage Characteristics The 12 types of lithium-ion batteries A to L produced as described above were charged at room temperature (25 ° C.) at a charge current of 1350 mA (1 C) until the battery voltage reached 4.1 V, and thereafter,
The battery is charged at a constant voltage of 4.1 V for 3 hours to be fully charged.
Then, after storing in an atmosphere of 60 ° C. for 20 days, 13
The battery was discharged at a discharge current of 50 mA (1 C) until the battery voltage reached 2.75 V, and the discharge capacity after high-temperature storage was determined from the discharge time. Then, when the ratio of the discharge capacity after high-temperature storage to the discharge capacity at room temperature determined above was calculated as a storage characteristic by the following mathematical formula 2, the results shown in Table 1 below were obtained.
【００５２】[0052]
【数２】保存特性＝（高温保存後の放電容量／室温での
放電容量）×１００％（２）## EQU2 ## Storage characteristics = (discharge capacity after high temperature storage / discharge capacity at room temperature) × 100% (2)
【００５３】[0053]
【表１】 [Table 1]
【００５４】上記表１から明らかなように、添加剤が無
添加の比較例１の電解液ｊを用いた電池Ｊは、過充電を
開始してから３２分後に破裂が発生したが、低温特性お
よび保存特性は共に良好であった。また、従来例の添加
剤であるビフェニルを添加した比較例２の電解液ｋを用
いた電池Ｋは、過充電を開始してから２０分後に充電電
流が遮断され、そのときの最高温度は８８℃であった。
そして、低温特性および保存特性は共に低い値となっ
た。さらに、従来例の添加剤である４−クロロアニソー
ルを添加した比較例３の電解液ｌを用いた電池Ｌは、過
充電を開始してから２１分後に充電電流が遮断され、そ
のときの最高温度は９０℃であった。そして、低温特性
および保存特性は共に低い値となった。As is evident from Table 1 above, the battery J using the electrolyte j of Comparative Example 1 in which no additive was added bursted 32 minutes after the start of overcharging, but the low-temperature characteristics And the storage characteristics were both good. Further, in the battery K using the electrolyte solution k of Comparative Example 2 to which biphenyl which is an additive of the conventional example was added, the charging current was interrupted 20 minutes after the start of overcharge, and the maximum temperature at that time was 88. ° C.
Then, both the low temperature characteristics and the storage characteristics were low values. Further, in the battery L using the electrolytic solution 1 of Comparative Example 3 to which 4-chloroanisole as a conventional additive was added, the charging current was interrupted 21 minutes after the start of overcharging, and the highest current at that time was observed. The temperature was 90C. Then, both the low temperature characteristics and the storage characteristics were low values.
【００５５】一方、上記化５の構造式で表される４−ビ
フェニリルアセテート、上記化６の構造式で表されるフ
ェニルプロピオネート、上記化７の構造式で表される４
−ビフェニリルベンゾエート、上記化８の構造式で表さ
れる４−ビフェニリルベンジルカルボキシレート、上記
化９の構造式で表される２−ビフェニリルプロピオネー
トを添加した実施例１、参考例１、実施例２〜８の電解
液ａ〜ｉを用いた電池Ａ〜Ｉは、過充電を開始してから
１８〜２０分後に充電電流が遮断され、そのときの最高
温度も７９〜８３℃と低く、かつ低温特性および保存特
性も共に良好であった。但し、フェニルプロピオネート
を添加した参考例１の電解液ｂを用いた電池Ｂの低温特
性は、各実施例の電池に比較して低温特性が若干劣る。
特に、プロピオネートのエステル誘導体である、フェニ
ルプロピオネートを添加した参考例の電解液ｂを用いた
電池Ｂと、２−ビフェニリルプロピオネートを添加した
実施例４の電解液ｅを用いた電池Ｅとを比較すると、電
池Ｅは電池Ｂに比較して低温特性および保存特性共によ
り良好である。これは、ビフェニリル基を有するエステ
ル誘導体がフェニル基を有するエステル誘導体に比較し
て、電解液の添加剤としてより良好であることを示して
いる。 [0055] hand, 4-biphenylyl acetate represented by the structural formula above hear 5, phenylpropionate represented by the structural formula of the formula 6, 4, represented by the above structural formula of 7
Example 1 and Reference Example 1 in which -biphenylyl benzoate, 4-biphenylylbenzylcarboxylate represented by the above formula (8), and 2-biphenylylpropionate represented by the above formula (9) were added. In the batteries A to I using the electrolytes a to i of Examples 2 to 8 , the charging current was interrupted 18 to 20 minutes after the start of overcharge, and the maximum temperature at that time was 79 to 83 ° C. It was low, and both low-temperature characteristics and storage characteristics were good. However, phenylpropionate
B of the battery B using the electrolyte solution b of Reference Example 1 in which
As for the properties, the low-temperature characteristics are slightly inferior to those of the batteries of the examples.
In particular, phenyl, an ester derivative of propionate,
The electrolyte solution b of the reference example to which lupropionate was added was used.
Battery B and 2-biphenylyl propionate were added.
A comparison with the battery E using the electrolyte solution e of Example 4 shows that
Pond E has better low-temperature and storage characteristics than battery B.
Better. This is an ester with a biphenylyl group.
Derivatives have a phenyl group compared to ester derivatives.
Shows that it is better as an electrolyte additive
I have.
【００５６】これは、電池電圧が４．１Ｖに達してから
過充電を行って過充電状態になると、４−ビフェニリル
アセテート、フェニルプロピオネート、４−ビフェニリ
ルベンゾエート、４−ビフェニリルベンジルカルボキシ
レート、２−ビフェニリルプロピオネートなどの添加剤
は分解反応を開始してガスを発生するようになる。これ
と同時に重合反応を開始して重合熱を発生する。この状
態で過充電をさらに続けると、ガスの発生量が増大し、
過充電を開始してから１８〜２０分後に電流遮断封口体
５０が作動して過充電電流を遮断する。これにより、電
池温度も徐々に低下することとなる。This is because when overcharging is performed after the battery voltage reaches 4.1 V and the battery is overcharged, 4-biphenylyl acetate, phenylpropionate, 4-biphenylylbenzoate, 4-biphenylylbenzylcarboxylate are obtained. , 2-biphenylyl propionate, etc., initiate a decomposition reaction to generate gas. At the same time, the polymerization reaction is started to generate polymerization heat. If overcharging is continued further in this state, the amount of generated gas will increase,
Eighteen to twenty minutes after the start of the overcharge, the current cutoff sealing body 50 operates to cut off the overcharge current. As a result, the battery temperature also gradually decreases.
【００５７】なお、電池Ａ〜Ｅと電池Ｆ〜Ｉを比較する
と明らかなように、電解液の有機溶媒の種類あるいは溶
質の種類を代えても格別の差異が認められないので、本
発明の添加剤は電解液の種類に関わらず同様な効果を発
揮するということができる。また、電池Ａ〜電池Ｅを比
較すると明らかなように、本発明の添加剤は上記化５の
構造式で表される４−ビフェニリルアセテート、上記化
７の構造式で表される４−ビフェニリルベンゾエート、
上記化８の構造式で表される４−ビフェニリルベンジル
カルボキシレート、上記化９の構造式で表される２−ビ
フェニリルプロピオネートから選択した少なくとも１種
を用いるのが好ましい。As apparent from comparison between the batteries A to E and the batteries F to I, no particular difference was observed even when the type of the organic solvent or the type of the solute in the electrolytic solution was changed. It can be said that the agent exerts the same effect regardless of the type of the electrolytic solution. Further, as is apparent from a comparison of cell A~ battery E, the additives of the present invention is 4-biphenylyl acetate tape preparative represented by structural formula of the formula 5 is represented by the structural formula above asked 7 4-biphenylyl benzoate,
It is preferable to use at least one selected from 4-biphenylylbenzylcarboxylate represented by the structural formula of the above formula (8) and 2-biphenylylpropionate represented by the structural formula of the above formula (9).
【００５８】７．添加剤の添加量の検討 ついで、添加剤の添加量について検討する。実施例９ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに上
記化５の構造式で表される４−ビフェニリルアセテート
を１重量％添加混合して作製した電解液ｍを実施例９の
電解液とする。7. Examination of the amount of additive to be added Next, the amount of additive to be added is examined. Example 9 In a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC),
An electrolyte m prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt, and further adding and mixing 1 wt% of 4-biphenylyl acetate represented by the structural formula shown above is used as an electrolyte of Example 9 .
【００５９】実施例１０ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに上
記化５の構造式で表される４−ビフェニリルアセテート
を３重量％添加混合して作製した電解液ｎを実施例１０
の電解液とする。 Example 10 In a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC),
An electrolyte n was prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt, and further adding and mixing 3 wt% of 4-biphenylyl acetate represented by the structural formula of the above formula ( 10).
Electrolyte solution.
【００６０】実施例１１ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに上
記化５の構造式で表される４−ビフェニリルアセテート
を５重量％添加混合して作製した電解液ｏを実施例１１
の電解液とする。 Example 11 In a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC),
Example 11 was prepared by adding and mixing 1M LiPF 6 as an electrolyte salt, and further adding and mixing 5% by weight of 4-biphenylyl acetate represented by the structural formula of the above formula ( 11).
Electrolyte solution.
【００６１】実施例１２ エチレンカーボネート（ＥＣ）４０重量部とジエチルカ
ーボネート（ＤＥＣ）６０重量部よりなる混合溶媒に、
電解質塩として１ＭＬｉＰＦ6を添加混合し、さらに上
記化５の構造式で表される４−ビフェニリルアセテート
を１０重量％添加混合して作製した電解液ｐを実施例１
２の電解液とする。 Example 12 In a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC),
Example 1 was prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 10 wt% of 4-biphenylyl acetate represented by the structural formula of the above formula ( 1).
2 electrolyte solution.
【００６２】この後、上述と同様にして、外装缶４０の
開口部に上述した電解液ｍ〜ｐをそれぞれ注入した後、
外装缶４０の開口部にポリプロピレン（ＰＰ）製の外装
缶用絶縁ガスケット４２を介して電流遮断封口体５０を
載置し、外装缶４０の開口部の上端部を電流遮断封口体
５０側にカシメて液密に封口して、リチウムイオン電池
Ｍ（電解液ｍを注入したもの）、リチウムイオン電池Ｎ
（電解液ｎを注入したもの）、リチウムイオン電池Ｏ
（電解液ｏを注入したもの）、リチウムイオン電池Ｐ
（電解液ｐを注入したもの）をそれぞれ作製する。Thereafter, in the same manner as described above, the above-described electrolytes m to p are respectively injected into the openings of the outer can 40, and then,
A current blocking sealing body 50 is placed in the opening of the outer can 40 via an insulating can insulating gasket 42 made of polypropylene (PP), and the upper end of the opening of the outer can 40 is swaged toward the current blocking sealing body 50. Lithium-ion battery M (with electrolyte m injected), lithium-ion battery N
(Injected electrolyte n), lithium ion battery O
(Injected electrolyte o), lithium ion battery P
(The one into which the electrolytic solution p is injected) is prepared.
【００６３】ついで、上述と同様にして、これらの各電
池Ｍ〜Ｐに過充電を施して、過充電を開始してから電流
遮断封口体５０が作動するまでの時間と、そのときの各
電池Ｍ〜Ｐの最高温度を測定すると、下記の表２に示す
ような結果となった。また、上述と同様にして、低温特
性および保存特性を測定すると、下記の表２に示すよう
な結果となった。Next, in the same manner as described above, these batteries M to P are overcharged, the time from the start of overcharge to the activation of the current cutoff sealing member 50, and the respective batteries at that time. When the maximum temperatures of M to P were measured, the results were as shown in Table 2 below. When the low-temperature characteristics and the storage characteristics were measured in the same manner as described above, the results shown in Table 2 below were obtained.
【００６４】[0064]
【表２】 [Table 2]
【００６５】上記表２より明らかなように、添加剤の添
加量が１〜１０重量％の範囲であれば、電流遮断時間、
最高温度、低温特性および保存特性において格別の差異
が認められなかった。このことから、添加剤の添加量は
１〜１０重量％の範囲にするのが望ましく、好ましくは
１〜５重量％とするのが望ましい。なお、表２には示し
ていないが、上記化５の構造式で表される４−ビフェニ
リルアセテート以外の添加剤、即ち、上記化７の構造式
で表される４−ビフェニリルベンゾエート、上記化８の
構造式で表される４−ビフェニリルベンジルカルボキシ
レート、上記化９の構造式で表される２−ビフェニリル
プロピオネートなどの他の添加剤を用いてもほぼ同様な
結果が得られた。As is clear from Table 2, when the amount of the additive is in the range of 1 to 10% by weight, the current interruption time,
No particular differences were observed in the maximum temperature, low temperature characteristics and storage characteristics. For this reason, the amount of the additive is desirably in the range of 1 to 10% by weight, and preferably 1 to 5% by weight. Although not shown in Table 2, additives other than 4-biphenylyl acetate represented by the structural formula of the formula 5, immediately Chi, represented by the structural formula above asked 7 4- biphenylyl benzoate Approximately the same results can be obtained by using other additives such as 4-biphenylylbenzylcarboxylate represented by the structural formula of Chemical Formula 8 and 2-biphenylylpropionate represented by the chemical formula of Chemical Formula 9 above. was gotten.
【００６６】８．電流遮断封口体を用いなかった場合 上述した実施形態においては、電流遮断封口体５０を備
えたリチウムイオン電池に本発明の添加剤を添加した電
解液を注入した例について説明したが、電流遮断封口体
を備えていない角形リチウムイオン電池に本発明の添加
剤を添加した電解液を注入した場合においても検討し
た。8. In the case where the current-blocking sealing body was not used In the above-described embodiment, an example was described in which the electrolyte solution to which the additive of the present invention was added was injected into the lithium ion battery including the current-blocking sealing body 50. Investigation was also made on a case where an electrolyte solution containing the additive of the present invention was injected into a prismatic lithium ion battery having no body.
【００６７】実施例１３ エチレンカーボネート（ＥＣ）４０重量部とメチルエチ
ルカーボネート（ＭＥＣ）６０重量部よりなる混合溶媒
に、電解質塩として１ＭＬｉＰＦ6を添加混合し、さら
に上記化５の構造式で表される４−ビフェニリルアセテ
ートを２重量％添加混合して作製した電解液ｑを実施例
１３の電解液とする。 Example 13 1 M LiPF 6 as an electrolyte salt was added to a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of methyl ethyl carbonate (MEC), and further mixed. The electrolyte q prepared by adding and mixing 2% by weight of 4-biphenylyl acetate in Example 1 was prepared.
This is the electrolyte of No. 13 .
【００６８】参考例２ エチレンカーボネート（ＥＣ）４０重量部とメチルエチ
ルカーボネート（ＭＥＣ）６０重量部よりなる混合溶媒
に、電解質塩として１ＭＬｉＰＦ6を添加混合し、さら
に上記化６の構造式で表されるフェニルプロピオネート
を２重量％添加混合して作製した電解液ｒを参考例２の
電解液とする。 REFERENCE EXAMPLE 2 1 M LiPF 6 as an electrolyte salt was added to a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of methyl ethyl carbonate (MEC), and the mixture was further expressed by the above structural formula. An electrolytic solution r prepared by adding and mixing 2% by weight of phenylpropionate was used as an electrolytic solution of Reference Example 2 .
【００６９】比較例４ エチレンカーボネート（ＥＣ）４０重量部とメチルエチ
ルカーボネート（ＭＥＣ）６０重量部よりなる混合溶媒
に、電解質塩として１ＭＬｉＰＦ6を添加混合して作製
した電解液ｓを比較例４の電解液とする。Comparative Example 4 An electrolyte s prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt to a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of methyl ethyl carbonate (MEC) was used. Electrolyte.
【００７０】この後、上述と同様にして、図示しない角
形外装缶の開口部に上述した電解液ｑ〜ｓをそれぞれ注
入し、リチウムイオン電池Ｑ（電解液ｑを注入したも
の）、リチウムイオン電池Ｒ（電解液ｒを注入したも
の）、リチウムイオン電池Ｓ（電解液ｓを注入したも
の）をそれぞれ作製する。このようにして作製した角形
の各リチウムイオン電池Ｑ〜Ｓの公称容量は６００ｍＡ
ｈとなる。Thereafter, in the same manner as described above, the above-mentioned electrolytes q to s were respectively injected into the openings of the rectangular outer can (not shown), and the lithium ion battery Q (the one into which the electrolyte q was injected), the lithium ion battery R (injected electrolyte r) and lithium ion battery S (injected electrolyte s) are prepared. The nominal capacity of each of the rectangular lithium-ion batteries Q to S thus manufactured is 600 mA.
h.
【００７１】上述のように作製した３種類の各リチウム
イオン電池Ｑ〜Ｓを６００ｍＡ（１Ｃ）の充電々流で電
池電圧が４．１Ｖになるまで充電し、その後４．１Ｖの
定電圧で３時間充電して満充電状態とする。このように
満充電された３種類の各リチウムイオン電池Ｑ〜Ｓの各
正・負極端子間に１２００ｍＡ（２Ｃ）の充電電流を流
して過充電を行い、各電池Ｑ〜Ｓの最高温度を測定する
過充電試験を行った。この結果は下記の表３に示すよう
な結果となった。The three types of lithium ion batteries Q to S prepared as described above were charged at a charging current of 600 mA (1 C) until the battery voltage reached 4.1 V, and then charged at a constant voltage of 4.1 V. The battery is charged for a time to reach a fully charged state. Overcharging is performed by passing a charging current of 1200 mA (2C) between the positive and negative terminals of each of the three types of lithium-ion batteries Q to S that are fully charged as described above, and the maximum temperature of each of the batteries Q to S is measured. Overcharge test was performed. The result was as shown in Table 3 below.
【００７２】ついで、上述のように作製した３種類の各
リチウムイオン電池Ｑ〜Ｓを、室温（２５℃）で６００
ｍＡ（１Ｃ）の充電々流で電池電圧が４．１Ｖになるま
で充電し、その後４．１Ｖの定電圧で３時間充電して満
充電状態とする。その後、室温で３時間休止させた後、
室温で６００ｍＡ（１Ｃ）の放電々流で終止電圧が２．
７５Ｖになるまで放電させ、放電時間から室温での放電
容量（ｍＡｈ）を求めた。Next, each of the three types of lithium ion batteries Q to S prepared as described above was placed at room temperature (25 ° C.) for 600 ° C.
The battery is charged at a charge current of mA (1C) until the battery voltage reaches 4.1 V, and then charged at a constant voltage of 4.1 V for 3 hours to obtain a fully charged state. Then, after resting at room temperature for 3 hours,
The cut-off voltage is 2. at a discharge current of 600 mA (1 C) at room temperature.
The battery was discharged until the voltage reached 75 V, and the discharge capacity (mAh) at room temperature was determined from the discharge time.
【００７３】一方、上述のように作製した３種類の各リ
チウムイオン電池Ｑ〜Ｓを、室温（２５℃）で６００ｍ
Ａ（１Ｃ）の充電々流で電池電圧が４．１Ｖになるまで
充電し、その後４．１Ｖの定電圧で３時間充電して満充
電状態とする。その後、０℃の温度で３時間休止させた
後、０℃の温度で６００ｍＡ（１Ｃ）の放電々流で終止
電圧が２．７５Ｖになるまで放電させ、放電時間から低
温での放電容量（ｍＡｈ）を求めた。On the other hand, each of the three types of lithium ion batteries Q to S manufactured as described above was placed at room temperature (25 ° C.) for 600 m.
The battery is charged by the charging current of A (1C) until the battery voltage reaches 4.1 V, and then charged at a constant voltage of 4.1 V for 3 hours to be fully charged. Thereafter, the battery was suspended at a temperature of 0 ° C. for 3 hours, and then discharged at a temperature of 0 ° C. with a discharge current of 600 mA (1 C) until the final voltage reached 2.75 V. From the discharge time, the discharge capacity at a low temperature (mAh) ).
【００７４】ついで、上述のように測定した各容量に基
づいて、室温での放電容量（ｍＡｈ）に対する低温での
放電容量（ｍＡｈ）の割合を低温特性として上述した数
１の数式により算出すると、下記の表３に示すような結
果となった。Next, based on each capacity measured as described above, the ratio of the discharge capacity (mAh) at a low temperature to the discharge capacity (mAh) at a room temperature is calculated as a low-temperature characteristic by the above-described equation (1). The results are as shown in Table 3 below.
【００７５】また、上述のように作製した３種類の各リ
チウムイオン電池Ｑ〜Ｓを、室温（２５℃）で６００ｍ
Ａ（１Ｃ）の充電々流で電池電圧が４．１Ｖになるまで
充電し、その後４．１Ｖの定電圧で３時間充電して満充
電状態とする。その後、６０℃の雰囲気中に２０日間保
存した後、６００ｍＡ（１Ｃ）の放電々流で電池電圧が
２．７５Ｖになるまで放電させ、放電時間から高温保存
後の放電容量を求めた。ついで、上記で求めた室温での
放電容量に対する高温保存後の放電容量の割合を保存特
性として、上述した数２の数式により算出すると、下記
の表３に示すような結果となった。Each of the three types of lithium ion batteries Q to S manufactured as described above was placed at room temperature (25 ° C.) for 600 m.
The battery is charged by the charging current of A (1C) until the battery voltage reaches 4.1 V, and then charged at a constant voltage of 4.1 V for 3 hours to be fully charged. Thereafter, the battery was stored in an atmosphere of 60 ° C. for 20 days, and then discharged at a discharge current of 600 mA (1 C) until the battery voltage reached 2.75 V, and the discharge capacity after high-temperature storage was determined from the discharge time. Then, when the ratio of the discharge capacity after high-temperature storage to the discharge capacity at room temperature determined above was calculated as the storage characteristic using the above-described formula 2, the results shown in Table 3 below were obtained.
【００７６】[0076]
【表３】 [Table 3]
【００７７】上記表３より明らかなように、添加剤が無
添加の比較例４の電解液ｓを用いた電池Ｓは、過充電に
より破裂が発生したが、低温特性および保存特性は共に
良好であった。一方、本発明の添加剤である上記化５の
構造式で表される４−ビフェニリルアセテートを添加し
た実施例１３の電解液ｑを用いた電池Ｑおよび上記化６
の構造式で表されるフェニルプロピオネートを添加した
参考例２の電解液ｒを用いた電池Ｒは、過充電を行うと
温度上昇は高いが破裂に至ることはなかった。また、低
温特性および保存特性も、添加剤が無添加のものとほぼ
同様な値を示して、共に良好であった。As is clear from Table 3, the battery S using the electrolyte s of Comparative Example 4 to which no additive was added was ruptured due to overcharge, but both low-temperature characteristics and storage characteristics were good. there were. On the other hand, a battery Q using the electrolytic solution q of Example 13 to which 4-biphenylyl acetate represented by the structural formula of the above formula (5), which is an additive of the present invention, was added, and
Phenylpropionate represented by the structural formula
In the battery R using the electrolyte solution r of Reference Example 2, the temperature rise was high when overcharging was performed, but the battery did not burst. In addition, the low-temperature characteristics and the storage characteristics were almost the same as those in the case where no additive was added, and both were good.
【００７８】上述したように、本発明の上記化５の構造
式で表される４−ビフェニリルアセテート、上記化７の
構造式で表される４−ビフェニリルベンゾエート、上記
化８の構造式で表される４−ビフェニリルベンジルカル
ボキシレート、上記化９の構造式で表される２−ビフェ
ニリルプロピオネートなどのエステル誘導体からなる添
加剤を電解液に添加して用いると、低温特性や保存特性
などの電池特性に悪影響を及ぼすことなく過充電に対し
ては有効に作用して、電池性能を劣化させることなく電
池の安全性を確保できるようになる。[0078] As described above, the present invention the chemical formula 5 in structural formula represented by 4-biphenylyl acetate tape DOO, 4-biphenylyl benzoate represented by the structural formula above hear 7, of the formula 8 When an additive composed of an ester derivative such as 4-biphenylylbenzylcarboxylate represented by the structural formula or 2-biphenylylpropionate represented by the structural formula shown above is used by adding to the electrolytic solution, It works effectively for overcharging without adversely affecting battery characteristics such as characteristics and storage characteristics, and can secure battery safety without deteriorating battery performance.
【００７９】なお、上述の実施形態においては、負極活
物質として天然黒鉛（ｄ＝３．３６）を用いる例につい
て説明したが、天然黒鉛以外に、リチウムイオンを吸蔵
・脱離し得るカーボン系材料、例えば、グラファイト、
カーボンブラック、コークス、ガラス状炭素、炭素繊
維、またはこれらの焼成体等が好適である。In the above embodiment, an example in which natural graphite (d = 3.36) is used as the negative electrode active material has been described. In addition to natural graphite, carbon-based materials capable of inserting and extracting lithium ions, For example, graphite,
Carbon black, coke, vitreous carbon, carbon fiber, or a fired body thereof are suitable.
【００８０】また、上述の実施形態においては、正極活
物質としてＬｉＣｏＯ2を用いる例について説明した
が、ＬｉＣｏＯ2以外に、リチウムイオンをゲストとし
て受け入れ得るリチウム含有遷移金属化合物、例えば、
ＬｉＮｉＯ2、ＬｉＣｏXＮｉ(1-X)Ｏ2、ＬｉＣｒＯ2、
ＬｉＶＯ2、ＬｉＭｎＯ2、αＬｉＦｅＯ2、ＬｉＴｉ
Ｏ2、ＬｉＳｃＯ2、ＬｉＹＯ2、ＬｉＭｎ2Ｏ4等が好ま
しいが、特に、ＬｉＮｉＯ2、ＬｉＣｏXＮｉ(1-X)Ｏ2を
単独で用いるかあるいはこれらの二種以上を混合して用
いるのが好適である。In the above-described embodiment, an example in which LiCoO 2 is used as the positive electrode active material has been described. In addition to LiCoO 2 , a lithium-containing transition metal compound capable of accepting lithium ions as a guest, for example,
LiNiO 2 , LiCo X Ni (1-X) O 2 , LiCrO 2 ,
LiVO 2 , LiMnO 2 , αLiFeO 2 , LiTi
O 2 , LiScO 2 , LiYO 2 , LiMn 2 O 4 and the like are preferable, and in particular, LiNiO 2 , LiCo X Ni (1-X) O 2 is used alone or a mixture of two or more thereof is used. Is preferred.
【００８１】さらに、電解液としては、有機溶媒に溶質
としてリチウム塩を溶解したイオン伝導体であって、イ
オン伝導率が高く、正・負の各電極に対して化学的、電
気化学的に安定で、使用可能温度範囲が広くかつ安全性
が高く、安価なものであれば使用することができる。例
えば、上記した有機溶媒以外に、プロピレンカーボネー
ト（ＰＣ）、スルフォラン（ＳＬ）、テトラハイドロフ
ラン（ＴＨＦ）、γブチロラクトン（ＧＢＬ）、等ある
いはこれらの混合溶媒が好適である。また、溶質として
は電子吸引性の強いリチウム塩を使用し、上記したＬｉ
ＰＦ6あるいはＬｉＢＦ4以外に、例えば、ＬｉＣｌ
Ｏ4、ＬｉＡｓＦ6、ＬｉＣＦ3ＳＯ3、Ｌｉ（ＣＦ3Ｓ
Ｏ2）2Ｎ、Ｌｉ（Ｃ2Ｆ5ＳＯ2）2Ｎ、ＬｉＣ4Ｆ9ＳＯ3
等が好適である。Further, the electrolyte is an ionic conductor in which a lithium salt is dissolved as a solute in an organic solvent, and has a high ionic conductivity and is chemically and electrochemically stable with respect to each of the positive and negative electrodes. In this case, any one that has a wide usable temperature range, high safety, and inexpensive can be used. For example, in addition to the above organic solvents, propylene carbonate (PC), sulfolane (SL), tetrahydrofuran (THF), γ-butyrolactone (GBL), and the like, or a mixed solvent thereof are suitable. As the solute, a lithium salt having a strong electron-withdrawing property is used, and the above-described Li is used.
Other than PF 6 or LiBF 4 , for example, LiCl
O 4 , LiAsF 6 , LiCF 3 SO 3 , Li (CF 3 S
O 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, LiC 4 F 9 SO 3
Etc. are preferred.
【図１】 本発明の電解液を備えた一実施形態の電池の
セパレータを介して重ね合わせた正・負極板を卷回して
外装缶内に収納した状態を示す断面図である。FIG. 1 is a cross-sectional view showing a state in which positive and negative electrode plates superimposed via a separator of a battery provided with an electrolytic solution of the present invention are wound and housed in an outer can.
【図２】 図１の外装缶の開口部に装着される電流遮断
封口体を示す一部破断図である。FIG. 2 is a partially cutaway view showing a current blocking sealing body attached to an opening of the outer can of FIG. 1;
１０…負極板、１０ａ…負極集電タブ、２０…正極板、
２０ａ…正極集電タブ、３０…セパレータ、４０…外装
缶、４１…スペーサ、４２…外装缶用絶縁ガスケット、
５０…電流遮断封口体10: negative electrode plate, 10a: negative electrode current collecting tab, 20: positive electrode plate,
20a: positive electrode current collecting tab, 30: separator, 40: outer can, 41: spacer, 42: insulating gasket for outer can,
50 ... current interrupting sealing body
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安部 浩司 山口県宇部市大字小串1978番地の５ 宇 部興産株式会社 宇部研究所内 (72)発明者 植木 明 山口県宇部市大字小串1978番地の５ 宇 部興産株式会社 宇部研究所内 (72)発明者 高井 勉 山口県宇部市大字小串1978番地の５ 宇 部興産株式会社 宇部研究所内 (56)参考文献 特開 平10−275632（ＪＰ，Ａ) 特開 平９−22722（ＪＰ，Ａ) 特開 平８−306387（ＪＰ，Ａ) 特開 平８−293323（ＪＰ，Ａ) 特開 昭63−114076（ＪＰ，Ａ) 特開 平７−22069（ＪＰ，Ａ) 特開 平８−96848（ＪＰ，Ａ) 特開 平９−92329（ＪＰ，Ａ) 特開 平９−147910（ＪＰ，Ａ) 特開 平９−306542（ＪＰ，Ａ) 特開 平10−92221（ＪＰ，Ａ) 特開 平10−92222（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 10/40 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koji Abe 5-1978 Kogushi, Oji, Ube City, Yamaguchi Prefecture Inside Ube Research Institute, Ltd. (72) Inventor: Tsutomu Takai 1978 Kogushi, Ube City, Ube-shi, Yamaguchi 5 Ube-Kosan Co., Ltd. Ube Laboratory (56) References JP-A-10-275632 (JP, A) JP JP-A-9-22722 (JP, A) JP-A-8-306387 (JP, A) JP-A-8-293323 (JP, A) JP-A-63-114076 (JP, A) JP-A-7-22069 (JP JP-A-8-96848 (JP, A) JP-A-9-92329 (JP, A) JP-A-9-147910 (JP, A) JP-A-9-306542 (JP, A) 10-92221 (JP, A) 222 (JP, A) (58) Field surveyed (Int. Cl. 6 , DB name) H01M 10/40
Claims (4)
した非水系電池用電解液であって、 前記有機溶媒に下記の化１の一般式で表されるエステル
誘導体が含有されていることを特徴とする非水系電池用
電解液。 【化１】 ただし、上記化１に示したＲ1 はビフェニリル基を示
し、Ｒ2は炭素数１〜６のアルキル基、フェニル基、ベ
ンジル基を示す。An electrolyte for a non-aqueous battery in which a lithium salt is dissolved as a solute in an organic solvent, wherein the organic solvent contains an ester derivative represented by the following general formula (1). Electrolyte for non-aqueous batteries. Embedded image However, R 1 shown in the chemical formula 1 represents a bi Feniriru group, R 2 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group.
ルアセテート、４−ビフェニリルベンゾエート、４−ビ
フェニリルベンジルカルボキシレートあるいは２−ビフ
ェニリルプロピオネートから選択した少なくとも１種を
備えていることを特徴とする請求項１に記載の非水系電
池用電解液。Wherein said ester derivative is 4-biphenylyl acetate tape bets, 4 - biphenylyl benzoate, that comprises at least one selected from 4-biphenylyl benzyl carboxylate or 2-biphenylyl propionate The electrolyte for a non-aqueous battery according to claim 1, wherein:
する正極と炭素を負極活物質とする負極とをセパレータ
を介して積層して構成された電極体を電池容器内に備え
るとともに、有機溶媒に溶質としてリチウム塩を溶解し
た電解液を備えた非水系二次電池であって、 前記電解液に下記の化２の一般式で表されるエステル誘
導体が含有されていることを特徴とする非水系二次電
池。 【化２】 ただし、上記化２に示したＲ1 はビフェニリル基を示
し、Ｒ2は炭素数１〜６のアルキル基、フェニル基、ベ
ンジル基を示す。3. A battery container comprising an electrode body formed by laminating a positive electrode using a lithium-containing metal oxide as a positive electrode active material and a negative electrode using carbon as a negative electrode active material in a battery container, and further comprising an organic solvent. A non-aqueous secondary battery provided with an electrolyte solution in which a lithium salt is dissolved as a solute, wherein the electrolyte solution contains an ester derivative represented by the following general formula (2). Water-based secondary battery. Embedded image However, R 1 shown in the chemical formula 2 represents an bi Feniriru group, R 2 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group.
ルアセテート、４−ビフェニリルベンゾエート、４−ビ
フェニリルベンジルカルボキシレートあるいは２−ビフ
ェニリルプロピオネートから選択した少なくとも１種を
備えていることを特徴とする請求項３に記載の非水系二
次電池。Wherein said ester derivative is 4-biphenylyl acetate tape bets, 4 - biphenylyl benzoate, that comprises at least one selected from 4-biphenylyl benzyl carboxylate or 2-biphenylyl propionate The non-aqueous secondary battery according to claim 3, wherein:
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|---|---|---|---|
| JP10217953A JP2963898B1 (en) | 1998-07-31 | 1998-07-31 | Electrolyte for non-aqueous battery and secondary battery using this electrolyte |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10217953A JP2963898B1 (en) | 1998-07-31 | 1998-07-31 | Electrolyte for non-aqueous battery and secondary battery using this electrolyte |
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| JP2000058112A JP2000058112A (en) | 2000-02-25 |
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ID=16712313
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|---|---|---|---|
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Cited By (1)
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|---|---|---|---|---|
| JP3402233B2 (en) * | 1998-12-28 | 2003-05-06 | 日本電池株式会社 | Non-aqueous electrolyte secondary battery |
| JP4940501B2 (en) * | 2001-03-21 | 2012-05-30 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery |
| KR100417084B1 (en) * | 2001-05-08 | 2004-02-05 | 주식회사 엘지화학 | New additives for electrolyte and lithium ion battery using the same |
| JP3512021B2 (en) | 2001-05-15 | 2004-03-29 | 株式会社日立製作所 | Lithium secondary battery |
| WO2002095861A1 (en) * | 2001-05-22 | 2002-11-28 | Lg Chem, Ltd. | Non-aqueous electrolyte additive for improving safety and lithium ion secondary battery comprising the same |
| JP2004063432A (en) * | 2002-06-05 | 2004-02-26 | Sony Corp | Battery |
| CN100438198C (en) | 2004-12-31 | 2008-11-26 | 比亚迪股份有限公司 | Mixed additive and electrolyte and lithium ion secondary battery containing same |
| JP5433529B2 (en) * | 2010-08-25 | 2014-03-05 | 株式会社日立製作所 | Lithium ion secondary battery |
| JP2014192153A (en) * | 2013-03-28 | 2014-10-06 | Fujifilm Corp | Electrolytic solution for nonaqueous secondary battery use, nonaqueous secondary battery, and additive agent for nonaqueous electrolytic solution use |
| EP3132486B1 (en) * | 2014-04-17 | 2018-06-06 | Gotion, Inc. | Alkylbenzoate derivatives as electrolyte additive for lithium based batteries |
| JP6673225B2 (en) * | 2014-12-24 | 2020-03-25 | 宇部興産株式会社 | Non-aqueous electrolyte and power storage device using the same |
| JP6759847B2 (en) * | 2016-08-19 | 2020-09-23 | 三菱ケミカル株式会社 | Non-aqueous electrolyte solution and non-aqueous electrolyte battery using it |
-
1998
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015111676A1 (en) | 2014-01-22 | 2015-07-30 | 三菱化学株式会社 | Non-aqueous electrolyte solution and non-aqueous electrolyte solution secondary battery using same |
| KR20160107262A (en) | 2014-01-22 | 2016-09-13 | 미쓰비시 가가꾸 가부시키가이샤 | Non-aqueous electrolyte solution and non-aqueous electrolyte solution secondary battery using same |
| US10177414B2 (en) | 2014-01-22 | 2019-01-08 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous electrolyte secondary battery using the same |
| US10777850B2 (en) | 2014-01-22 | 2020-09-15 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous electrolyte secondary battery using the same |
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|---|---|
| JP2000058112A (en) | 2000-02-25 |
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