JP3080609B2 - 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
- JP3080609B2 JP3080609B2 JP10217992A JP21799298A JP3080609B2 JP 3080609 B2 JP3080609 B2 JP 3080609B2 JP 10217992 A JP10217992 A JP 10217992A JP 21799298 A JP21799298 A JP 21799298A JP 3080609 B2 JP3080609 B2 JP 3080609B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- battery
- electrolyte
- weight
- biphenylylmethyl
- 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
Landscapes
- Secondary Cells (AREA)
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カーボネート誘導
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はフェニル基、ビフェニリル基、アルキルフ
ェニル基を示し、R2は炭素数1〜6のアルキル基、フ
ェニル基を示す。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 a carbonate derivative represented by the following general formula (3). It is characterized by the following. However, R 1 shown in Chemical formula 3 represents a phenyl group, a biphenylyl group or an alkylphenyl group, and R 2 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.
【0011】[0011]
【化3】 Embedded image
【0012】上記化3の一般式で表されるカーボネート
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カー
ボネート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、カーボネート誘導体が重合反応
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カーボネー
ト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。The carbonate 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. Therefore, the electrolytic solution containing the carbonate derivative represented by the general formula (3) does not deteriorate the battery performance. Further, the polymer produced by the polymerization reaction of the carbonate derivative is a substance that is unlikely to be redissolved in the electrolytic solution, and thus effectively acts on overcharging. Therefore, by using the electrolyte containing the carbonate derivative represented by the general formula (3), the safety of the battery can be ensured.
【0013】そして、上記カーボネート誘導体は、2−
ビフェニリルメチルカーボネート、4−ビフェニリルメ
チルカーボネート、4−ビフェニリルブチルカーボネー
ト、3−ビフェニリルメチルカーボネート、4−ビフェ
ニリルフェニルカーボ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。The above carbonate derivative is 2-
Biphenylylmethyl carbonate, 4-biphenylyl methyl carbonate, 4-biphenylyl-butyl carbonate, 3 - biphenylylmethyl carbonate, 4-biphenylyl phenyl carbonate Natick DOO or selected at least 1
It is preferred to have seeds.
【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カーボネー
ト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 a carbonate derivative represented by the following general formula (4). I do. However,
R 1 shown in Chemical Formula 4 represents a biphenylyl group , and R 2 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.
【0015】[0015]
【化4】 Embedded image
【0016】上記化4の一般式で表されるカーボネート
誘導体は電解液中の有機溶媒との親和性が良いため、こ
のようなカーボネート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 carbonate 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 a carbonate 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、
このようなカーボネート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 electrolytic solution in which such a carbonate 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 does not affect battery safety. 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ジフェニルカーボネートを
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)
An electrolyte a prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 2% by weight of diphenyl carbonate represented by the following structural formula is used as an electrolyte of Example 1.
【0025】[0025]
【化5】 Embedded image
【0026】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6の構造式で表される2−ビフェニリルメチルカ
ーボネートを2重量%添加混合して作製した電解液b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),
An electrolyte b prepared by adding and mixing 1M LiPF 6 as an electrolyte salt and further adding and mixing 2% by weight of 2-biphenylylmethyl carbonate represented by the following structural formula is used as an electrolyte of Example 2. .
【0027】[0027]
【化6】 Embedded image
【0028】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7の構造式で表される4−ビフェニリルメチルカ
ーボネートを2重量%添加混合して作製した電解液c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 solution c prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 2 wt% of 4-biphenylylmethyl carbonate represented by the following structural formula is used as an electrolyte solution of Example 3. .
【0029】[0029]
【化7】 Embedded image
【0030】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8の構造式で表される4−ビフェニリルブチルカ
ーボネートを2重量%添加混合して作製した電解液d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),
An electrolyte solution d prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 2 wt% of 4-biphenylylbutyl carbonate represented by the following structural formula is used as an electrolyte solution of Example 4. .
【0031】[0031]
【化8】 Embedded image
【0032】実施例5 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メチル2,4,6−トリメ
チルフェニルカーボネートを2重量%添加混合して作製
した電解液eを実施例5の電解液とする。Example 5 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 solution e prepared in Example 5 was prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt, and further adding and mixing 2% by weight of methyl 2,4,6-trimethylphenyl carbonate represented by the following structural formula. Electrolyte.
【0033】[0033]
【化9】 Embedded image
【0034】実施例6 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10の構造式で表される3−ビフェニリルメチル
カーボネートを2重量%添加混合して作製した電解液f
を実施例6の電解液とする。Example 6 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 f prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt, and further adding and mixing 2 wt% of 3-biphenylylmethyl carbonate represented by the following structural formula.
Is used as the electrolyte of Example 6.
【0035】[0035]
【化10】 Embedded image
【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)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11の構造式で表される4−ビフェニリルフェニ
ルカーボネートを2重量%添加混合して作製した電解液
gを実施例7の電解液とする。Example 7 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 g prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 2 wt% of 4-biphenylylphenyl carbonate represented by the following structural formula 11 is used as an electrolyte of Example 7. .
【0037】[0037]
【化11】 Embedded image
【0038】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1MLiPF6を添加混合し、さらに下
記の化12の構造式で表されるベンジル4−ビフェニリ
ルカーボネートを2重量%添加混合して作製した電解液
h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
An electrolyte h prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 2% by weight of benzyl 4-biphenylyl carbonate represented by the following structural formula is used as an electrolyte of Example 8. .
【0039】[0039]
【化12】 Embedded image
【0040】実施例9 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ジフェニルカーボネートを2
重量%添加混合して作製した電解液iを実施例9の電解
液とする。Example 9 In a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of dimethyl carbonate (DMC),
1M LiPF 6 was added and mixed as an electrolyte salt, and diphenyl carbonate represented by the structural formula (5) was added to 2
The electrolytic solution i prepared by adding and mixing the weight% is used as the electrolytic solution of Example 9.
【0041】実施例10 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ジフェニルカーボネート
を2重量%添加混合して作製した電解液jを実施例10
の電解液とする。Example 10 1M LiPF 6 as an electrolyte salt was added to and mixed with a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of methyl ethyl carbonate (MEC). An electrolyte j prepared by adding and mixing 2% by weight of diphenyl carbonate was used in Example 10.
Electrolyte solution.
【0042】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)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
構造式で表されるジフェニルカーボネートを2重量%添
加混合して作製した電解液kを実施例11の電解液とす
る。Example 11 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 k prepared by adding and mixing 2% by weight of diphenyl carbonate represented by the structural formula of Chemical Formula 5 is used as an electrolytic solution of Example 11.
【0043】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ジフ
ェニルカーボネートを2重量%添加混合して作製した電
解液lを実施例12の電解液とする。Example 12 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 2% by weight of diphenyl carbonate represented by the structural formula (1) is added and mixed.
【0044】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m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 m prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt is used as an electrolyte of Comparative Example 1.
【0045】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n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)
An electrolyte n 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.
【0046】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o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) was
1M LiPF 6 was added and mixed as an electrolyte salt.
-An electrolyte solution o prepared by adding and mixing 2% by weight of chloroanisole is used as an electrolyte solution of Comparative Example 3.
【0047】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.
【0048】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.
【0049】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, a power lead-out plate 57 which is deformed when the gas pressure inside the battery rises to a predetermined pressure or more 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).
【0050】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.
【0051】ついで、外装缶40の開口部に上述した電
解液a〜o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、15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〜Oの公称容量は1350mAhとな
る。Then, after the above-mentioned electrolytes a to o were respectively injected into the opening of the outer can 40, the current interruption sealing was 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, thereby producing 15 types of cylindrical lithium ion batteries. The nominal capacity of each of the lithium ion batteries A to O thus produced is 1350 mAh.
【0052】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は実施例10の電解液jを注入したものであ
り、電池Kは実施例11の電解液kを注入したものであ
り、電池Lは実施例12の電解液lを注入したものであ
り、電池Mは比較例1の電解液mを注入したものであ
り、電池Nは比較例2の電解液nを注入したものであ
り、電池Oは比較例3の電解液oを注入したものであ
る。The battery A was prepared by injecting the electrolytic solution a of Example 1, the battery B was obtained by injecting the electrolytic solution b of Example 2, and the battery C was prepared by injecting the electrolytic solution 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 was injected, the battery J was injected with the electrolyte j of Example 10, the battery K was injected with the electrolyte k of Example 11, and the battery L was injected with the electrolyte of Example 12. The liquid M was injected, the battery M was injected with the electrolyte m of Comparative Example 1, and the battery N was injected with the battery of Comparative Example 2. Is obtained by injecting the solution was n, the battery O is obtained by injecting an electrolyte solution o of Comparative Example 3.
【0053】6.試験 a.過充電試験 上述のように作製した15種類の各リチウムイオン電池
A〜O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15種類の各リチウムイオン電池A〜O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〜O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 15 types of lithium ion batteries A to O 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 fifteen fully charged lithium ion batteries A to O in this manner.
Overcharging is performed by flowing a charging current of 2700 mA (2C) between the negative electrode terminals, and 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 O at that time are measured. The results were as shown in Table 1 below.
【0054】b.低温特性 上述のように作製した15種類の各リチウムイオン電池
A〜O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 Each of the 15 types of lithium ion batteries A to O produced as described above was charged at room temperature (25 ° C.) with 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.
【0055】一方、上述のように作製した15種類の各
リチウムイオン電池A〜O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 fifteen kinds of lithium ion batteries A to O produced as described above was used at room temperature (25 ° C.) for 135
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) ).
【0056】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.
【0057】[0057]
【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15種類の各リチウムイオン電池
A〜O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 characteristics = (discharge capacity at low temperature / discharge capacity at room temperature) × 100% (1) c. Storage Characteristics Each of the 15 types of lithium ion batteries A to O prepared as described above is charged at room temperature (25 ° C.) at a charge current of 1350 mA (1 C) until the battery voltage reaches 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.
【0058】[0058]
【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)
【0059】[0059]
【表1】 [Table 1]
【0060】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mを用いた電池M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nを用
いた電池N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oを用いた電池O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 clear from Table 1, the battery M using the electrolyte solution m of Comparative Example 1 in which no additive was added bursted 32 minutes after the start of overcharge, but the low-temperature characteristics And the storage characteristics were both good. In addition, in the battery N using the electrolyte n of Comparative Example 2 to which biphenyl as the conventional additive 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 O using the electrolyte solution o of Comparative Example 3 to which 4-chloroanisole as a conventional additive was added, the charging current was cut off 21 minutes after the start of overcharge, 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.
【0061】一方、本発明の添加剤である上記化5の構
造式で表されるジフェニルカーボネート、上記化6の構
造式で表される2−ビフェニリルメチルカーボネート、
上記化7の構造式で表される4−ビフェニリルメチルカ
ーボネート、上記化8の構造式で表される4−ビフェニ
リルブチルカーボネート、上記化9の構造式で表される
メチル2,4,6−トリメチルフェニルカーボネート、
上記化10の構造式で表される3−ビフェニリルメチル
カーボネート、上記化11の構造式で表される4−ビフ
ェニリルフェニルカーボネート、上記化12の構造式で
表されるベンジル4−ビフェニリルカーボネートを添加
した実施例1〜実施例12の電解液a〜lを用いた電池
A〜Lは、過充電を開始してから15〜20分後に充電
電流が遮断され、そのときの最高温度も75〜84℃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。On the other hand, diphenyl carbonate represented by the above formula (5), 2-biphenylylmethyl carbonate represented by the above formula (6), which is an additive of the present invention,
4-biphenylylmethyl carbonate represented by the structural formula of formula 7, 4-biphenylylbutyl carbonate represented by the structural formula of formula 8, and methyl 2,4,6 represented by the structural formula of formula 9 -Trimethylphenyl carbonate,
3-biphenylylmethyl carbonate represented by the structural formula of the above formula 10, 4-biphenylylphenyl carbonate represented by the structural formula of the above formula 11, benzyl 4-biphenylyl carbonate represented by the structural formula of the above formula 12 In the batteries A to L using the electrolytes a to l of Examples 1 to 12 to which the electrolyte was added, the charging current was interrupted 15 to 20 minutes after the start of overcharging, and the maximum temperature at that time was 75 8484 ° C., and both low-temperature characteristics and storage characteristics were good.
【0062】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、ジフェニルカーボ
ネート、2−ビフェニリルメチルカーボネート、4−ビ
フェニリルメチルカーボネート、4−ビフェニリルブチ
ルカーボネート、メチル2,4,6−トリメチルフェニ
ルカーボネート、3−ビフェニリルメチルカーボネー
ト、4−ビフェニリルフェニルカーボネート、ベンジル
4−ビフェニリルカーボ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15〜20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 the battery is overcharged after the battery voltage reaches 4.1 V and becomes overcharged, diphenyl carbonate, 2-biphenylylmethyl carbonate, 4-biphenylylmethyl carbonate, 4-biphenylylbutyl carbonate , Methyl 2,4,6-trimethyl phenyl carbonate, 3-biphenylylmethyl carbonate, 4-biphenylyl phenyl carbonate, benzyl 4-biphenylyl carbonate, etc., start a decomposition reaction to generate gas. . At the same time, the polymerization reaction is started to generate polymerization heat. If overcharging is further continued in this state, the amount of generated gas increases, and the current cutoff sealing body 50 operates 15 to 20 minutes after the start of overcharging to cut off the overcharge current. As a result, the battery temperature also gradually decreases.
【0063】なお、電池A〜Hと電池I〜L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Hを比
較すると明らかなように、添加剤を代えても格別の差異
が認められないので、本発明の添加剤は上記化5の構造
式で表されるジフェニルカーボネート、上記化6の構造
式で表される2−ビフェニリルメチルカーボネート、上
記化7の構造式で表される4−ビフェニリルメチルカー
ボネート、上記化8の構造式で表される4−ビフェニリ
ルブチルカーボネート、上記化9の構造式で表されるメ
チル2,4,6−トリメチルフェニルカーボネート、上
記化10の構造式で表される3−ビフェニリルメチルカ
ーボネート、上記化11の構造式で表される4−ビフェ
ニリルフェニルカーボネート、上記化12の構造式で表
されるベンジル4−ビフェニリルカーボネートから選択
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 H and the batteries I to L, 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 clear from the comparison of the batteries A to H, no particular difference was observed even when the additives were changed, so that the additive of the present invention was obtained from the diphenyl carbonate represented by the structural formula (5), 2-biphenylylmethyl carbonate represented by the chemical formula of Chemical Formula 6, 4-biphenylylmethyl carbonate represented by the chemical formula of Chemical Formula 7, 4-biphenylylbutyl carbonate represented by the chemical formula of Chemical Formula 8, Methyl 2,4,6-trimethylphenyl carbonate represented by the chemical formula of the above chemical formula 9, 3-biphenylylmethyl carbonate represented by the chemical formula of the above chemical formula 10, and 4- represented by the chemical formula of the above chemical formula 11 It is preferable to use at least one selected from biphenylylphenyl carbonate and benzyl 4-biphenylyl carbonate represented by the above structural formula.
【0064】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13 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ジフェニルカーボネートを1
重量%添加混合して作製した電解液pを実施例13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 13 In 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, and diphenyl carbonate represented by the above-mentioned formula (5) was added to the mixture.
The electrolytic solution p prepared by adding and mixing by weight% is used as the electrolytic solution of Example 13.
【0065】実施例14 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ジフェニルカーボネートを3
重量%添加混合して作製した電解液qを実施例14の電
解液とする。Example 14 A mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC) was
1M LiPF 6 was added and mixed as an electrolyte salt, and diphenyl carbonate represented by the structural formula (5) was added to 3
The electrolyte q prepared by adding and mixing the components by weight was used as the electrolyte of Example 14.
【0066】実施例15 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ジフェニルカーボネートを5
重量%添加混合して作製した電解液rを実施例15の電
解液とする。Example 15 A mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC) was
1M LiPF 6 was added and mixed as an electrolyte salt, and diphenyl carbonate represented by the above formula (5) was added to the mixture.
The electrolytic solution r prepared by adding and mixing by weight% is used as the electrolytic solution of Example 15.
【0067】実施例16 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ジフェニルカーボネートを1
0重量%添加混合して作製した電解液sを実施例16の
電解液とする。Example 16 In 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, and diphenyl carbonate represented by the above-mentioned formula (5) was added to the mixture.
The electrolytic solution s produced by adding and mixing 0% by weight is used as the electrolytic solution of Example 16.
【0068】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p〜s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
P(電解液pを注入したもの)、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。Thereafter, in the same manner as described above, the above-mentioned electrolytes p to s 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 P (injected electrolyte p), lithium-ion battery Q
(Injected electrolyte q), lithium ion battery R
(Injected electrolyte r), lithium ion battery S
(The one into which the electrolytic solution s is injected) is prepared.
【0069】ついで、上述と同様にして、これらの各電
池P〜S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P〜S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 P to S are overcharged, the time from the start of overcharging to the activation of the current cutoff sealing member 50, and the respective batteries at that time. When the maximum temperatures of PS were measured, the results shown in Table 2 below were obtained. 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.
【0070】[0070]
【表2】 [Table 2]
【0071】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ジフェニルカ
ーボネート以外の添加剤、即ち、上記化6の構造式で表
される2−ビフェニリルメチルカーボネート、上記化7
の構造式で表される4−ビフェニリルメチルカーボネー
ト、上記化8の構造式で表される4−ビフェニリルブチ
ルカーボネート、上記化9の構造式で表されるメチル
2,4,6−トリメチルフェニルカーボネート、上記化
10の構造式で表される3−ビフェニリルメチルカーボ
ネート、上記化11の構造式で表される4−ビフェニリ
ルフェニルカーボネート、上記化12の構造式で表され
るベンジル4−ビフェニリルカーボ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, an additive other than diphenyl carbonate represented by the structural formula of the above formula 5, namely 2-biphenylylmethyl carbonate represented by the structural formula of the above formula 6,
4-biphenylylmethyl carbonate represented by the following structural formula: 4-biphenylyl butyl carbonate represented by the above-mentioned chemical formula, and methyl 2,4,6-trimethylphenyl represented by the above-mentioned structural formula: Carbonate, 3-biphenylylmethyl carbonate represented by the above formula, 4-biphenylylphenyl carbonate represented by the above formula, benzyl 4-biphenyl represented by the above formula Approximately similar results were obtained with other additives such as rilcarbonate.
【0072】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.
【0073】実施例17 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ジフェニルカーボネート
を2重量%添加混合して作製した電解液tを実施例17
の電解液とする。Example 17 1M LiPF 6 as an electrolyte salt was added to and mixed with a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of methyl ethyl carbonate (MEC). Example 17 was prepared using an electrolyte t prepared by adding and mixing 2% by weight of diphenyl carbonate.
Electrolyte solution.
【0074】実施例18 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2−ビフェニリルメチル
カーボネートを2重量%添加混合して作製した電解液u
を実施例18の電解液とする。Example 18 1M 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. Electrolytic solution u prepared by adding and mixing 2% by weight of 2-biphenylylmethyl carbonate
Is the electrolyte solution of Example 18.
【0075】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vを比較例4の電解液とする。Comparative Example 4 An electrolytic solution v 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.
【0076】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t〜vをそれぞれ注
入し、リチウムイオン電池T(電解液tを注入したも
の)、リチウムイオン電池U(電解液uを注入したも
の)、リチウムイオン電池V(電解液v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T〜Vの公称容量は600mA
hとなる。Thereafter, in the same manner as described above, the above-mentioned electrolytes t to v are respectively injected into the openings of the rectangular outer can (not shown), and the lithium ion battery T (injection of the electrolyte t) and the lithium ion battery U (the one into which the electrolyte u was injected) and the lithium ion battery V (the one into which the electrolyte v was injected) are prepared. The nominal capacity of each of the rectangular lithium ion batteries T to V thus manufactured is 600 mA.
h.
【0077】上述のように作製した3種類の各リチウム
イオン電池T〜V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T〜V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T〜V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 T to V produced as described above are charged at a charging current of 600 mA (1 C) until the battery voltage reaches 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 T to V that are fully charged as described above, and the maximum temperature of each of the batteries T to V is measured. Overcharge test was performed. The result was as shown in Table 3 below.
【0078】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T〜V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, the three types of lithium ion batteries TV prepared as described above were placed at room temperature (25 ° C.) at 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.
【0079】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T〜V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 TV prepared 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) ).
【0080】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 of the capacities measured 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 above-described equation (1). The results are as shown in Table 3 below.
【0081】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T〜V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 TV prepared 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.
【0082】[0082]
【表3】 [Table 3]
【0083】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vを用いた電池V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
構造式で表されるジフェニルカーボネートを添加した実
施例17の電解液tを用いた電池Tおよび上記化6の構
造式で表される2−ビフェニリルメチルカーボネートを
添加した実施例18の電解液uを用いた電池U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 V using the electrolyte solution v of Comparative Example 4 to which no additive was added was ruptured due to overcharging, but both low-temperature characteristics and storage characteristics were good. there were. On the other hand, a battery T using the electrolytic solution t of Example 17 to which diphenyl carbonate represented by the above formula (5) as an additive of the present invention was added, and 2-biphenyl represented by the above formula (6) In the battery U using the electrolyte solution u of Example 18 to which rilmethyl carbonate was added, the temperature rise was high but the battery did not burst when overcharged. 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.
【0084】上述したように、本発明の上記化5の構造
式で表されるジフェニルカーボネート、上記化6の構造
式で表される2−ビフェニリルメチルカーボネート、上
記化7の構造式で表される4−ビフェニリルメチルカー
ボネート、上記化8の構造式で表される4−ビフェニリ
ルブチルカーボネート、上記化9の構造式で表されるメ
チル2,4,6−トリメチルフェニルカーボネート、上
記化10の構造式で表される3−ビフェニリルメチルカ
ーボネート、上記化11の構造式で表される4−ビフェ
ニリルフェニルカーボネート、上記化12の構造式で表
されるベンジル4−ビフェニリルカーボネートなどのカ
ーボネート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。As described above, diphenyl carbonate of the present invention represented by the structural formula of the above formula (5), 2-biphenylylmethyl carbonate represented by the structural formula of the above formula (6), and the structural formula of the above formula (7) 4-biphenylylmethyl carbonate, 4-biphenylyl butyl carbonate represented by the structural formula of the above formula 8, methyl 2,4,6-trimethylphenyl carbonate represented by the structural formula of the above formula 9, Carbonate derivatives such as 3-biphenylylmethyl carbonate represented by the structural formula, 4-biphenylylphenyl carbonate represented by the structural formula 11 and benzyl 4-biphenylyl carbonate represented by the structural formula 12 When an additive consisting of is added to the electrolyte solution, it can be used without adversely affecting battery characteristics such as low-temperature characteristics and storage characteristics. Act effectively against electrostatic, it becomes possible to ensure the safety of the battery without deteriorating the battery performance.
【0085】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.
【0086】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 that can accept 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.
【0087】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9−22722(JP,A) 特開 平8−298137(JP,A) 特開 平8−293323(JP,A) 特開 平8−306387(JP,A) 特開 平8−106909(JP,A) 特開 平11−329497(JP,A) (58)調査した分野(Int.Cl.7,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, Inventor: Tsutomu Takai 1978 Kogushi, Ogushi, Ube City, Yamaguchi Prefecture Ube Industries, Ltd .: Ube Research Laboratory (56) References JP 9-22722 (JP, A) JP JP-A-8-298137 (JP, A) JP-A-8-293323 (JP, A) JP-A-8-306387 (JP, A) JP-A-8-106909 (JP, A) JP-A-11-329497 (JP) , A) (58) Field surveyed (Int.Cl. 7 , 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カーボネ
ート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 a carbonate derivative represented by the following general formula (1). Electrolyte for non-aqueous batteries. Embedded image However, R 1 shown in the chemical formula 1 is a biphenylyl group shows <br/>, R 2 represents an alkyl group, a phenyl group having 1 to 6 carbon atoms.
ニリルメチルカーボネート、4−ビフェニリルメチルカ
ーボネート、4−ビフェニリルブチルカーボネート、3
−ビフェニリルメチルカーボネート、4−ビフェニリル
フェニルカーボ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。2. The carbonate derivative may be 2 -biphenylylmethyl carbonate, 4-biphenylylmethyl carbonate, 4-biphenylylbutyl carbonate , or 3 -biphenylylmethyl carbonate .
- biphenylylmethyl carbonate, a non-aqueous battery electrolyte according to claim 1, characterized in that it comprises at least one selected et al or 4-biphenylyl phenyl carbonate Natick bets.
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カーボネー
ト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 comprising an electrolyte solution in which a lithium salt is dissolved as a solute, wherein the electrolyte solution contains a carbonate derivative represented by the following general formula (2). Water-based secondary battery. Embedded image Here, R 1 shown in Chemical Formula 2 represents a biphenylyl group , and R 2 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.
ニリルメチルカーボネート、4−ビフェニリルメチルカ
ーボネート、4−ビフェニリルブチルカーボネート、3
−ビフェニリルメチルカーボネート、4−ビフェニリル
フェニルカーボ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。4. The carbonate derivative may be 2 -biphenylyl methyl carbonate, 4-biphenylyl methyl carbonate, 4-biphenylyl butyl carbonate ,
- biphenylylmethyl carbonate, a non-aqueous secondary battery according to claim 3, characterized in that it comprises at least one selected et 4- biphenylene or alkylphenyl carbonate Natick bets.
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JP10217992A JP3080609B2 (en) | 1998-07-31 | 1998-07-31 | Electrolyte for non-aqueous battery and secondary battery using this electrolyte |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002280068A (en) * | 2001-03-21 | 2002-09-27 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
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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 |
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1998
- 1998-07-31 JP JP10217992A patent/JP3080609B2/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002280068A (en) * | 2001-03-21 | 2002-09-27 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
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