JP2000058113A - Nonaqueous battery electrolyte and secondary battery using the same - Google Patents
Nonaqueous battery electrolyte and secondary battery using the sameInfo
- Publication number
- JP2000058113A JP2000058113A JP10217970A JP21797098A JP2000058113A JP 2000058113 A JP2000058113 A JP 2000058113A JP 10217970 A JP10217970 A JP 10217970A JP 21797098 A JP21797098 A JP 21797098A JP 2000058113 A JP2000058113 A JP 2000058113A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- electrolyte
- weight
- diphenoxybenzene
- lithium
- 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.)
- Granted
Links
Classifications
-
- Y02E60/122—
Abstract
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、特開平９−５０８２２号公報族化合物は、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 fragrance, a compound of JP-A-9-50822, 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２価フェノール誘
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，Ｒ2はフェニル基を示す。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 dihydric phenol derivative represented by the following general formula (3). It is characterized by having. However, Chemical 3
R 1 and R 2 shown in the above are phenyl groups.
【００１１】[0011]
【化３】 Embedded image
【００１２】上記化３の一般式で表される２価フェノー
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
２価フェノー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、２価フェノール誘導体が
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２価
フェノー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 dihydric phenol 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 dihydric phenol derivative represented by the general formula (3) does not deteriorate the battery performance. Further, the polymer produced by the polymerization reaction of the dihydric phenol derivative is a substance that is unlikely to be redissolved in the electrolytic solution, and thus effectively acts on overcharging. Therefore, the use of the electrolytic solution containing the dihydric phenol derivative represented by the above general formula 3 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、
１，４−ジフェノキシベンゼンあるいは１，３−ジフェ
ノキシベンゼン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:
It is preferable to provide at least one selected from 1,4-diphenoxybenzene and 1,3-diphenoxybenzene.
【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２価フェノ
ー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，Ｒ2はフェニル基を示す。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 including an electrolyte in which a lithium salt is dissolved as a solute in an organic solvent, wherein the electrolyte contains a dihydric phenol derivative represented by the following general formula (4). Features. However, R 1 and R 2 shown in Chemical formula 4 represent phenyl groups.
【００１５】[0015]
【化４】 Embedded image
【００１６】上記化４の一般式で表される２価フェノー
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２価フェノー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 dihydric phenol derivative represented by the general formula (4) has a good affinity for an organic solvent in an electrolytic solution,
The use of an electrolytic solution in which such a dihydric phenol derivative is added together with a lithium salt in an organic solvent 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２価フェノー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 electrolytic solution in which such a dihydric phenol 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, without deteriorating battery performance. Security can be ensured.
【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１，４−ジフェノキシベン
ゼンを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 1M LiPF 6 as an electrolyte salt and further adding and mixing 2% by weight of 1,4-diphenoxybenzene represented by the following structural formula is mixed with the electrolyte of Example 1. I do.
【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１，３−ジフェノキシベン
ゼンを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 solution b prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 2% by weight of 1,3-diphenoxybenzene represented by the following structural formula is combined with the electrolyte solution of Example 2. I do.
【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１，４−ジフェノキシベンゼ
ンを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 dimethyl carbonate (DMC),
Example 3 was prepared by adding and mixing 1M LiPF 6 as an electrolyte salt, and further adding and mixing 2% by weight of 1,4-diphenoxybenzene represented by the structural formula of the above formula (3).
Electrolyte solution.
【００２９】実施例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、さら
に上記化５の構造式で表される１，４−ジフェノキシベ
ンゼンを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 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. The electrolyte d prepared by adding and mixing 2 wt% of 1,4-diphenoxybenzene was used as the electrolyte of Example 4.
【００３０】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）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１，４−ジフェノキシベンゼンを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 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 electrolyte e prepared by adding and mixing 2% by weight of 1,4-diphenoxybenzene represented by the structural formula of Chemical Formula 5 is used as an electrolyte of Example 5.
【００３１】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１，
４−ジフェノキシベンゼンを２重量％添加混合して作製
した電解液ｆ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),
0.5 M LiPF 6 and 0.5 M LiBF 4 as electrolyte salts
Are added and mixed, and 1,1 represented by the structural formula
An electrolytic solution prepared by adding and mixing 2% by weight of 4-diphenoxybenzene f The electrolytic solution of Example 6 was used.
【００３２】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ｇ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 g prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt is used as an electrolyte of Comparative Example 1.
【００３３】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ｈ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 h prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 2 wt% of biphenyl is used as an electrolyte of Comparative Example 2.
【００３４】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ｉ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.
-Electrolyte solution i prepared by adding and mixing 2% by weight of chloroanisole is used as an electrolyte solution of Comparative Example 3.
【００３５】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.
【００３６】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 cutoff 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.
【００３７】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 that 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).
【００３８】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。A part of the upper portion 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 an overcurrent or a short-circuit current is cut off.
【００３９】ついで、外装缶４０の開口部に上述した電
解液ａ〜ｉ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、９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〜Ｉの公称容量は１３５０ｍＡｈとなる。Then, after the above-mentioned electrolytes a to i are respectively injected into the opening of the outer can 40, the current blocking sealing is performed 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 toward the current blocking sealing body 50 and sealed in a liquid-tight manner to produce nine types of cylindrical lithium ion batteries. The nominal capacity of each of the lithium ion batteries A to I thus produced is 1350 mAh.
【００４０】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は比較例１の電解液ｇを注入したものであ
り、電池Ｈは比較例２の電解液ｈを注入したものであ
り、電池Ｉは比較例３の電解液ｉ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 h of Comparative Example 1, the battery H was injected with the electrolyte h of Comparative Example 2, and the battery I was the electrolyte of Comparative Example 3. i.
【００４１】６．試験 ａ．過充電試験 上述のように作製した９種類の各リチウムイオン電池Ａ
〜Ｉ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９種類の各リチウムイオン電池Ａ〜Ｉ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〜Ｉ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 Nine kinds of lithium ion batteries A produced as described above
ＩI is charged at a charge current of 1350 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 obtain a fully charged state. Overcharging is performed by passing a charging current of 2700 mA (2C) between the positive and negative terminals of each of the nine types of lithium-ion batteries A to I which are fully charged in this manner. When the time until the operation and the maximum temperatures of the batteries A to I at that time were measured, the results shown in Table 1 below were obtained.
【００４２】ｂ．低温特性 上述のように作製した９種類の各リチウムイオン電池Ａ
〜Ｉ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１３５０ｍ
Ａ（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。B. Low-temperature characteristics Nine types of lithium-ion batteries A produced as described above
ＩI at room temperature (25 ° C.) with a charge current of 1350 mA (1 C) until the battery voltage reaches 4.1 V, and then
The battery is charged at a constant voltage of 4.1 V for 3 hours to be fully charged.
Then, after stopping at room temperature for 3 hours, 1350 m at room temperature
A (1C) discharge was performed until the final voltage reached 2.75 V, and the discharge capacity at room temperature (mAh) was calculated from the discharge time.
I asked.
【００４３】一方、上述のように作製した９種類の各リ
チウムイオン電池Ａ〜Ｉを、室温（２５℃）で１３５０
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、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, the nine types of lithium ion batteries A to I manufactured as described above were subjected to 1350 at room temperature (25 ° C.).
The battery is charged at a charging 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. 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) ).
【００４４】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.
【００４５】[0045]
【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９種類の各リチウムイオン電池Ａ
〜Ｉ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 Nine kinds of lithium ion batteries A produced as described above
To I at room temperature (25 ° C.) with a charge current of 1350 mA (1 C) until the battery voltage reaches 4.1 V, and then
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.
【００４６】[0046]
【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)
【００４７】[0047]
【表１】 [Table 1]
【００４８】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ｇを用いた電池Ｇ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ｈを用
いた電池Ｈ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ｉを用いた電池Ｉ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 G using the electrolyte solution g of Comparative Example 1 containing no additive was ruptured 32 minutes after the start of overcharge. And the storage characteristics were both good. In the battery H using the electrolyte h of Comparative Example 2 to which biphenyl as 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 I using the electrolyte solution i 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 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.
【００４９】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１，４−ジフェノキシベンゼンおよび上
記化６の構造式で表される１，３−ジフェノキシベンゼ
ンを添加した実施例１〜実施例６電解液ａ〜ｆを用いた
電池Ａ〜Ｆは、過充電を開始してから１９〜２０分後に
充電電流が遮断され、そのときの最高温度も８４〜８５
℃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, 1,4-diphenoxybenzene represented by the structural formula of the above formula and 1,3-diphenoxybenzene represented by the structural formula of the above formula, which are additives of the present invention, were added. In the batteries A to F using the electrolytes a to f, the charging current was interrupted 19 to 20 minutes after the overcharge was started, and the maximum temperature at that time was also 84 to 85.
° C, and both low-temperature characteristics and storage characteristics were good.
【００５０】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、上記化５の構造式
で表される１，４−ジフェノキシベンゼンおよび上記化
６の構造式で表される１，３−ジフェノキシベンゼンな
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１９〜２０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, the 1,4-diphenoxybenzene represented by the structural formula and the structure of the chemical formula An additive such as 1,3-diphenoxybenzene represented by the formula starts 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 19 to 20 minutes after the start of overcharging to cut off the overcharge current. As a result, the battery temperature also gradually decreases.
【００５１】なお、電池Ａ〜Ｂと電池Ｃ〜Ｆ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と電池Ｂ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１，４−ジフェノキシベンゼンおよび上記
化６の構造式で表される１，３−ジフェノキシベンゼン
から選択した少なくとも１種を用いるのが好ましい。As is apparent from comparison between the batteries A and B and the batteries C and F, 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 between the battery A and the battery B, no particular difference was observed even when the additive was changed, so that the additive of the present invention was 1,4-formula represented by the above structural formula (5). It is preferable to use at least one selected from diphenoxybenzene and 1,3-diphenoxybenzene represented by the structural formula (6).
【００５２】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、さらに上
記化５の構造式で表される１，４−ジフェノキシベンゼ
ンを１重量％添加混合して作製した電解液ｊを実施例７
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 7 In a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC),
Example 7 was prepared by adding and mixing 1M LiPF 6 as an electrolyte salt, and further adding and mixing 1% by weight of 1,4-diphenoxybenzene represented by the structural formula (1).
Electrolyte solution.
【００５３】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、さらに上
記化５の構造式で表される１，４−ジフェノキシベンゼ
ンを３重量％添加混合して作製した電解液ｋを実施例８
の電解液とする。Example 8 In a mixed solvent consisting of 40 parts by weight of ethylene carbonate (EC) and 60 parts by weight of diethyl carbonate (DEC),
Example 8 was prepared by adding and mixing 1M LiPF 6 as an electrolyte salt, and further adding and mixing 3% by weight of 1,4-diphenoxybenzene represented by the structural formula (5).
Electrolyte solution.
【００５４】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１，４−ジフェノキシベンゼ
ンを５重量％添加混合して作製した電解液ｌ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 diethyl carbonate (DEC),
Example 9 was prepared by adding and mixing 1M LiPF 6 as an electrolyte salt, and further adding and mixing 5% by weight of 1,4-diphenoxybenzene represented by the structural formula (5).
Electrolyte solution.
【００５５】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１，４−ジフェノキシベンゼ
ンを１０重量％添加混合して作製した電解液ｍ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 solution m prepared by adding and mixing 1 M LiPF 6 as an electrolyte salt and further adding and mixing 10 wt% of 1,4-diphenoxybenzene represented by the structural formula of the above formula 5 is used as an electrolyte solution of Example 10. .
【００５６】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ｊ〜ｍ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
Ｊ（電解液ｊを注入したもの）、リチウムイオン電池Ｋ
（電解液ｋを注入したもの）、リチウムイオン電池Ｌ
（電解液ｌを注入したもの）、リチウムイオン電池Ｍ
（電解液ｍ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 j to m are respectively injected into the openings of the outer can 40, and then,
A current blocking sealing body 50 is placed on the opening of the outer can 40 via an insulating gasket 42 for the outer can 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 J (injection of electrolyte j) and lithium-ion battery K
(Injection of electrolyte k), lithium ion battery L
(Injected electrolyte 1), lithium ion battery M
(To which the electrolytic solution m is injected) are prepared.
【００５７】ついで、上述と同様にして、これらの各電
池Ｊ〜Ｍ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, each of the batteries J to M is overcharged, the time from the start of overcharge to the activation of the current cutoff sealing member 50, and the time of each battery 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.
【００５８】[0058]
【表２】 [Table 2]
【００５９】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１，４−ジフ
ェノキシベンゼンに代えて、上記化６の構造式で表され
る１，３−ジフェノキシベンゼン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, 1,3-diphenoxybenzene represented by the structural formula of the above formula is replaced with 1,3-diphenoxybenzene represented by the chemical formula of the above formula (5). Approximately the same results were obtained when used.
【００６０】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.
【００６１】実施例１１ 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１，４−ジフェノキシベ
ンゼンを２重量％添加混合して作製した電解液ｎ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) and 60 parts by weight of methyl ethyl carbonate (MEC), and further mixed. The electrolyte n prepared by adding and mixing 2% by weight of 1,4-diphenoxybenzene was used as the electrolyte of Example 11.
【００６２】実施例１２ 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１，３−ジフェノキシベ
ンゼンを２重量％添加混合して作製した電解液ｏを実施
例１２の電解液とする。Example 12 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 o prepared by adding and mixing 2% by weight of 1,3-diphenoxybenzene was used as the electrolyte of Example 12.
【００６３】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ｐを比較例４の電解液とする。Comparative Example 4 An electrolytic solution p 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.
【００６４】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ｎ〜ｐをそれぞれ注
入し、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。このようにして作製した角形
の各リチウムイオン電池Ｎ〜Ｐの公称容量は６００ｍＡ
ｈとなる。Thereafter, in the same manner as described above, the above-mentioned electrolytes n to p were respectively injected into the openings of the rectangular outer can (not shown), and the lithium ion battery N (the one into which the electrolyte n was injected), the lithium ion battery O (the one into which the electrolyte o was injected) and the lithium ion battery P (the one into which the electrolyte p was injected) are produced. The nominal capacity of each of the rectangular lithium-ion batteries N to P thus manufactured is 600 mA.
h.
【００６５】上述のように作製した３種類の各リチウム
イオン電池Ｎ〜Ｐ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Ｎ〜Ｐ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Ｎ〜Ｐ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 N to P produced 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 N to P that are fully charged in this way, and the maximum temperature of each of the batteries N to P is measured. Overcharge test was performed. The result was as shown in Table 3 below.
【００６６】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Ｎ〜Ｐ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 N to P produced as described above were placed at room temperature (25 ° C.) for 600 hours.
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.
【００６７】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Ｎ〜Ｐ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 N to P produced 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) ).
【００６８】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 the respective 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 the low-temperature characteristic by the above-described equation (1). The results are as shown in Table 3 below.
【００６９】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Ｎ〜Ｐ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 N to P 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.
【００７０】[0070]
【表３】 [Table 3]
【００７１】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ｐを用いた電池Ｐ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１，４−ジフェノキシベンゼンを添加
した実施例１１の電解液ｎを用いた電池Ｎおよび上記化
６の構造式で表される１，３−ジフェノキシベンゼンを
添加した実施例１２の電解液ｏを用いた電池Ｏ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
ものほぼ同等の値を示し、共に良好であった。As is clear from Table 3, the battery P using the electrolyte p 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 N using the electrolyte solution n of Example 11 to which 1,4-diphenoxybenzene represented by the structural formula of the above formula (5), which is an additive of the present invention, was added, and In the battery O using the electrolyte solution o of Example 12 to which 1,3-diphenoxybenzene was added, the temperature rise was high when overcharging was performed, but the battery did not burst. In addition, the low-temperature characteristics and the preservation characteristics exhibited almost the same values when no additive was added, and both were good.
【００７２】上述したように、本発明の上記化５の構造
式で表される１，４−ジフェノキシベンゼンあるいは上
記化６の構造式で表される１，３−ジフェノキシベンゼ
ンなどの２価フェノー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。As described above, divalent compounds such as 1,4-diphenoxybenzene represented by the structural formula of the above formula (1) or 1,3-diphenoxybenzene represented by the structural formula of the present invention of the present invention are used. When an additive composed of a phenol derivative is used by adding it to the electrolyte, it works effectively against overcharging without adversely affecting battery characteristics such as low-temperature characteristics and storage characteristics, and does not deteriorate battery performance. Battery safety can be ensured.
【００７３】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-described 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, a carbon-based material capable of inserting and extracting lithium ions, For example, graphite,
Carbon black, coke, vitreous carbon, carbon fiber, or a fired body thereof are suitable.
【００７４】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.
【００７５】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。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 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 山口 尚範 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (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 Ｆターム(参考） 5H029 AJ07 AK03 AL07 AM04 AM07 BJ02 BJ14 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naoyama Yamaguchi 2-5-5 Keihanhondori, Moriguchi City, Osaka Prefecture Inside Sanyo Electric Co., Ltd. (72) Inventor Koji Abe 1978 Kogushi, 1978, Oji, Ube City, Yamaguchi Prefecture Ube Industries, Ltd.Ube Research Laboratory (72) Inventor Akira Ueki, 1919 Kobe, Ogushi, Ube City, Yamaguchi Prefecture 5 F-term in Ube Laboratory Co., Ltd. (reference) 5H029 AJ07 AK03 AL07 AM04 AM07 BJ02 BJ14
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２価フェ
ノー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，Ｒ2はフェニル基を示
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 dihydric phenol derivative represented by the following general formula: An electrolytic solution for a non-aqueous battery. Embedded image However, R 1 and R 2 shown in the above formula 1 represent a phenyl group.
ジフェノキシベンゼンあるいは１，３−ジフェノキシベ
ンゼン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 method according to claim 1, wherein the dihydric phenol derivative is 1,4-
The electrolyte for a non-aqueous battery according to claim 1, comprising at least one selected from diphenoxybenzene and 1,3-diphenoxybenzene.
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２価フェノ
ー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，Ｒ2はフェニル基を示
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 dihydric phenol derivative represented by the following general formula (2). Non-aqueous secondary battery. Embedded image However, R 1 and R 2 shown in Chemical formula 2 above represent a phenyl group.
ジフェノキシベンゼンあるいは１，３−ジフェノキシベ
ンゼン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 dihydric phenol derivative is 1,4-
The non-aqueous secondary battery according to claim 3, comprising at least one selected from diphenoxybenzene and 1,3-diphenoxybenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10217970A JP2928779B1 (en) | 1998-07-31 | 1998-07-31 | Electrolyte for non-aqueous battery and secondary battery using this electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10217970A JP2928779B1 (en) | 1998-07-31 | 1998-07-31 | Electrolyte for non-aqueous battery and secondary battery using this electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2928779B1 JP2928779B1 (en) | 1999-08-03 |
| JP2000058113A true JP2000058113A (en) | 2000-02-25 |
Family
ID=16712597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10217970A Expired - Fee Related JP2928779B1 (en) | 1998-07-31 | 1998-07-31 | Electrolyte for non-aqueous battery and secondary battery using this electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2928779B1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001006731A (en) * | 1999-06-24 | 2001-01-12 | Sony Corp | Nonaqueous electrolyte secondary battery |
| JP2002279960A (en) * | 2001-03-21 | 2002-09-27 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte 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 |
| KR100424259B1 (en) * | 2001-10-20 | 2004-03-22 | 삼성에스디아이 주식회사 | Non aqueous electrolyte for improving overcharge safety and lithium battery using the same |
| US7074523B2 (en) | 2001-05-15 | 2006-07-11 | Hitachi, Ltd. | Lithium secondary battery |
| US7560195B2 (en) | 2004-03-30 | 2009-07-14 | Samsung Sdi Co., Ltd. | Electrolyte for lithium battery and lithium battery comprising the same |
| US7615311B2 (en) | 2005-02-23 | 2009-11-10 | Panasonic Corporation | Non-aqueous electrolyte and electrochemical device using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161757B (en) * | 2015-07-24 | 2017-08-22 | 张家港市国泰华荣化工新材料有限公司 | A kind of lithium-ion battery electrolytes containing the anti-overcharge additive of oxidation-reduction type |
-
1998
- 1998-07-31 JP JP10217970A patent/JP2928779B1/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001006731A (en) * | 1999-06-24 | 2001-01-12 | Sony Corp | Nonaqueous electrolyte secondary battery |
| JP4501177B2 (en) * | 1999-06-24 | 2010-07-14 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| JP2002279960A (en) * | 2001-03-21 | 2002-09-27 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| US7074523B2 (en) | 2001-05-15 | 2006-07-11 | Hitachi, Ltd. | 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 |
| US7217477B2 (en) | 2001-05-22 | 2007-05-15 | Lg Chem, Ltd. | Non-aqueous electrolyte additive for improving safety and lithium ion secondary battery comprising the same |
| CN1316671C (en) * | 2001-05-22 | 2007-05-16 | Lg化学株式会社 | Non-aqueous electrolyte additive for improving safety and lightium ion secondary battery comprising same |
| KR100424259B1 (en) * | 2001-10-20 | 2004-03-22 | 삼성에스디아이 주식회사 | Non aqueous electrolyte for improving overcharge safety and lithium battery using the same |
| US7560195B2 (en) | 2004-03-30 | 2009-07-14 | Samsung Sdi Co., Ltd. | Electrolyte for lithium battery and lithium battery comprising the same |
| US7615311B2 (en) | 2005-02-23 | 2009-11-10 | Panasonic Corporation | Non-aqueous electrolyte and electrochemical device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2928779B1 (en) | 1999-08-03 |
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