JPH11176470A - Organic electrolyte secondary battery - Google Patents
Organic electrolyte secondary batteryInfo
- Publication number
- JPH11176470A JPH11176470A JP10248895A JP24889598A JPH11176470A JP H11176470 A JPH11176470 A JP H11176470A JP 10248895 A JP10248895 A JP 10248895A JP 24889598 A JP24889598 A JP 24889598A JP H11176470 A JPH11176470 A JP H11176470A
- Authority
- JP
- Japan
- Prior art keywords
- organic electrolyte
- negative electrode
- battery
- carbonate
- secondary battery
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機電解液二次電
池に関し、さらに詳しくは、高容量で、かつ安全性の高
い有機電解液二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electrolyte secondary battery, and more particularly, to a high-capacity and highly safe organic electrolyte secondary battery.
【０００２】[0002]
【従来の技術】リチウムイオン二次電池に代表される有
機電解液二次電池は、高容量で、かつ高電圧、高エネル
ギーであることから、その発展に対して大きな期待が寄
せられている。2. Description of the Related Art An organic electrolyte secondary battery represented by a lithium ion secondary battery has a high capacity, a high voltage and a high energy.
【０００３】この有機電解液二次電池では、負極活物質
としてリチウムまたはリチウム合金が用いられてきた
が、これらの負極活物質による場合、高容量化を期待で
きるものの、充電時のリチウムのデンドライト成長によ
り内部短絡を起こしやすく、そのため、電池性能が低下
したり、安全性に欠けるという問題があった。In this organic electrolyte secondary battery, lithium or a lithium alloy has been used as a negative electrode active material. In the case of using such a negative electrode active material, a high capacity can be expected, but lithium dendrite growth during charging is required. As a result, an internal short circuit is likely to occur, and therefore, there has been a problem that the battery performance is reduced or the safety is lacking.
【０００４】そこで、リチウムやリチウム合金に代え
て、リチウムイオンをドープ・脱ドープすることが可能
な活性炭や黒鉛などの炭素材料を負極活物質として用い
ることが提案されている（特公平４−２４８３１号公
報、特公平５−１７６６９号公報など）。Therefore, it has been proposed to use a carbon material such as activated carbon or graphite capable of doping and undoping lithium ions as a negative electrode active material instead of lithium or a lithium alloy (Japanese Patent Publication No. 4-24831). And Japanese Patent Publication No. 5-17669).
【０００５】上記黒鉛は、炭素原子６個に対して１個の
リチウムイオンを捕らえることができ、これを単位体積
当たりの容量で示すと８３０ｍＡｈ／ｍｌに相当する。
しかし、この黒鉛は、充放電によるリチウムイオンの出
入りにより、完全充電（３７２ｍＡｈ／ｇ相当のリチウ
ムを含む状態）時には、完全放電（リチウムを含まない
状態）に対して層間距離が約１０％拡大し、充電、放電
を繰り返すと、この伸び縮みにより負極活物質の黒鉛が
集電体から剥離したり、微粉化が生じて電池性能が低下
する。そのため、黒鉛で５００サイクル以上の寿命を得
るためには、通常２５０ｍＡｈ／ｇ（６００ｍＡｈ／ｍ
ｌ）以下の範囲で使用しなければならないという制約が
あった。[0005] The above graphite can capture one lithium ion per six carbon atoms, which corresponds to 830 mAh / ml in terms of capacity per unit volume.
However, when fully charged (a state containing lithium equivalent to 372 mAh / g), the interlayer distance of this graphite is increased by about 10% with respect to a complete discharge (a state containing no lithium) due to the inflow and out of lithium ions due to charge and discharge. When charge and discharge are repeated, the expansion / contraction causes graphite as the negative electrode active material to peel off from the current collector or to be pulverized, thereby lowering battery performance. Therefore, to obtain a life of 500 cycles or more with graphite, usually 250 mAh / g (600 mAh / m
l) There is a restriction that the device must be used in the following range.
【０００６】この黒鉛よりも高容量のものとしては低結
晶炭素がある。この低結晶炭素は層間以外にも非晶質部
分の空隙にリチウムイオンを挿入することができ、しか
も充放電中に格子間隔の伸び縮みがほとんどないので、
サイクル寿命が長くなるものと期待されている。ところ
が、この低結晶炭素は理論上最大１２００ｍＡｈ／ｇ
（すなわち、Ｃ2 Ｌｉの状態）まで高容量化が期待でき
るものの、真密度が低いため、体積当たりの容量では黒
鉛と大差がない。As a material having a higher capacity than graphite, there is low-crystalline carbon. Since this low-crystalline carbon can insert lithium ions into the voids of the amorphous portion in addition to between the layers, and since there is almost no expansion and contraction of the lattice spacing during charge and discharge,
It is expected that the cycle life will be longer. However, this low-crystalline carbon theoretically has a maximum of 1200 mAh / g.
Although a high capacity can be expected up to (that is, a state of C 2 Li), since the true density is low, the capacity per volume is not much different from graphite.
【０００７】そのため、ニッケルケイ化物やマンガンケ
イ化物などの半金属と遷移金属との合金を負極活物質と
して用いることによって高容量化を図ることが提案され
ている（特開平８−１５３５１７号公報、特開平８−１
５３５３８号公報など）。Therefore, it has been proposed to increase the capacity by using an alloy of a transition metal and a semimetal such as nickel silicide or manganese silicide as a negative electrode active material (Japanese Patent Laid-Open No. 8-153517, JP-A-8-1
53538 and the like).
【０００８】[0008]
【発明が解決しようとする課題】ところで、上記のよう
な有機電解液二次電池では、電解液の構成溶媒として有
機溶媒を使用するため、引火・発火の危険性がないこと
が要求され、そのような要求に応えるべく、保護回路な
どを設け、それによって過充電を防止して内部短絡が生
じないようにするなどの対策が行われており、また、一
般の内部短絡では電池が発熱するだけで安全性にまでは
問題が生じないようにされている。In the above-described organic electrolyte secondary battery, since an organic solvent is used as a constituent solvent of the electrolyte, it is required that there is no danger of ignition or ignition. In order to respond to such demands, protection circuits are provided to prevent overcharge and prevent internal short-circuits.In general, internal short-circuits only generate heat. In order to prevent problems even in safety.
【０００９】しかしながら、上記のような高容量化が期
待できる負極活物質を用いて高容量化を図った場合やユ
ーザーから要求される仕様によっては、電池の構成を充
分に工夫しておかないと、故意の異常使用を想定した苛
酷な条件下での安全性確認試験である圧壊試験や釘刺し
試験をした場合に、安全性が低下する傾向にあることが
判明した。However, depending on the case where the capacity is increased by using the above-mentioned negative electrode active material which can be expected to have a high capacity or depending on the specifications required by the user, it is necessary to devise the structure of the battery sufficiently. It has been found that when a crush test or a nail penetration test, which is a safety confirmation test under severe conditions supposing intentional abnormal use, is performed, the safety tends to decrease.
【００１０】このような圧壊試験や釘刺し試験は、電池
が故意あるいは何らかの事故などにより破壊された場合
を想定したものであって、通常の使用条件下では起こり
得ないものであるか、電池をこのような圧壊試験や釘刺
し試験においても引火・発火の危険性のない安全性の高
いものにしておくことが望ましい。特に前記のようなニ
ッケルケイ化物やマンガンケイ化物などの半金属と遷移
金属との合金からなる負極活物質は、リチウムを多量に
包摂できるので高容量化に適しているものの、短絡する
と瞬時に膨大な電流が流れ、そのジュール熱により急激
に発熱して高温に達するため、異常使用時などにおいて
は引火・発火の可能性が高くなるという問題があった。Such a crush test or nail penetration test is based on the assumption that the battery is destroyed intentionally or by some kind of accident or the like. Even in such a crush test or nail penetration test, it is desirable to provide a highly safe one with no danger of ignition or ignition. In particular, the negative electrode active material composed of an alloy of a transition metal and a semimetal such as nickel silicide or manganese silicide is suitable for high capacity because it can contain a large amount of lithium. As a result, a large amount of current flows, and the Joule heat causes a rapid rise in heat to reach a high temperature. Therefore, there is a problem that the possibility of ignition or ignition increases during abnormal use.
【００１１】本発明は、上記のような高容量化を図った
場合の異常使用によって生じ得る安全性面での問題点を
解決し、高容量化が期待できる負極活物質を用いた場合
でも、引火・発火の危険性を解消し、高容量で、かつ安
全性の高い有機電解液二次電池を提供することを目的と
する。The present invention solves the problem of safety that can be caused by abnormal use when the capacity is increased as described above, and even when a negative electrode active material that can be expected to have a high capacity is used, An object of the present invention is to provide a high-capacity and highly safe organic electrolyte secondary battery that eliminates the danger of ignition and ignition.
【００１２】[0012]
【課題を解決するための手段】本発明は、負極活物質と
してＳｉ、Ｓｎ、Ｐｂおよびこれらの合金よりなる群か
ら選ばれる少なくとも１種を用い、かつ有機電解液中に
環状炭酸エステルまたは炭酸エステルの多量体のうち少
なくとも１種と、リン酸トリエステルとを含有させるこ
とによって、上記課題を解決したものである。According to the present invention, there is provided a negative electrode active material comprising at least one selected from the group consisting of Si, Sn, Pb and an alloy thereof, and a cyclic carbonate or a carbonate ester in an organic electrolyte. The above object has been achieved by including at least one of the multimers of the above and a phosphoric acid triester.
【００１３】本発明においては、上記のように、負極活
物質としてＳｉ、Ｓｎ、Ｐｂおよびこれらの合金よりな
る群から選ばれる少なくとも１種を用いることによっ
て、高電位で、高容量の有機電解液二次電池を得ること
ができる。In the present invention, as described above, by using at least one selected from the group consisting of Si, Sn, Pb and alloys thereof as the negative electrode active material, a high potential, high capacity organic electrolyte A secondary battery can be obtained.
【００１４】そして、有機電解液中にリン酸トリエステ
ルを含有させることによって引火・発火の危険性を解消
し、環状炭酸エステルまたは炭酸エステルの多量体の少
なくとも１種を上記リン酸トリエステルと併用すること
によって、上記リン酸トリエステルの使用に基づく放電
容量の低下を防止し、上記特定の負極活物質の使用と相
まって、高容量で、かつ安全性の高い有機電解液二次電
池を得ることができる。The risk of ignition or ignition is eliminated by incorporating a phosphate triester into the organic electrolyte, and at least one of cyclic carbonate or a polymer of carbonate is used in combination with the phosphate triester. By doing so, it is possible to prevent a decrease in discharge capacity due to the use of the phosphate triester, and to obtain a high-capacity and highly safe organic electrolyte secondary battery in combination with the use of the specific negative electrode active material. Can be.
【００１５】[0015]
【発明の実施の形態】本発明においては、上記のよう
に、Ｓｉ、Ｓｎ、Ｐｂおよびこれらの合金よりなる群か
ら選ばれる少なくとも１種を負極活物質として用いるこ
とにより、高電位で、かつ高容量の有機電解液二次電池
を得ることができるが、それらの中でも特にＳｉ、Ｓｎ
などが好ましい。また、それらＳｉ、Ｓｎ、Ｐｂなどの
合金化にあたって、それらの金属または半金属と組み合
わせる合金原料としては、例えば、Ａｌ、Ｂｉ、Ｇｅな
どの周期律表で１３族から１５族の金属または半金属、
Ｍｇ、Ｃａなどのアルカリ土類金属、Ｆｅ、Ｍｎ、Ｎ
ｉ、Ｃｏ、Ｃｕなどの遷移金属が挙げられ、これらの中
でも特に遷移金属が好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, as described above, by using at least one selected from the group consisting of Si, Sn, Pb and their alloys as a negative electrode active material, a high potential and a high potential can be obtained. It is possible to obtain an organic electrolyte secondary battery having a large capacity.
Are preferred. In alloying Si, Sn, Pb, etc., as an alloy raw material to be combined with the metal or metalloid, for example, a metal or metalloid of Group 13 to Group 15 in the periodic table such as Al, Bi, Ge, etc. ,
Alkaline earth metals such as Mg and Ca, Fe, Mn, N
Transition metals such as i, Co, and Cu are exemplified, and among these, transition metals are particularly preferable.
【００１６】上記のような合金の具体例としては、例え
ば、Ｍｇ、Ｓｉ、ＮｉＳｉ2 、Ｆｅ 2 Ｓｉ、ウッド合金
（Ｂｉ50Ｐｂ25Ｃｄ12.5Ｓｎ12.5）などが挙げられ、そ
れらの中でもＮｉＳｉ2 、Ｆｅ2 Ｓｉなどのリチウムと
合金化しない金属との合金は、化成時の正極のリチウム
イオンの利用効率を高め、かつサイクル中もＦｅやＮｉ
などのリチウムと合金化しない骨格構造を有するので、
サイクルに伴って生じる活物質（ＳｉＬｉ4 やＳｎＬｉ
4 など）の微粉化や凝集によるサイクル特性の低下を防
止することができ、特に好ましい。このような合金は必
ずしも単一相で構成されていなくてもよく、２以上の相
が共存する複合合金であってもよい。例えば、ＮｉＳｉ
2 はＮｉＳｉ相とＳｉ相の共存する複合合金であるが、
このＮｉＳｉ2 などのような複合合金も単一相合金と同
様に使用できる。このような複合合金においては各相が
緻密に分散している方が好ましく、そのためには合金の
溶解後急冷することが好ましい。Specific examples of the above alloys include, for example,
For example, Mg, Si, NiSiTwo, Fe TwoSi, wood alloy
(Bi50Pbtwenty fiveCd12.5Sn12.5).
Among them, NiSiTwo, FeTwoWith lithium such as Si
The alloy with the unalloyed metal is lithium for the positive electrode during chemical formation.
Improve the efficiency of ion use and keep Fe and Ni
Since it has a skeletal structure that does not alloy with lithium such as
Active material (SiLi)FourAnd SnLi
FourTo prevent deterioration of cycle characteristics due to pulverization and aggregation of
Can be stopped, which is particularly preferable. Such alloys are indispensable
It does not have to be composed of a single phase.
May be a composite alloy that coexists. For example, NiSi
TwoIs a composite alloy in which a NiSi phase and a Si phase coexist,
This NiSiTwoComposite alloys such as
Can be used in any way. Each phase in such a composite alloy is
It is preferable that they are finely dispersed.
It is preferable to cool rapidly after dissolution.
【００１７】上記のようにＳｉ、Ｓｎ、Ｐｂおよびこれ
らの合金よりなる群から選ばれる少なくとも１種を負極
活物質として用いることにより、高電位で、かつ高容量
の有機電解液二次電池が得られるが、これらの負極活物
質は内包するエネルギーが大きいため、従来の安全弁や
ＰＴＣ素子などの安全素子による対策では急激な発熱を
抑えられず、異常が発生した場合には引火・発火が生じ
る恐れがある。しかしながら、高容量化を達成していく
ためには、このような高容量化が期待できる負極活物質
を使用していかなければならない。As described above, by using at least one selected from the group consisting of Si, Sn, Pb and alloys thereof as a negative electrode active material, a high potential and high capacity organic electrolyte secondary battery can be obtained. However, since these negative electrode active materials contain large amounts of energy, conventional measures such as safety valves and PTC elements cannot prevent rapid heat generation, and if abnormalities occur, ignition or ignition may occur. There is. However, in order to achieve a higher capacity, it is necessary to use a negative electrode active material that can be expected to have such a higher capacity.
【００１８】そこで、本発明では、有機電解液中にリン
酸トリエステルを含有させることにより、引火・発火の
問題を解決したのである。上記リン酸トリエステルは、
一般式：（ＲＯ）3 Ｐ＝Ｏ（ただし、Ｒは有機基で３個
の有機基は同一であってもよく、また異なっていてもよ
い）で表され、引火性の低い有機溶媒であって、前記の
ような高容量化が期待できる負極活物質を用いた有機電
解液二次電池でも、充分に安全性を向上させることがで
きる。特に苛酷な条件下での安全性確認試験、例えば、
釘刺し試験などでは強制的に内部短絡を発生させ、有機
電解液を電池外に漏出させるが、このような釘刺し試験
においてもリン酸トリエステルを有機電解液中に含有さ
せておくことにより、引火・発火の危険性を低減させる
ことができる。このようなリン酸トリエステルとして
は、上記一般式（ＲＯ）3 Ｐ＝Ｏにおいて、Ｒが炭素数
１〜６のアルキル基であるリン酸トリアルキル、例え
ば、リン酸トリメチル、リン酸トリエチル、リン酸トリ
プロピル、リン酸トリブチルなどが好適に用いられる。Therefore, in the present invention, the problem of ignition / ignition has been solved by incorporating phosphoric acid triester into the organic electrolyte. The phosphoric acid triester is
General formula: (RO) 3 P = O (where R is an organic group and the three organic groups may be the same or different), and is an organic solvent having low flammability. Thus, the safety can be sufficiently improved even in the organic electrolyte secondary battery using the negative electrode active material which can be expected to have a high capacity as described above. Safety confirmation test under particularly severe conditions, for example,
In a nail piercing test etc., an internal short circuit is forcibly generated and the organic electrolyte leaks out of the battery, but in such a nail piercing test, the phosphate triester is contained in the organic electrolyte, The risk of ignition / ignition can be reduced. Examples of such a phosphoric acid triester include a trialkyl phosphate in which R is an alkyl group having 1 to 6 carbon atoms in the above general formula (RO) 3 P = O, for example, trimethyl phosphate, triethyl phosphate, phosphorus Tripropyl phosphate, tributyl phosphate and the like are preferably used.
【００１９】しかし、リン酸トリエステルを有機電解液
中に含有させると、前記のようなＳｉ、Ｓｎ、Ｐｂやそ
れらの合金などからなる負極活物質では放電容量が著し
く低下し、場合によってはまったく放電しなくなること
がある。この原因は必ずしも明確ではないが、負極表面
にリン酸トリエステルの分解によって生じた被膜が形成
され、それがリチウムイオンの移動を妨げることによる
ものと考えられる。However, when the phosphoric acid triester is contained in the organic electrolyte, the discharge capacity of the negative electrode active material composed of Si, Sn, Pb, an alloy thereof, or the like is significantly reduced, and in some cases, the discharge capacity is completely reduced. Discharging may not be possible. Although the cause is not necessarily clear, it is considered that a film formed by the decomposition of the phosphoric acid triester is formed on the negative electrode surface, which hinders the movement of lithium ions.
【００２０】そこで、本発明では、環状炭酸エステルま
たは炭酸エステルの多量体のうち少なくとも１種を上記
リン酸トリエステルと併用することにより、リン酸トリ
エステルの使用に基づく放電容量の低下を抑制し、高容
量で、かつ安全性の高い有機電解液二次電池を得ること
に成功したのである。すなわち、環状炭酸エステルまた
は炭酸エステルの多量体のうち少なくとも１種を併用す
ることにより、負極の表面に上記のようなリン酸トリエ
ステルに基づく被膜が形成されるよりも先に充放電反応
に適した環状炭酸エステルまたは炭酸エステルの多量体
のうち少なくとも１種に基づく被膜が形成され、負極の
表面にこの環状炭酸エステルまたは炭酸エステルの多量
体のうち少なくとも１種に基づく被膜が形成されると、
その環状炭酸エステルまたは炭酸エステルの多量体のう
ち少なくとも１種に基づく被膜が負極の表面を不活性化
するリン酸トリエステルが負極の表面に直接接触するの
を防止し、しかもこの環状炭酸エステルまたは炭酸エス
テルの多量体のうち少なくとも１種に基づく被膜がイオ
ン伝導にも寄与するので、リチウムイオンのドープ・脱
ドープが円滑に行われるようになり、リン酸トリエステ
ルの使用に基づく放電容量の低下を防止することができ
る。Therefore, in the present invention, by using at least one of cyclic carbonates or multimers of carbonates together with the above-mentioned phosphate triester, a decrease in discharge capacity due to the use of the phosphate triester can be suppressed. Thus, a high-capacity and highly safe organic electrolyte secondary battery was successfully obtained. That is, by using at least one of cyclic carbonates or multimers of carbonates in combination, it is suitable for the charge / discharge reaction before the above-mentioned coating based on phosphoric acid triester is formed on the surface of the negative electrode. When a coating based on at least one of the cyclic carbonates or multimers of the carbonate is formed, and a coating based on at least one of the cyclic carbonates or the multimers of the carbonate is formed on the surface of the negative electrode,
A coating based on at least one of the cyclic carbonate or the carbonate ester multimer prevents the phosphate triester, which inactivates the surface of the negative electrode, from coming into direct contact with the surface of the negative electrode. Since the coating based on at least one of the carbonate ester multimers also contributes to ionic conduction, lithium ion doping and undoping can be performed smoothly, and the discharge capacity decreases due to the use of phosphate triester. Can be prevented.
【００２１】上記のような環状炭酸エステルとしては、
例えば、エチレンカーボネート、プロピレンカーボネー
ト、ブチレンカーボネート、ペンテンカーボネートなど
が挙げられるが、特にエチレンカーボネート、プロピレ
ンカーボネートなどが好ましい。The above-mentioned cyclic carbonates include:
For example, ethylene carbonate, propylene carbonate, butylene carbonate, pentene carbonate and the like can be mentioned, and particularly, ethylene carbonate and propylene carbonate are preferable.
【００２２】また、上記のような炭酸エステルの多量体
としては、一般式：Ｒ1 ＯＣ（Ｏ）ＯＲ2 ＯＣ（Ｏ）Ｏ
Ｒ3 （ただし、Ｒ1 、Ｒ3 は炭素数１〜４のアルキル
基、Ｒ 2 は炭素数２〜４のアルキル基であり、それぞれ
同一であってもよく、また異なってもよい）で表される
もので、例えば、１，２−ビスメトキシカルボニルオキ
シエチレン、１，２−ビスメトキシカルボニルオキシプ
ロピレン、１，２−ビスエトキシカルボニルオキシエチ
レン、１，２−ビスエトキシカルボニルオキシプロピレ
ンなどが挙げられる。Also, the above-mentioned carbonate ester multimer
Has the general formula: R1OC (O) ORTwoOC (O) O
RThree(However, R1, RThreeIs alkyl having 1 to 4 carbon atoms
Group, R TwoIs an alkyl group having 2 to 4 carbon atoms,
May be the same or may be different)
For example, 1,2-bismethoxycarbonyloxy
Siethylene, 1,2-bismethoxycarbonyloxyp
Ropylene, 1,2-bisethoxycarbonyloxyethyl
Len, 1,2-bisethoxycarbonyloxypropyl
And the like.
【００２３】上記環状炭酸エステルと炭酸エステルの多
量体とは、いずれか一方を用いればよいが、両者を併用
してもよい。Either the cyclic carbonate or the carbonate ester multimer may be used, or both may be used in combination.
【００２４】リン酸トリエステルと環状炭酸エステルま
たは炭酸エステルの多量体のうち少なくとも１種との混
合比は、体積比で９９：１〜５０：５０にすることが好
ましく、９８：２〜８０：２０にすることがより好まし
い。リン酸トリエステルの量が環状炭酸エステルまたは
炭酸エステルの多量体のうち少なくとも１種との合計量
に対して体積比（全体の体積を１００とする体積比）で
５０以上（つまり、５０体積％以上）にすることにより
有機電解液の引火性を充分に低下することができ、ま
た、環状炭酸エステルまたは炭酸エステルの多量体のう
ち少なくとも１種の量をリン酸トリエステルとの合計量
に対して体積比で１以上（つまり、１体積％以上）にす
ることにより高い誘導率を確保することができ、高容量
化を達成することができる。The mixing ratio of the phosphoric acid triester and at least one of the cyclic carbonate or the polymer of the carbonate is preferably 99: 1 to 50:50 by volume, and 98: 2 to 80: More preferably, it is set to 20. The amount of the phosphoric acid triester is 50 or more (that is, 50% by volume) in a volume ratio (volume ratio with the total volume being 100) with respect to a total amount of the cyclic carbonate or at least one of the carbonate multimers. The above) can sufficiently reduce the flammability of the organic electrolytic solution, and the amount of at least one of the cyclic carbonate or the polymer of the carbonate can be reduced with respect to the total amount with the phosphate triester. By setting the volume ratio to 1 or more (that is, 1% by volume or more), a high induction rate can be secured, and a high capacity can be achieved.
【００２５】また、上記電解液には従来から使用されて
いる有機溶媒を添加してもよく、そのような有機溶媒と
しては、例えば、鎖状エステル、鎖状エーテル、環状エ
ーテル、鎖状炭酸エステルなどが挙げられるが、この場
合、これらの有機溶媒の添加量としては、リン酸トリエ
ステルと環状炭酸エステルまたは炭酸エステルの多量体
のうち少なくとも１種とに基づく効果を確保するため
に、有機電解液の構成溶媒全体に対して５０体積％以下
が好ましく、２０体積％以下がより好ましく、５体積％
以下がさらに好ましい。なお、この場合においても、リ
ン酸トリエステルと環状炭酸エステルまたは炭酸エステ
ルの多量体のうち少なくとも１種とは前記の混合比にす
ることが好ましい。A conventional organic solvent may be added to the electrolytic solution. Examples of such an organic solvent include a chain ester, a chain ether, a cyclic ether, and a chain carbonate. In this case, the amount of the organic solvent to be added may be selected from organic electrolysis in order to secure an effect based on the phosphoric acid triester and at least one of cyclic carbonate or a polymer of carbonate. It is preferably 50% by volume or less, more preferably 20% by volume or less, and more preferably 5% by volume with respect to the whole solvent constituting the liquid.
The following are more preferred. Also in this case, it is preferable that the mixing ratio of the phosphate triester and at least one of the cyclic carbonate or the polymer of the carbonate is the same as described above.
【００２６】上記有機電解液の電解質としては、例え
ば、ＬｉＣｌＯ4 、ＬｉＰＦ6 、ＬｉＢＦ4 、ＬｉＡｓ
Ｆ6 、ＬｉＳｂＦ6 、ＬｉＣＦ3 ＳＯ3 、ＬｉＣ4 Ｆ9
ＳＯ3、ＬｉＣＦ3 ＣＯ2 、Ｌｉ2 Ｃ2 Ｆ4 （ＳＯ3 ）
2 、ＬｉＮ（ＣＦ3 ＳＯ2 ）2、ＬｉＣ（ＣＦ3 Ｓ
Ｏ2 ）3 、ＬｉＣn Ｆ2n+1ＳＯ3 （ｎ≧２）などが、単
独でまたは２種以上混合して用いられる。それらの中で
も、ＬｉＰＦ6 やＬｉＣ4 Ｆ 9 ＳＯ3 は充放電特性が良
好なので、特に好適に用いられる。これらの電解質の有
機電解液中の濃度は、特に限定されるものではないが、
通常、０．１〜２モル／リットル、特に０．４〜１モル
／リットル程度が好ましい。As the electrolyte of the above organic electrolyte, for example,
For example, LiClOFour, LiPF6, LiBFFour, LiAs
F6, LiSbF6, LiCFThreeSOThree, LiCFourF9
SOThree, LiCFThreeCOTwo, LiTwoCTwoFFour(SOThree)
Two, LiN (CFThreeSOTwo)Two, LiC (CFThreeS
OTwo)Three, LiCnF2n + 1SOThree(N ≧ 2)
Used alone or as a mixture of two or more. Among them
Also, LiPF6And LiCFourF 9SOThreeHas good charge / discharge characteristics
Because it is good, it is particularly preferably used. The presence of these electrolytes
The concentration in the electrolyte is not particularly limited,
Usually 0.1 to 2 mol / l, especially 0.4 to 1 mol
Per liter is preferred.
【００２７】さらに、本発明においては、上記のような
有機電解液中に二酸化炭素を溶解させると、高容量化が
達成されやすくなる。これは、有機電解液二次電池で
は、負極活物質と有機電解液の構成溶媒との反応が起こ
りやすく、その反応生成物によって、充放電反応が阻害
されたり、容量が低下する傾向がみられるが、有機電解
液中に二酸化炭素を含有させておくと、二酸化炭素によ
ってそれを防止できるからである。これを詳しく説明す
ると、有機電解液中に二酸化炭素を含有させておくと、
負極活物質の表面に有機・無機の炭酸塩を主体とする薄
い被膜が形成され、この被膜により負極活物質と有機電
解液の構成溶媒との反応が抑制され、しかもその被膜が
充放電反応に悪影響を及ぼさず、また容量の低下を引き
起こさないので、正極材料、負極材料の有する能力を最
大限に発揮させることができ、電池の容量を向上させる
ことができる。Further, in the present invention, when carbon dioxide is dissolved in the above-mentioned organic electrolytic solution, a high capacity can be easily achieved. This is because, in the organic electrolyte secondary battery, the reaction between the negative electrode active material and the constituent solvent of the organic electrolyte tends to occur, and the reaction product tends to inhibit the charge / discharge reaction or decrease the capacity. However, if carbon dioxide is contained in the organic electrolyte, it can be prevented by carbon dioxide. To explain this in detail, if carbon dioxide is contained in the organic electrolytic solution,
A thin film mainly composed of an organic or inorganic carbonate is formed on the surface of the negative electrode active material, and this film suppresses the reaction between the negative electrode active material and the constituent solvent of the organic electrolytic solution. Since it has no adverse effect and does not cause a decrease in capacity, the ability of the positive electrode material and the negative electrode material can be maximized, and the capacity of the battery can be improved.
【００２８】また、有機電解液中への二酸化炭素の含有
は、正極活物質としてＬｉＮｉＯ2、ＬｉＣｏＯ2 、Ｌ
ｉＭｎＯ4 などの充電時の閉路電圧がＬｉ基準で４Ｖ以
上を示すリチウム複合酸化物を用いたときに、特に有効
である。これらの正極活物質は高電位であり、通常の条
件では有機電解液の構成溶媒が酸化されて放電性能が低
下するが、有機電解液中に耐酸化性の優れた二酸化炭素
を含有させておくと、二酸化炭素が正極表面での酸化に
よる有機電解液の構成溶媒の分解を抑制する。特にＬｉ
ＮｉＯ2 は他の金属酸化物より有機電解液の構成溶媒と
の反応性が強いことから使用しにくかったが、有機電解
液中に二酸化炭素を含有させておくことにより、このよ
うなＬｉＮｉＯ2 を用いる場合でも有機電解液の構成溶
媒との反応性が抑制されて、電池の高容量化が達成され
る。The content of carbon dioxide in the organic electrolyte is determined by using LiNiO 2 , LiCoO 2 , L
It is particularly effective when a lithium composite oxide such as iMnO 4 having a closed circuit voltage of 4 V or more based on Li when charged is used. These positive electrode active materials have a high potential, and under normal conditions, the constituent solvent of the organic electrolyte is oxidized and the discharge performance is reduced, but carbon dioxide with excellent oxidation resistance is contained in the organic electrolyte. And carbon dioxide suppresses decomposition of the constituent solvent of the organic electrolyte solution due to oxidation on the positive electrode surface. Especially Li
NiO 2 is difficult to use because it has a higher reactivity with the constituent solvent of the organic electrolyte than other metal oxides. However, by containing carbon dioxide in the organic electrolyte, such LiNiO 2 can be used. Even when it is used, the reactivity of the organic electrolyte with the constituent solvent is suppressed, and the capacity of the battery is increased.
【００２９】本発明においては、負極の作製にあたり、
上記負極活物質に、必要に応じて、導電助剤や結着剤な
どを添加することができる。上記導電助剤としては、例
えば、ニッケル粉末などの非炭素系材料や、黒鉛、アセ
チレンブラック、カーボンブラック、コークスなどの炭
素系材料が挙げられ、これらの導電助剤の中でも（００
２）面の層間距離（ｄ002 ）が０．３３８ｎｍ以上の低
結晶炭素材料が好ましい。この導電助剤の添加量は、特
に制限されることはないが、負極活物質に対して１〜３
０重量％が好ましく、特に２〜１５重量％が好ましい。
また、結着剤としては、例えば、ポリアクリル酸、カル
ボキシメチルセルロース、ポリフッ化ビニリデン、ポリ
テトラフルオロエチレン、エチレンプロピレンジエンゴ
ムなどが挙げられ、特にポリアクリル酸、カルボキシメ
チルセルロースなどが好ましい。この結着剤の添加量
は、特に制限されることはないが、負極活物質に対して
１〜５０重量％が好ましく、特に２〜２０重量％が好ま
しい。In the present invention, when producing the negative electrode,
A conductive assistant, a binder, and the like can be added to the negative electrode active material as needed. Examples of the conductive aid include non-carbon-based materials such as nickel powder, and carbon-based materials such as graphite, acetylene black, carbon black, and coke. Among these conductive aids, (00)
2) A low crystalline carbon material having an interlayer distance (d 002 ) of 0.338 nm or more is preferred. The amount of the conductive additive is not particularly limited, but may be 1 to 3 with respect to the negative electrode active material.
0% by weight is preferred, and 2-15% by weight is particularly preferred.
Examples of the binder include polyacrylic acid, carboxymethyl cellulose, polyvinylidene fluoride, polytetrafluoroethylene, ethylene propylene diene rubber, and the like, and polyacrylic acid, carboxymethyl cellulose, and the like are particularly preferable. The amount of the binder added is not particularly limited, but is preferably 1 to 50% by weight, and particularly preferably 2 to 20% by weight, based on the negative electrode active material.
【００３０】負極の作製にあたっては、例えば、上記の
ような負極活物質と導電助剤、結着剤などからなる負極
合剤に、水または溶剤を加え、混合してスラリー状の塗
料を調製し、その塗料を集電体に塗布し、乾燥して、塗
膜を形成する工程を経て負極を作製する方法が採用され
る。ただし、負極の作製方法は上記方法に限られること
なく、他の方法を採用してもよい。In the preparation of the negative electrode, for example, water or a solvent is added to a negative electrode mixture composed of the above-mentioned negative electrode active material, a conductive auxiliary agent, a binder, and the like, and mixed to prepare a slurry-like paint. A method of applying the paint to a current collector, drying the paint, and forming a coating film to produce a negative electrode is adopted. However, the method for manufacturing the negative electrode is not limited to the above method, and another method may be adopted.
【００３１】本発明において、正極活物質としては、特
に限定されることなく各種のものを用い得るが、例え
ば、ＬｉＮｉＯ2 、ＬｉＣｏＯ2 、ＬｉＭｎ2 Ｏ4 など
のリチウム複合酸化物が高電圧が得られることから好適
に用いられる。そして、正極の作製にあたっては、例え
ば、上記正極活物質に、必要に応じて、導電助剤、結着
剤などを加え、さらに水または溶剤などを加え、混合し
てスラリー状の塗料を作製し、乾燥して、塗膜を形成す
る工程を経て正極を作製する方法が採用される。ただ
し、正極の作製方法は上記例示のものに限られることな
く、他の方法を採用してもよい。また、導電助剤や結着
剤としては、前記負極の場合と同様のものを用いること
ができ、それらの正極活物質に対する使用量も前記負極
活物質に対する使用量と同程度でよい。In the present invention, as the positive electrode active material, various materials can be used without particular limitation. For example, a lithium composite oxide such as LiNiO 2 , LiCoO 2 , LiMn 2 O 4 can obtain a high voltage. Therefore, it is preferably used. Then, in producing the positive electrode, for example, to the above-mentioned positive electrode active material, if necessary, a conductive auxiliary, a binder and the like are added, and water or a solvent is added and mixed to prepare a slurry-like paint. Then, a method of producing a positive electrode through a step of drying and forming a coating film is employed. However, the method for manufacturing the positive electrode is not limited to the above-described example, and another method may be adopted. Further, as the conductive auxiliary agent and the binder, the same ones as in the case of the above-mentioned negative electrode can be used, and the usage amount of the positive electrode active material may be substantially the same as the usage amount of the negative electrode active material.
【００３２】本発明において、上記負極活物質や正極活
物質などを含有する塗料を集電体に塗布する際の塗布方
法としては、例えば、押し出しコーター、リバースロー
ラー、ドクターフレードなどをはじめ、各種の塗布方法
を採用することができる。In the present invention, as a method of applying a paint containing the above-mentioned negative electrode active material and positive electrode active material to a current collector, for example, various methods including an extrusion coater, a reverse roller, a doctor blade and the like can be used. Can be adopted.
【００３３】また、本発明において、正極、負極などの
電極の集電体としては、例えば、アルミニウム、ステン
レス鋼、チタン、銅などの金属の網、パンチドメタル、
エキスパンドメタル、フォームメタル、箔などが用いら
れる。In the present invention, the current collector of the electrodes such as the positive electrode and the negative electrode may be, for example, a metal mesh such as aluminum, stainless steel, titanium, copper, punched metal, or the like.
Expanded metal, foam metal, foil and the like are used.
【００３４】セパレータとしては、例えば、厚さ１０〜
１５μｍで、開孔率３０〜７０％の微多孔性ポリエチレ
ンフィルムや微多孔性ポリプロピレンフィルムなどが好
適に用いられる。As the separator, for example, a thickness of 10
A microporous polyethylene film or a microporous polypropylene film having a pore size of 15 μm and a porosity of 30 to 70% is suitably used.
【００３５】電池は、例えば、上記のように作製された
正極と負極との間にセパレータを介在させて重ね合わ
せ、それを渦巻状に巻回して作製した渦巻状電極体など
の巻回構造の電極体をニッケルメッキを施した鉄やステ
ンレス鋼製の電池ケース内に挿入し、封口する工程を経
て作製される。また、上記電池には、通常、電池内部に
発生したガスをある一定圧力まで上昇した段階で電池外
部に排出して、電池の高圧下での破裂を防止するための
防爆機構が取り入れられる。The battery has, for example, a wound structure such as a spiral electrode body produced by superposing a separator between the positive electrode and the negative electrode produced as described above with a separator interposed therebetween, and spirally winding the resultant. It is manufactured through a process of inserting the electrode body into a nickel-plated iron or stainless steel battery case and sealing the battery case. Further, the battery usually incorporates an explosion-proof mechanism for discharging the gas generated inside the battery to the outside of the battery when the pressure has risen to a certain pressure, thereby preventing the battery from bursting under high pressure.
【００３６】[0036]
【実施例】つぎに、実施例を挙げて本発明をより具体的
に説明する。ただし、本発明はそれらの実施例のみに限
定されるものではない。Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.
【００３７】実施例１ ＬｉＰＦ6 をリン酸トリメチルに溶解させた後、エチレ
ンカーボネートを加えて混合することにより、リン酸ト
リメチルとエチレンカーボネートとの体積比９８：２の
混合溶媒にＬｉＰＦ6 を１．０モル／リットル溶解させ
た有機電解液を調製した。[0037] After the Example 1 LiPF 6 was dissolved in trimethyl phosphate, by mixing the addition of ethylene carbonate, the volume ratio of the trimethyl phosphate and ethylene carbonate 98: a LiPF 6 in a mixed solvent of 2 1. An organic electrolyte in which 0 mol / liter was dissolved was prepared.
【００３８】また、リチウムコバルト酸化物（ＬｉＣｏ
Ｏ2 ）９１重量部に黒鉛６重量部とポリフッ化ビニリデ
ン３重量部とを加えて混合して正極合剤を調製し、それ
をＮ−メチルピロリドンで分散させてスラリー状の塗料
を調製した。この正極合剤を含有するスラリー状の塗料
を厚さ２０μｍのアルミニウム箔からなる正極集電体の
両面に均一に塗布し、乾燥して正極合剤からなる塗膜を
形成した後、ローラプレス機により圧縮成形し、リード
体の溶接を行い、厚さ１６０μｍのシート状の正極を作
製した。Further, lithium cobalt oxide (LiCo
O 2 ) 91 parts by weight, 6 parts by weight of graphite and 3 parts by weight of polyvinylidene fluoride were added and mixed to prepare a positive electrode mixture, which was dispersed with N-methylpyrrolidone to prepare a slurry coating. A slurry-like paint containing the positive electrode mixture is uniformly applied to both surfaces of a positive electrode current collector made of an aluminum foil having a thickness of 20 μm, and dried to form a coating film made of the positive electrode mixture. To form a sheet-shaped positive electrode having a thickness of 160 μm.
【００３９】上記とは別に、Ｓｉ（ケイ素）４５重量部
に黒鉛４０重量部とポリアクリル酸１５重量部とを混合
して負極合剤を調製し、それを水で分散させてスラリー
状の塗料を調製した。この負極合剤を含有するスラリー
状の塗料を厚さ１８μｍの銅箔からなる負極集電体の両
面に均一に塗布し、乾燥して負極合剤からなる塗膜を形
成した後、ローラープレス機で圧縮成形し、リード体の
溶接を行って、厚さ４０μｍのシート状の負極を作製し
た。Separately from the above, 45 parts by weight of Si (silicon) are mixed with 40 parts by weight of graphite and 15 parts by weight of polyacrylic acid to prepare a negative electrode mixture, which is dispersed in water to prepare a slurry-like coating material. Was prepared. The slurry-like paint containing the negative electrode mixture is uniformly applied to both surfaces of a negative electrode current collector made of a copper foil having a thickness of 18 μm, and dried to form a coating film made of the negative electrode mixture. Then, the lead body was welded to produce a sheet-shaped negative electrode having a thickness of 40 μm.
【００４０】つぎに、上記シート状の正極とシート状の
負極を両者の間に厚さ２５μｍの微多孔性ポリエチレン
フィルムからなるセパレータを介在させて重ね合わせ、
渦巻状に巻回して渦巻状電極体を作製し、その渦巻状電
極体を外径１８ｍｍの有底円筒状の電池ケース内に充填
し、ついで、電池ケースの開口部を封口して、図１に示
す筒形の有機電解液二次電池を作製した。Next, the sheet-shaped positive electrode and the sheet-shaped negative electrode were overlapped with a separator made of a microporous polyethylene film having a thickness of 25 μm interposed therebetween.
The spirally wound electrode body is manufactured by spirally winding the spirally wound electrode body, and the spirally wound electrode body is filled in a bottomed cylindrical battery case having an outer diameter of 18 mm. Then, the opening of the battery case is sealed, and FIG. The organic electrolyte secondary battery having a cylindrical shape shown in FIG.
【００４１】図１に示す電池について説明すると、１は
前記の正極で、２は負極である。ただし、図１では、煩
雑化を避けるため、正極１や負極２の作製に当たって使
用した集電体として金属箔などは図示していない。そし
て、これらの正極１と負極２はセパレータ３を介して渦
巻状に巻回され、渦巻状電極体として上記の有機電解液
４と共に電池ケース５内に収容されている。Referring to the battery shown in FIG. 1, reference numeral 1 denotes the positive electrode and 2 denotes the negative electrode. However, in FIG. 1, a metal foil or the like is not shown as a current collector used in manufacturing the positive electrode 1 and the negative electrode 2 in order to avoid complication. The positive electrode 1 and the negative electrode 2 are spirally wound with a separator 3 interposed therebetween, and are housed in a battery case 5 together with the organic electrolytic solution 4 as a spiral electrode body.
【００４２】電池ケース５はステンレス鋼製で、負極端
子を兼ねており、この電池ケース５の底部には上記渦巻
状電極体の挿入に先立って、ポリテトラフルオロエチレ
ンからなる絶縁体６が配置されている。封口板７はアル
ミニウム製で、円板状をしていて、中央部に薄肉部７ａ
を設け、かつ上記薄肉部７ａの周囲に電池内圧を防爆弁
９に作用させるために圧力導入口７ｂとしての孔が設け
られている。そして、この薄肉部７ａの上面に防爆弁９
の突出部９ａが溶接され、溶接部分１１を構成してい
る。なお、上記の封口板７に設けた薄肉部７ａや防爆弁
９の突出部９ａなどは、図面上での理解がしやすいよう
に、切断面のみを図示しており、切断面後方の輪郭線は
図示を省略している。また、封口版７の薄肉部７ａと防
爆弁９の突出部９ａとの溶接部分１１も、図面上での理
解が容易なように、実際よりは誇張した状態に図示して
いる。The battery case 5 is made of stainless steel and also serves as a negative electrode terminal. Before inserting the spiral electrode body, an insulator 6 made of polytetrafluoroethylene is arranged at the bottom of the battery case 5. ing. The sealing plate 7 is made of aluminum, has a disk shape, and has a thin portion 7a at the center.
And a hole serving as a pressure introduction port 7b is provided around the thin portion 7a in order to cause the battery internal pressure to act on the explosion-proof valve 9. An explosion-proof valve 9 is provided on the upper surface of the thin portion 7a.
Are welded to form a welded portion 11. In addition, the thin portion 7a provided on the sealing plate 7 and the protruding portion 9a of the explosion-proof valve 9 are illustrated only in a cut plane so as to be easily understood in the drawings, and a contour line behind the cut plane is shown. Is not shown. Also, the welded portion 11 between the thin portion 7a of the sealing plate 7 and the protruding portion 9a of the explosion-proof valve 9 is shown in an exaggerated state in order to facilitate understanding on the drawing.
【００４３】端子板８は、圧延銅製で表面にニッケルメ
ッキが施され、周縁部が鍔状になった帽子状をしてお
り、この端子板８にはガス排出孔８ａが設けられてい
る。防爆弁９は、アルミニウム製で、円板状をしてお
り、その中央部には発電要素側（図１では、下側）に先
端部を有する突出部９ａが設けられ、その突出部９ａの
下面が、前記したように、封口板７の薄肉部７ａの上面
に溶接され、溶接部分１１を構成している。絶縁パッキ
ング１０は、ポリプロピレン製で、環状をしており、封
口板７の周縁部の上部に配置され、その上部に防爆弁９
が配置していて、封口板７と防爆弁９を絶縁するととも
に、両者の間から有機電解液が漏れないように両者の間
隙を封止している。環状ガスケット１２はポリプロピレ
ン製で、リード体１３はアルミニウム製で、前記封口板
７と正極１とを接続し、渦巻状電極体の上部には絶縁体
１４が配置され、負極２と電池ケース５の底部とはニッ
ケル製のリード体１５で接続されている。The terminal plate 8 is made of rolled copper, nickel-plated on the surface, and has a hat-like shape with a peripheral edge formed in a flange shape. The terminal plate 8 is provided with a gas discharge hole 8a. The explosion-proof valve 9 is made of aluminum and is in the shape of a disk, and a central portion is provided with a projecting portion 9a having a tip on the power generation element side (the lower side in FIG. 1). As described above, the lower surface is welded to the upper surface of the thin portion 7a of the sealing plate 7 to form a welded portion 11. The insulating packing 10 is made of polypropylene and has an annular shape. The insulating packing 10 is disposed above the peripheral edge of the sealing plate 7 and has an explosion-proof valve 9
Are arranged to insulate the sealing plate 7 and the explosion-proof valve 9 and seal the gap between the two so that the organic electrolyte does not leak from between the two. The annular gasket 12 is made of polypropylene, and the lead body 13 is made of aluminum. The sealing plate 7 and the positive electrode 1 are connected to each other. An insulator 14 is disposed above the spiral electrode body. The bottom portion is connected by a lead body 15 made of nickel.
【００４４】前記のように、電池ケース５の底部には絶
縁体６が配置され、前記正極１、負極２およびセパレー
タ３からなる渦巻状電極体や、有機電解液４、渦巻状電
極体上部の絶縁体１４などは、この電池ケース５内に収
容され、それらの収容後、電池ケース５の開口端近傍部
分に底部が内方に突出した環状の溝が形成される。そし
て、上記電池ケース５の開口部に、封口板７、絶縁パッ
キング１０、防爆弁９が挿入された環状ガスケット１２
を入れ、さらにその上から端子板８を挿入し、電池ケー
ス５の溝から先の部分を内方に締め付けることによっ
て、電池ケース５の開口部が封口されている。ただし、
上記のような電池組立にあたっては、あらかじめ負極２
と電池ケース５とをリード体１５で接続し、正極１と封
口板７とをリード体１３で接続しておくことが好まし
い。As described above, the insulator 6 is disposed at the bottom of the battery case 5, and the spiral electrode body including the positive electrode 1, the negative electrode 2, and the separator 3, the organic electrolytic solution 4, and the upper part of the spiral electrode body are provided. The insulator 14 and the like are housed in the battery case 5, and after the housing, an annular groove having a bottom protruding inward is formed in the vicinity of the open end of the battery case 5. An annular gasket 12 having a sealing plate 7, an insulating packing 10, and an explosion-proof valve 9 inserted into the opening of the battery case 5 is provided.
, And the terminal plate 8 is inserted from above, and the portion of the battery case 5 beyond the groove is fastened inward, whereby the opening of the battery case 5 is sealed. However,
When assembling the battery as described above, the anode 2
It is preferable that the battery case 5 is connected to the positive electrode 1 and the sealing plate 7 by the lead 13.
【００４５】上記のようにして組み立てられた電池にお
いては、封口板７の薄肉部７ａと防爆弁９の突出部９ａ
とが溶接部分１１で接触し、防爆弁９の周縁部と端子板
８の周縁部とが接触し、正極１と封口板７とは正極側の
リード体１３で接続されているので、正極１と端子板８
とはリード体１３、封口板７、防爆弁９およびそれらの
溶接部分１１によって電気的接続が得られ、電路として
正常に機能する。In the battery assembled as described above, the thin portion 7a of the sealing plate 7 and the projection 9a of the explosion-proof valve 9 are provided.
Contact at the welded portion 11, the peripheral portion of the explosion-proof valve 9 and the peripheral portion of the terminal plate 8 come into contact, and the positive electrode 1 and the sealing plate 7 are connected by the lead 13 on the positive electrode side. And terminal plate 8
The electrical connection is obtained by the lead body 13, the sealing plate 7, the explosion-proof valve 9 and the welded portion 11 thereof, and the lead body normally functions as an electric circuit.
【００４６】そして、電池に異常が起こり、電池内部に
ガスが発生して電池の内圧が上昇した場合には、その内
圧上昇により、防爆弁９の中央部が内圧方向（図１で
は、上側の方向）に変形に、それに伴って溶接部分１１
で一体化されている薄肉部７ａに剪弾力が働いて、該薄
肉部７ａが破断するか、または防爆弁９の突出部９ａと
封口板７の薄肉部７ａとの溶接部分１１が剥離し、それ
によって、正極１と端子板８との電気的接続が消失し
て、電流が遮断されるようになる。その結果、電池反応
が進行しなくなるので、過充電時や短絡時でも、充電電
流や短絡電流による電池の温度上昇や内圧上昇がそれ以
上進行しなくなって、電池の発火や破裂を防止できるよ
うに設計されている。When an abnormality occurs in the battery and gas is generated inside the battery and the internal pressure of the battery rises, the internal pressure rises, so that the central portion of the explosion-proof valve 9 moves in the direction of the internal pressure (in FIG. Direction) and the corresponding welded portion 11
A shear force acts on the thin portion 7a integrated by the above, the thin portion 7a is broken, or the welded portion 11 between the projection 9a of the explosion-proof valve 9 and the thin portion 7a of the sealing plate 7 peels off, As a result, the electrical connection between the positive electrode 1 and the terminal plate 8 is lost, and the current is interrupted. As a result, the battery reaction does not proceed, so that even during overcharge or short circuit, the battery temperature rise and internal pressure rise due to the charging current and short circuit current do not progress further, so that ignition and rupture of the battery can be prevented. Designed.
【００４７】なお、上記防爆弁９には薄肉部９ｂが設け
られており、例えば、充電が極度に進行して有機電解液
や活物質などの発電要素が分解し、大量のガスが発生し
た場合は、防爆弁９が変形して、防爆弁９の突出部分９
ａと封口板７の薄肉部７ａとの溶接部分１１が剥離した
後、この防爆弁９に設けた薄肉部９ｂが開裂してガスを
端子板８のガス排出孔８ａから電池外部に排出させて電
池の破裂を防止することができるように設計されてい
る。The explosion-proof valve 9 is provided with a thin portion 9b. For example, when the charging proceeds extremely and power generation elements such as an organic electrolyte and an active material are decomposed and a large amount of gas is generated. Means that the explosion-proof valve 9 is deformed,
After the welded portion 11 of the sealing plate 7 and the thin portion 7a of the sealing plate 7 are peeled off, the thin portion 9b provided on the explosion-proof valve 9 is ruptured to discharge gas from the gas discharge hole 8a of the terminal plate 8 to the outside of the battery. It is designed to prevent battery rupture.
【００４８】実施例２ 実施例１の有機電解液二次電池において、負極活物質と
してＳｎ（錫）を用いた以外は、実施例１と同様にして
有機電解液二次電池を作製した。Example 2 An organic electrolyte secondary battery was produced in the same manner as in Example 1 except that Sn (tin) was used as the negative electrode active material in the organic electrolyte secondary battery of Example 1.
【００４９】実施例３ 有機電解液の構成溶媒として、エチレンカーボネートに
代えてプロピレンカーボネートを用いた以外は、実施例
１と同様にして有機電解液二次電池を作製した。Example 3 An organic electrolyte secondary battery was produced in the same manner as in Example 1, except that propylene carbonate was used instead of ethylene carbonate as a constituent solvent of the organic electrolyte.
【００５０】実施例４ 有機電解液の構成溶媒として、エチレンカーボネートに
代えて１，２−ビスエトキシカルボニルオキシエチレン
を用いた以外は、実施例１と同様にして有機電解液二次
電池を作製した。Example 4 An organic electrolyte secondary battery was produced in the same manner as in Example 1, except that 1,2-bisethoxycarbonyloxyethylene was used instead of ethylene carbonate as a constituent solvent of the organic electrolyte. .
【００５１】比較例１ 有機電解液の構成溶媒として、リン酸トリメチルに代え
てメチルエチルカーボネートを用いた以外は、実施例１
と同様にして有機電解液二次電池を作製した。Comparative Example 1 Example 1 was repeated except that methyl ethyl carbonate was used instead of trimethyl phosphate as a constituent solvent of the organic electrolytic solution.
In the same manner as in the above, an organic electrolyte secondary battery was produced.
【００５２】比較例２ 有機電解液の構成溶媒として、リン酸トリメチルのみを
用いた以外は、実施例１と同様にして有機電解液二次電
池を作製した。Comparative Example 2 An organic electrolyte secondary battery was produced in the same manner as in Example 1, except that only trimethyl phosphate was used as a constituent solvent of the organic electrolyte.
【００５３】上記のようにして得られた実施例１〜４お
よび比較例１〜２の電池の放電容量を測定し、かつ引火
性試験および発火性試験を行った。それらの測定方法や
試験方法はつぎの通りである。The discharge capacities of the batteries of Examples 1 to 4 and Comparative Examples 1 and 2 obtained as described above were measured, and a flammability test and an ignition test were performed. The measuring method and test method are as follows.
【００５４】放電容量：実施例１〜４および比較例１〜
２の電池を２０℃、０．２Ｃで電圧２．７５〜４．１Ｖ
の範囲で充放電させ、初回の放電容量を測定した。得ら
れた放電容量を負極活物質の単位体積当たりの容量に換
算した値で表１に示す。Discharge capacity: Examples 1-4 and Comparative examples 1
Battery at 2.degree. C. and 0.2 C at 2.75 to 4.1 V
And the initial discharge capacity was measured. Table 1 shows the values obtained by converting the obtained discharge capacities into capacities per unit volume of the negative electrode active material.
【００５５】引火性試験：実施例１〜４および比較例１
〜２の電池について、電池が高温に加熱されて、安全弁
が作動した状態（すなわち、図１に示す電池において、
有機電解液中からの構成溶媒の蒸発などにより、電池内
部にガスが発生し、電池内圧が上昇して、所定の圧力に
達したとき、封口板７の厚み方向の両端面より内部側に
設けた薄肉部７ａが防爆弁９の内圧方向への変化に伴っ
て生じる剪断力により破壊され、電池内部のガスがガス
排出孔８ａから電池外部の排出される状態）になったこ
とを想定し、あらかじめ封口板７の薄肉部７ａを破壊し
ておき、その状態で電池を１００℃まで加熱し、電池の
ガス排出孔８ａに火を近づけて、引火するか否かを調べ
た。その結果を表１に示す。Flammability test: Examples 1-4 and Comparative Example 1
2, the batteries were heated to a high temperature and the safety valve was activated (that is, in the battery shown in FIG. 1,
Gas is generated inside the battery due to evaporation of the constituent solvent from the organic electrolytic solution, etc., and when the internal pressure of the battery rises and reaches a predetermined pressure, it is provided on the inner side from both end surfaces in the thickness direction of the sealing plate 7. The thin portion 7a is broken by the shearing force caused by the change of the explosion-proof valve 9 in the internal pressure direction, and the gas inside the battery is discharged from the gas discharge hole 8a to the outside of the battery. The thin portion 7a of the sealing plate 7 was destroyed in advance, and the battery was heated to 100 ° C. in that state, and a fire was approached to the gas discharge hole 8a of the battery to check whether or not to ignite. Table 1 shows the results.
【００５６】発火性試験：実施例１〜４および比較例１
〜２の電池について、釘刺し試験を行った。釘刺し試験
では、電池を４．１８Ｖまで充電した状態にし、４５℃
の恒温槽中に４時間放置した後、直径３ｍｍのステンレ
ス鋼製釘を、治具を用いて電池の側面から電池の直径１
／２のところまで突き刺し、各電池５個中で発火する電
池の数を調べた。その結果を表１に示す。表１中におい
て、発火性試験の結果を示す数値の分母は試験に供した
電池個数であり、分子は発火した電池個数である。Ignitability test: Examples 1-4 and Comparative Example 1
A nail penetration test was performed on the batteries of Nos. 1 to 2. In the nail penetration test, the battery was charged to 4.18 V,
After being left in a constant temperature bath for 4 hours, a stainless steel nail having a diameter of 3 mm was inserted from the side of the battery using a jig to a diameter of 1 mm.
/ 2, and the number of ignited batteries among the five batteries was examined. Table 1 shows the results. In Table 1, the denominator of the numerical value indicating the result of the ignition test is the number of batteries used for the test, and the numerator is the number of batteries that fired.
【００５７】[0057]
【表１】 [Table 1]
【００５８】表１に示す放電容量の測定結果から明らか
なように、リン酸トリメチルを単独で有機電解液の構成
溶媒として用いた比較例２は、まったく放電しなかっ
た。しかし、リン酸トリメチルにエチレンカーボネート
やプロピレンカーボネートなどの環状炭酸エステルまた
は１，２−ビスエトキシカルボニルオキシエチレンなど
の炭酸エステルの多量体を併用した実施例１〜４では、
高容量が得られた。As is clear from the measurement results of the discharge capacity shown in Table 1, Comparative Example 2 using trimethyl phosphate alone as a constituent solvent of the organic electrolyte did not discharge at all. However, in Examples 1-4 in which a cyclic carbonate such as ethylene carbonate or propylene carbonate or a polymer of a carbonate such as 1,2-bisethoxycarbonyloxyethylene was used in combination with trimethyl phosphate,
High capacity was obtained.
【００５９】また、引火性試験の結果から明らかなよう
に、リン酸トリメチルを含有しない通常の有機電解液を
用いた比較例１では、約４０℃に加熱した時点で引火
し、燃えだしたが、有機電解液中にリン酸トリメチルを
含有させた実施例１〜４では、１００℃まで加熱しても
引火せず、火災に対して高い安全性を有していた。Further, as is apparent from the results of the flammability test, in Comparative Example 1 using a normal organic electrolyte solution containing no trimethyl phosphate, it ignited when heated to about 40 ° C., and started burning. In Examples 1 to 4 in which trimethyl phosphate was contained in the organic electrolytic solution, even if heated to 100 ° C., no ignition occurred, and the fire safety was high.
【００６０】また、発火性試験の結果から明らかなよう
に、通常の有機電解液を用いた比較例１は、発火がみら
れたが、有機電解液中にリン酸トリメチルを含有させた
実施例１〜４では、発火することなく、釘刺しにより内
部短絡が生じても安全性の高い電池が得られた。As is clear from the results of the ignition test, Comparative Example 1 in which a normal organic electrolyte was used was ignited, but the example in which trimethyl phosphate was contained in the organic electrolyte was used. In Nos. 1 to 4, batteries with high safety were obtained even if an internal short circuit occurred due to nail penetration without firing.
【００６１】[0061]
【発明の効果】以上説明したように、本発明では、高容
量で、かつ安全性の高い有機電解液二次電池を提供する
ことができた。As described above, according to the present invention, a high-capacity and highly safe organic electrolyte secondary battery can be provided.
【図１】本発明の有機電解液二次電池の一実施例を模式
的に示す縦断面図である。FIG. 1 is a longitudinal sectional view schematically showing one embodiment of an organic electrolyte secondary battery of the present invention.
１ 正極 ２ 負極 ３ セパレータ ４ 有機電解液 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Organic electrolyte
Claims (1)
出し得る負極および正極と、リチウムイオン伝導性の有
機電解液を有する有機電解液二次電池において、負極活
物質がＳｉ、Ｓｎ、Ｐｂおよびこれらの合金よりなる群
から選ばれる少なくとも１種であり、かつ上記有機電解
液中に環状炭酸エステルまたは炭酸エステルの多量体の
うち少なくとも１種と、リン酸トリエステルとを含有す
ることを特徴とする有機電解液二次電池。1. An organic electrolyte secondary battery having a negative electrode and a positive electrode capable of occluding and releasing lithium ions by charge and discharge, and an organic electrolyte secondary battery having a lithium ion conductive organic electrolyte, wherein the negative electrode active material is Si, Sn, Pb and At least one selected from the group consisting of alloys of the above, and the organic electrolyte solution contains at least one of cyclic carbonate or a polymer of carbonate and a phosphate triester. Organic electrolyte secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10248895A JPH11176470A (en) | 1997-10-07 | 1998-09-03 | Organic electrolyte secondary battery |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-291594 | 1997-10-07 | ||
| JP29159497 | 1997-10-07 | ||
| JP10248895A JPH11176470A (en) | 1997-10-07 | 1998-09-03 | Organic electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11176470A true JPH11176470A (en) | 1999-07-02 |
Family
ID=26538991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10248895A Pending JPH11176470A (en) | 1997-10-07 | 1998-09-03 | Organic electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11176470A (en) |
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| WO2000014817A1 (en) * | 1998-09-08 | 2000-03-16 | Sumitomo Metal Industries, Ltd. | Negative electrode material for nonaqueous electrode secondary battery and method for producing the same |
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-
1998
- 1998-09-03 JP JP10248895A patent/JPH11176470A/en active Pending
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