JP2002117896A - Flat lithium secondary battery - Google Patents
Flat lithium secondary batteryInfo
- Publication number
- JP2002117896A JP2002117896A JP2000306657A JP2000306657A JP2002117896A JP 2002117896 A JP2002117896 A JP 2002117896A JP 2000306657 A JP2000306657 A JP 2000306657A JP 2000306657 A JP2000306657 A JP 2000306657A JP 2002117896 A JP2002117896 A JP 2002117896A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- lithium
- lithium secondary
- secondary battery
- flat
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、扁平形リチウム二
次電池に関し、特にリフロー法等の高温条件下で表面実
装を行うことが可能な扁平形リチウム二次電池に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flat lithium secondary battery, and more particularly to a flat lithium secondary battery which can be surface-mounted under high-temperature conditions such as a reflow method.
【０００２】[0002]
【従来の技術】近年、扁平形のリチウム二次電池は、携
帯電話等の携帯端末のメモリバックアップ用電源として
利用されるようになった。この場合、電池は、プリント
基板に表面実装される。表面実装の方法としては、生産
性の観点から、基板上にハンダ（融点：１８６℃程度）
および接続リード端子を取り付けた電池を載置した状態
で、部品（端子）温度が２００℃以上になるように設定
したリフロー炉内を通過させる方法（リフロー法）を用
いることが望ましい。2. Description of the Related Art In recent years, flat lithium secondary batteries have been used as power sources for memory backup of portable terminals such as portable telephones. In this case, the battery is surface-mounted on a printed circuit board. As a method of surface mounting, from the viewpoint of productivity, solder (melting point: about 186 ° C.)
In addition, it is desirable to use a method (reflow method) in which a battery having connection lead terminals mounted thereon is passed through a reflow furnace set so that the component (terminal) temperature becomes 200 ° C. or higher.
【０００３】ところで、従来より、リチウム二次電池の
負極には、リチウム−アルミニウム合金等が用いられ、
正極には、例えば、特開昭６３−１１４０６４号公報に
開示されているようにリチウム含有マンガン複合酸化物
等が用いられる。このような電池は、高温下に保存され
るとリチウム含有マンガン複合酸化物と電解液とが反応
して正極側でガスが発生することが知られており、耐熱
温度は６０℃程度である。Conventionally, a lithium-aluminum alloy or the like has been used for a negative electrode of a lithium secondary battery.
For the positive electrode, for example, a lithium-containing manganese composite oxide or the like is used as disclosed in JP-A-63-114064. Such a battery is known to react with the lithium-containing manganese composite oxide and the electrolytic solution when stored at a high temperature to generate gas on the positive electrode side, and has a heat-resistant temperature of about 60 ° C.
【０００４】したがって、従来のリチウム二次電池をリ
フロー炉内の高温環境に晒すと、ガスが激しく発生し
て、電池の内部抵抗が大きく上昇してしまうため、これ
まで以上の耐熱性を備え、リフロー法を適用できるリチ
ウム二次電池の開発が強く求められていた。Therefore, when a conventional lithium secondary battery is exposed to a high-temperature environment in a reflow furnace, gas is violently generated, and the internal resistance of the battery is greatly increased. There has been a strong demand for the development of a lithium secondary battery to which the reflow method can be applied.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記の事情
に鑑みなされたものであり、その目的は、リフロー法等
によって２００℃を超える高温環境下に晒されても電池
の内部抵抗が大きく上昇せず、良好な電池特性を維持で
きる扁平形リチウム二次電池を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in consideration of the above circumstances, and has as its object to increase the internal resistance of a battery even when exposed to a high temperature environment exceeding 200 ° C. by a reflow method or the like. An object of the present invention is to provide a flat lithium secondary battery that does not rise and can maintain good battery characteristics.
【０００６】[0006]
【課題を解決するための手段】上記の課題を解決するた
め、請求項１に記載の発明は、正極と負極とをセパレー
タを介して対向させてなる電極体と、非水電解液と、前
記電極体と非水電解液とを収納する電池外装缶と、前記
電池外装缶の開口部を封口する電池封口缶とを有する扁
平形リチウム二次電池において、前記正極は、ＢＥＴ法
により測定した比表面積が２．０ｍ2 ／ｇ以下のリチウ
ム含有金属酸化物を活物質とすることを特徴とする。Means for Solving the Problems In order to solve the above-mentioned problems, the invention according to claim 1 provides an electrode body having a positive electrode and a negative electrode facing each other via a separator, a non-aqueous electrolyte, In a flat lithium secondary battery having a battery outer can containing an electrode body and a non-aqueous electrolyte and a battery sealing can sealing an opening of the battery outer can, the positive electrode has a ratio measured by a BET method. A lithium-containing metal oxide having a surface area of 2.0 m 2 / g or less is used as an active material.
【０００７】リチウム含有金属酸化物としては、例えば
前記特開昭６３−１１４０６４号公報に開示のリチウム
含有マンガン複合酸化物が知られているが、これは、図
１に示すように、外形が略球形であって、表面から内部
に向かって延びる空隙部１を有する形状をしている。こ
のため、比表面積が大きいものは空隙部が多く、このよ
うなものを用いた電池をリフロー法で表面実装すると、
電解液との接触面積が大きく、しかも高温に晒されるこ
とになるので多量にガスが発生する。そのため、電池内
部の圧力が上昇して電池外装缶や電池封口缶が変形し、
その結果として正極および負極との接触不良によって内
部抵抗の上昇を引き起こす。これに対して、比表面積が
２．０ｍ2 ／ｇ以下であるものは、電解液との接触面積
が小さいので、多量にガスが発生せず、電池外装缶や電
池封口缶の変形が起こらないため、内部抵抗が大きく上
昇することはない。よって、リフロー法等を適用したと
しても、良好な電池特性を維持した扁平形リチウム二次
電池となる。As the lithium-containing metal oxide, for example, a lithium-containing manganese composite oxide disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 63-114064 is known. It is spherical and has a shape having a cavity 1 extending from the surface toward the inside. For this reason, those with a large specific surface area have many voids, and when a battery using such a thing is surface-mounted by a reflow method,
A large amount of gas is generated because the contact area with the electrolytic solution is large and it is exposed to a high temperature. As a result, the pressure inside the battery rises and the battery outer can and the battery sealing can deform,
As a result, poor contact between the positive electrode and the negative electrode causes an increase in internal resistance. On the other hand, those having a specific surface area of 2.0 m 2 / g or less do not generate a large amount of gas because the contact area with the electrolyte is small, and do not cause deformation of the battery outer can or the battery can. Therefore, the internal resistance does not increase significantly. Therefore, even when the reflow method or the like is applied, the flat lithium secondary battery maintains good battery characteristics.
【０００８】ここで、本発明において、ＢＥＴ法とは、
窒素吸着によるＢ．Ｅ．Ｔ１点法をいう。Here, in the present invention, the BET method is
B. by nitrogen adsorption E. FIG. It refers to the T1 point method.
【０００９】請求項２に記載の発明は、請求項１に記載
の発明において、前記リチウム含有金属酸化物が、スピ
ネル構造を有するリチウム含有マンガン複合酸化物であ
ることを特徴とする。According to a second aspect of the present invention, in the first aspect, the lithium-containing metal oxide is a lithium-containing manganese composite oxide having a spinel structure.
【００１０】リチウム二次電池の正極活物質として従来
から用いられているリチウム含有金属酸化物、例えば前
記特開昭６３−１１４０６４号公報に開示のリチウム含
有マンガン複合酸化物は、５００℃を超える温度で焼成
を行うと、結晶構造を保持できないので、比表面積を
２．０ｍ2 ／ｇ以下にするのは困難である。これに対し
て、スピネル構造を有するリチウム含有マンガン複合酸
化物は、８５０℃で焼成を行ってもその結晶構造を維持
できるため、比表面積を２．０ｍ2 ／ｇ以下にすること
は容易である。また、スピネル構造を有するリチウム含
有マンガン複合酸化物は、比表面積を小さくしても電池
容量が大きく低下しないという特徴を有する。よって、
正極活物質としてスピネル構造を有するリチウム含有マ
ンガン複合酸化物を用いれば、簡便にリフロー対応の扁
平型リチウム二次電池を提供できる。また、スピネル構
造を有するリチウム含有マンガン複合酸化物は２．０〜
３．２Ｖの電圧で使用可能であるため、従来から使用さ
れている電池とは電池電圧で互換性を有する電池を提供
できるという利点もある。A lithium-containing metal oxide conventionally used as a positive electrode active material of a lithium secondary battery, for example, a lithium-containing manganese composite oxide disclosed in Japanese Patent Application Laid-Open No. 63-114064, has a temperature exceeding 500 ° C. If baking is performed, the crystal structure cannot be maintained, and it is difficult to reduce the specific surface area to 2.0 m 2 / g or less. On the other hand, since the lithium-containing manganese composite oxide having a spinel structure can maintain its crystal structure even when fired at 850 ° C., it is easy to reduce the specific surface area to 2.0 m 2 / g or less. . Further, the lithium-containing manganese composite oxide having a spinel structure has a feature that even when the specific surface area is reduced, the battery capacity does not significantly decrease. Therefore,
When a lithium-containing manganese composite oxide having a spinel structure is used as the positive electrode active material, a flat lithium secondary battery compatible with reflow can be easily provided. The lithium-containing manganese composite oxide having a spinel structure is 2.0 to
Since the battery can be used at a voltage of 3.2 V, there is also an advantage that a battery having a battery voltage compatible with a conventionally used battery can be provided.
【００１１】請求項３に記載の発明は、請求項１または
２に記載の発明において、前記非水電解液が、溶媒とし
て少なくともカーボネート系有機溶媒を含むものである
ことを特徴とする。A third aspect of the present invention is characterized in that, in the first or second aspect, the non-aqueous electrolyte contains at least a carbonate-based organic solvent as a solvent.
【００１２】カーボネート系有機溶媒は、リチウム含有
マンガン酸化物と反応して、多量のガス（二酸化炭素）
が発生するので、この溶媒を含んだ非水電解液であれ
ば、本発明による改善効果が高い。The carbonate-based organic solvent reacts with the lithium-containing manganese oxide to produce a large amount of gas (carbon dioxide).
Therefore, a non-aqueous electrolyte containing this solvent has a high effect of improvement according to the present invention.
【００１３】請求項４に記載の発明は、請求項１〜３の
いずれか１項に記載の発明において、前記電池外装缶と
電池封口缶とが、電池外装缶の内側縁部に配置された絶
縁ガスケットを介してかしめ固定されており、かつ、前
記セパレータと前記絶縁ガスケットとが耐熱樹脂からな
り、前記非水電解液が、溶媒として少なくとも高沸点有
機溶媒を含むとともに、溶質としてＬｉＣＦ3ＳＯ3、Ｌ
ｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2からな
る群から選択される少なくとも１種のリチウム塩を含む
ものであることを特徴とする。According to a fourth aspect of the present invention, in the first aspect of the present invention, the battery outer can and the battery sealing can are arranged at an inner edge of the battery outer can. The separator and the insulating gasket are fixed by caulking via an insulating gasket, and the separator and the insulating gasket are made of a heat-resistant resin. The nonaqueous electrolyte contains at least a high-boiling organic solvent as a solvent, and LiCF 3 SO 3 as a solute. , L
It is characterized by containing at least one lithium salt selected from the group consisting of iN (CF 3 SO 2 ) 2 and LiN (C 2 F 5 SO 2 ) 2 .
【００１４】上記のような、セパレータ、絶縁ガスケッ
ト、非水電解液を用いれば、リフロー法を適用するのに
最適な扁平形リチウム二次電池となる。The use of the separator, the insulating gasket, and the non-aqueous electrolyte as described above provides a flat lithium secondary battery which is most suitable for applying the reflow method.
【００１５】[0015]
【発明の実施の形態】本発明の実施の形態を、扁平形の
リチウム二次電池を例として、図面を用いて説明する。
図２は、この電池の構成を示す断面図である。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described with reference to the drawings, taking a flat type lithium secondary battery as an example.
FIG. 2 is a sectional view showing the configuration of this battery.
【００１６】図２に示すように、この電池は、外観が扁
平形状であって、ステンレス製の電池外装缶（正極缶）
２を有しており、この正極缶２内には、スピネル構造を
有するリチウム含有マンガン複合酸化物（ＢＥＴ法によ
る比表面積：０．４ｍ2 ／ｇ）を活物質とする正極３
と、リチウム−アルミニウム合金を活物質とする負極４
と、両極を離間するポリフェニレンサルファイド不織布
からなるセパレータ５とから構成される電極体６が収容
されている。なお、上記セパレータ５には、プロピレン
カーボネートとジエチレングリコールジメチルエーテル
とを体積比で３：７で配合してなる混合溶媒に、ＬｉＮ
（ＣＦ3 ＳＯ2）2を０．５Ｍ（モル／リットル）の割合
で溶かしてなる電解液が含浸されている。そして、上記
正極缶２の開口部には、リング形状の絶縁ガスケット７
を介して、ステンレスとアルミニウムとからなるクラッ
ド材製の電池封口缶（負極キャップ）８がかしめ固定さ
れ、封口されている。As shown in FIG. 2, this battery has a flat appearance and a stainless steel battery outer can (a positive electrode can).
In the positive electrode can 2, a positive electrode 3 containing a lithium-containing manganese composite oxide having a spinel structure (specific surface area by BET method: 0.4 m 2 / g) as an active material
And a negative electrode 4 using a lithium-aluminum alloy as an active material
And an electrode body 6 comprising a separator 5 made of a non-woven fabric of polyphenylene sulfide which separates both electrodes. In the separator 5, a mixed solvent of propylene carbonate and diethylene glycol dimethyl ether in a volume ratio of 3: 7 is mixed with LiN.
An electrolytic solution obtained by dissolving (CF 3 SO 2 ) 2 at a ratio of 0.5 M (mol / liter) is impregnated. A ring-shaped insulating gasket 7 is provided in the opening of the positive electrode can 2.
, A battery sealing can (negative electrode cap) 8 made of a clad material made of stainless steel and aluminum is caulked and fixed and sealed.
【００１７】上記構造のリチウム二次電池を、以下のよ
うにして作製した。A lithium secondary battery having the above structure was manufactured as follows.
【００１８】〔正極の作製〕まず、二酸化マンガンと水
酸化リチウムとをモル比で２：１で混合した後、空気中
にて８５０℃で１５時間焼成して、比表面積が０．４ｍ
2 ／ｇであるリチウム含有マンガン複合酸化物を得た。
つぎに、得られたリチウム含有マンガン複合酸化物と、
導電剤としての炭素系導電剤（アセチレンブラック）
と、結着剤としてのフッ素樹脂（ＰＶｄＦ）とを、９
２．１：６．４：１．５の質量比で混合し、混練して、
正極合剤を得た。そして、この正極合剤を、９ton/cm2
の圧力により加圧成形して、直径９ｍｍで厚み０．１５
ｍｍの円板状の正極を作製した。[Preparation of Positive Electrode] First, manganese dioxide and lithium hydroxide were mixed at a molar ratio of 2: 1 and calcined in air at 850 ° C. for 15 hours to give a specific surface area of 0.4 m.
2 / g of a lithium-containing manganese composite oxide was obtained.
Next, the obtained lithium-containing manganese composite oxide,
Carbon-based conductive agent (acetylene black) as conductive agent
And a fluororesin (PVdF) as a binder,
2.1: 6.4: 1.5 mixed at a mass ratio, kneaded,
A positive electrode mixture was obtained. Then, this positive electrode mixture was mixed with 9 ton / cm 2
Pressure molding with a pressure of 9 mm in diameter and 0.15 in thickness
A disk-shaped positive electrode having a thickness of 2 mm was prepared.
【００１９】〔電池の作製〕ステンレス板とアルミニウ
ム板とを貼り合わせ、内面がアルミニウム板になるよう
にしたクラッド材製の電池封口缶（負極キャップ）を準
備し、内面のアルミニウム板の表面に金属リチウム板を
圧着して、直径９ｍｍで厚み０．０４ｍｍの円板状の負
極を作製した。なお、アルミニウム板表面に圧着した金
属リチウム板は、電池封口後に合金化反応が起こるの
で、負極活物質は、リチウム−アルミニウム合金であ
る。つぎに、この負極上に、ポリフェニレンサルファイ
ド不織布からなるセパレータを載置し、そのセパレータ
に対して電解液を注液した。その後、その上に、前記正
極を載置し、さらにポリフェニレンサルファイド製の絶
縁ガスケットを介して、ステンレス製の正極缶を被せか
しめることにより、電池径（直径）１２ｍｍで厚み０．
６ｍｍのリチウム二次電池を製造した。[Preparation of Battery] A stainless steel plate and an aluminum plate are bonded to each other to prepare a battery sealing can (negative electrode cap) made of a clad material in which the inner surface is an aluminum plate. A lithium plate was crimped to produce a disc-shaped negative electrode having a diameter of 9 mm and a thickness of 0.04 mm. In addition, since the metal lithium plate pressed on the aluminum plate surface undergoes an alloying reaction after the battery is sealed, the negative electrode active material is a lithium-aluminum alloy. Next, a separator made of a nonwoven fabric of polyphenylene sulfide was placed on the negative electrode, and an electrolytic solution was injected into the separator. Thereafter, the positive electrode was placed thereon, and further covered with a stainless steel positive electrode can via an insulating gasket made of polyphenylene sulfide, so that the battery diameter (diameter) was 12 mm and the thickness was 0.1 mm.
A 6 mm lithium secondary battery was manufactured.
【００２０】〔その他の事項〕なお、上記実施の形態に
おいては、正極活物質として、比表面積０．４ｍ2 ／ｇ
であるスピネル構造を有するリチウム含有マンガン複合
酸化物を用いたが、これに限定するものではない。上記
以外の正極活物質としては、リチウム含有コバルト複合
酸化物、リチウム含有ニッケル複合酸化物等のリチウム
含有金属酸化物を用いることができる。また、リチウム
含有金属酸化物のマンガン、コバルト、ニッケル等の一
部を他の元素で置換した酸化物であってもよい。ただ
し、これらはＢＥＴ法により測定した比表面積が２．０
ｍ2 ／ｇ以下である必要がある。比表面積が２．０ｍ2
／ｇを超えると、発生するガスによって電池性能の低下
を招くからである。なお、比表面積が小さすぎると、電
池反応が不充分になるおそれがあるため、比表面積の好
適な範囲は、０．２〜２．０ｍ2 ／ｇである。なお、比
表面積は、焼成温度や焼成時間等を調節することによっ
て所望の値に設定することができる。例えば、焼成温度
を高めるかあるいは焼成時間を長くすれば比表面積を小
さくできる。[Other Matters] In the above embodiment, the specific surface area of the positive electrode active material is 0.4 m 2 / g.
Although a lithium-containing manganese composite oxide having a spinel structure was used, the present invention is not limited to this. As the positive electrode active material other than the above, a lithium-containing metal oxide such as a lithium-containing cobalt composite oxide and a lithium-containing nickel composite oxide can be used. Further, an oxide in which a part of manganese, cobalt, nickel, or the like of a lithium-containing metal oxide is replaced with another element may be used. However, these have a specific surface area of 2.0 as measured by the BET method.
m 2 / g or less. Specific surface area is 2.0m 2
If it exceeds / g, the generated gas will cause a decrease in battery performance. If the specific surface area is too small, the battery reaction may be insufficient. Therefore, a preferable range of the specific surface area is 0.2 to 2.0 m 2 / g. The specific surface area can be set to a desired value by adjusting the firing temperature, the firing time, and the like. For example, the specific surface area can be reduced by raising the firing temperature or lengthening the firing time.
【００２１】また、負極活物質としては、金属リチウ
ム、リチウム−アルミニウム合金等を用いることができ
る。As the negative electrode active material, metallic lithium, lithium-aluminum alloy, or the like can be used.
【００２２】さらに、非水電解液の溶質としては、上記
ＬｉＮ（ＣＦ3ＳＯ2）2の他に、例えば、熱分解温度が
高い、ＬｉＣＦ3ＳＯ3、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2 等が
好適に用いられる。これらは単独であるいは２種以上併
せて用いてもよい。また、溶媒としては、上記で用いた
ものの他に、例えば、エチレンカーボネート、ブチレン
カーボネート、ジメチルカーボネート、ジエチルカーボ
ネート、エチルメチルカーボネート等のカーボネート系
有機溶媒や、トリエチレングリコールジメチルエーテル
等の高沸点エーテル系有機溶媒を用いることができる。
ここで、本発明において、高沸点とは、沸点が１５０℃
以上をいい、特に２００℃以上が好適である。これらは
単独であるいは２種以上併せて用いられる。Furthermore, in addition to the above-mentioned LiN (CF 3 SO 2 ) 2 , for example, as a solute of the non-aqueous electrolyte, for example, LiCF 3 SO 3 or LiN (C 2 F 5 SO 2 ) 2 having a high thermal decomposition temperature. Etc. are preferably used. These may be used alone or in combination of two or more. As the solvent, in addition to those used above, for example, carbonate-based organic solvents such as ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, and high-boiling ether-based organic solvents such as triethylene glycol dimethyl ether Solvents can be used.
Here, in the present invention, the high boiling point means that the boiling point is 150 ° C.
The above is mentioned, and particularly preferably 200 ° C. or more. These may be used alone or in combination of two or more.
【００２３】また、上記の例では、セパレータや絶縁ガ
スケットの形成材料として、ポリフェニレンサルファイ
ドを用いたが、これに限定するものではない。例えば、
ポリエーテルエーテルケトン、ポリエーテルケトン、ポ
リエチレンテレフタレート、ポリブチレンテレフタレー
ト、ポリアリレート等の荷重たわみ温度（１．８２ＭＰ
ａ荷重時、ＪＩＳ Ｋ ７１９１に準拠）が１００℃以
上の耐熱樹脂が好適である。なお、ガスケットについて
は、強度を高めるため、チタン酸カリウム繊維、アルミ
ナ繊維、炭化ケイ素繊維、窒化ケイ素繊維、ジルコニア
繊維等のセラミックス系繊維や、ガラス繊維、炭素繊維
等の無機繊維を添加してもよい。ここで、セパレータと
絶縁ガスケットは、互いに同一の耐熱樹脂材料で成形さ
れたものであってもよいし、異なる材料で成形されたも
のであってもよい。In the above example, polyphenylene sulfide was used as a material for forming the separator and the insulating gasket. However, the present invention is not limited to this. For example,
Deflection temperature under load (1.82MP) of polyetheretherketone, polyetherketone, polyethyleneterephthalate, polybutyleneterephthalate, polyarylate, etc.
A heat-resistant resin having a load of 100 ° C. or more under JIS K 7191 under load is suitable. For the gasket, in order to increase the strength, ceramic fibers such as potassium titanate fiber, alumina fiber, silicon carbide fiber, silicon nitride fiber, and zirconia fiber, and glass fiber, and inorganic fiber such as carbon fiber may be added. Good. Here, the separator and the insulating gasket may be formed of the same heat-resistant resin material, or may be formed of different materials.
【００２４】本発明は、上記のような絶縁ガスケットを
用いて封口した電池に限定するものではなく、例えばレ
ーザー溶接等で封口した電池にも適用することができ
る。The present invention is not limited to a battery sealed by using the above-mentioned insulating gasket, but can also be applied to a battery sealed by, for example, laser welding.
【００２５】[0025]
【実施例】つぎに、本発明について、実施例および比較
例に基づいてさらに詳細に説明するが、本発明は下記の
実施例に限定されるものではない。Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００２６】（実施例１）実施例１としては、上記発明
の実施の形態に示す方法と同様の方法にて作製したリチ
ウム二次電池を用いた。Example 1 In Example 1, a lithium secondary battery manufactured by the same method as that described in the embodiment of the present invention was used.
【００２７】（実施例２）正極活物質として、ＢＥＴ法
により測定した比表面積が２．０ｍ2 ／ｇであるスピネ
ル構造を有するリチウム含有マンガン複合酸化物を用い
た他は、実施例１と同様にして、リチウム二次電池を製
造した。Example 2 The same as Example 1 except that a lithium-containing manganese composite oxide having a spinel structure and having a specific surface area of 2.0 m 2 / g measured by the BET method was used as a positive electrode active material. Thus, a lithium secondary battery was manufactured.
【００２８】（実施例３）正極活物質として、ＢＥＴ法
により測定した比表面積が０．２ｍ2 ／ｇであるスピネ
ル構造を有するリチウム含有マンガン複合酸化物を用い
た他は、実施例１と同様にして、リチウム二次電池を製
造した。Example 3 The same as Example 1 except that a lithium-containing manganese composite oxide having a spinel structure and having a specific surface area of 0.2 m 2 / g measured by the BET method was used as a positive electrode active material. Thus, a lithium secondary battery was manufactured.
【００２９】（比較例１）正極活物質として、ＢＥＴ法
により測定した比表面積が７．６ｍ2 ／ｇであるスピネ
ル構造を有するリチウム含有マンガン複合酸化物を用い
た他は、実施例１と同様にして、リチウム二次電池を製
造した。Comparative Example 1 The same as Example 1 except that a lithium-containing manganese composite oxide having a spinel structure and having a specific surface area of 7.6 m 2 / g measured by a BET method was used as a positive electrode active material. Thus, a lithium secondary battery was manufactured.
【００３０】（比較例２）正極活物質として、ＢＥＴ法
により測定した比表面積が１４．７ｍ2 ／ｇであるスピ
ネル構造を有するリチウム含有マンガン複合酸化物を用
いた他は、実施例１と同様にして、リチウム二次電池を
製造した。Comparative Example 2 The same as Example 1 except that a lithium-containing manganese composite oxide having a spinel structure and having a specific surface area of 14.7 m 2 / g measured by a BET method was used as a positive electrode active material. Thus, a lithium secondary battery was manufactured.
【００３１】（比較例３）正極活物質として、ＢＥＴ法
により測定した比表面積が１９．７ｍ2 ／ｇであるスピ
ネル構造を有するリチウム含有マンガン複合酸化物を用
いた他は、実施例１と同様にして、リチウム二次電池を
製造した。Comparative Example 3 The same as Example 1 except that a lithium-containing manganese composite oxide having a spinel structure and having a specific surface area of 19.7 m 2 / g measured by a BET method was used as a positive electrode active material. Thus, a lithium secondary battery was manufactured.
【００３２】このようにして得られたリチウム二次電池
について、下記に示す実験１、２、３を行った。Experiments 1, 2, and 3 shown below were performed on the thus obtained lithium secondary battery.
【００３３】（実験１）各リチウム二次電池に用いたス
ピネル構造を有するリチウム含有マンガン複合酸化物１
０ｍｇと、プロピレンカーボネート５ｍｇとを混合した
後、２３５℃で５分間加熱して、二酸化炭素発生量を測
定した。その結果を、図３に示す。(Experiment 1) Lithium-containing manganese composite oxide 1 having a spinel structure used for each lithium secondary battery
After mixing 0 mg and 5 mg of propylene carbonate, the mixture was heated at 235 ° C. for 5 minutes, and the amount of carbon dioxide generated was measured. The result is shown in FIG.
【００３４】（実験２）各リチウム二次電池を、電池表
面温度が最大２４０℃となるように設定した炉内に投入
し、電池全体が２００℃以上で約４０秒間晒される条件
で高温処理を行った。この高温処理を２回行った後、内
部抵抗を測定した。その結果を、図４に示す。なお、高
温処理前の電池は、全て５０〜６０Ωの範囲内であっ
た。(Experiment 2) Each lithium secondary battery is put into a furnace set so that the battery surface temperature is 240 ° C. at the maximum, and the high temperature treatment is performed under the condition that the whole battery is exposed at 200 ° C. or more for about 40 seconds. went. After performing this high-temperature treatment twice, the internal resistance was measured. The result is shown in FIG. The batteries before the high temperature treatment were all in the range of 50 to 60Ω.
【００３５】（実験３）各リチウム二次電池について、
実験２の高温処理を行わない電池と高温処理を行った電
池の放電容量を測定した。測定は、室温（約２０℃）に
て１５０ｋΩの定抵抗放電を行い、電池電圧が２．０Ｖ
になるまでの放電容量を求めた。その結果を表１に示
す。(Experiment 3) For each lithium secondary battery,
The discharge capacity of the battery not subjected to the high-temperature treatment in Experiment 2 and the battery subjected to the high-temperature treatment were measured. The measurement was performed at room temperature (approximately 20 ° C.) at a constant resistance of 150 kΩ and the battery voltage was 2.0 V
The discharge capacity up to was obtained. Table 1 shows the results.
【００３６】[0036]
【表１】 [Table 1]
【００３７】実験１、２の結果から、内部抵抗の上昇と
ガス発生との間に相関関係があることが確認できた。ま
た、比表面積が２．０ｍ2 ／ｇ以下であるスピネル構造
を有するリチウム含有マンガン複合酸化物を用いた電池
（実施例１〜３）は、それよりも大きい比表面積を有す
るスピネル構造を有するリチウム含有マンガン複合酸化
物を用いた電池（比較例１〜３）に比べ、ガス発生量は
少なく、内部抵抗もかなり小さかったことがわかった。
具体的には、実施例１〜３の各電池は、内部抵抗が２０
０Ω以下であったのに対し、比較例１〜３の各電池は、
２００Ωを超えていた。一般に内部抵抗が２００Ωを超
える電池は、実使用に耐えることができない。From the results of Experiments 1 and 2, it was confirmed that there was a correlation between the increase in internal resistance and the generation of gas. In addition, the batteries using the lithium-containing manganese composite oxide having a spinel structure having a specific surface area of 2.0 m 2 / g or less (Examples 1 to 3) were prepared using lithium having a spinel structure having a larger specific surface area. It was found that the amount of generated gas was small and the internal resistance was considerably small as compared with the batteries using the contained manganese composite oxide (Comparative Examples 1 to 3).
Specifically, each of the batteries of Examples 1 to 3 has an internal resistance of 20
In contrast to 0 Ω or less, the batteries of Comparative Examples 1 to 3 were:
It exceeded 200Ω. Generally, a battery having an internal resistance exceeding 200 Ω cannot withstand actual use.
【００３８】また、実験３の結果から、スピネル構造を
有するリチウム含有マンガン複合酸化物の比表面積が小
さくなっても、高温処理前の放電容量が大きく減少しな
いことがわかった。また、比表面積が２．０ｍ2 ／ｇよ
り大きいスピネル構造を有するリチウム含有マンガン複
合酸化物を用いた電池は、高温処理後の放電容量が大き
く低下したのに対し、２．０ｍ2 ／ｇ以下の比表面積の
ものを用いた電池は、高温処理後の放電容量の低下が極
めて小さかったことがわかった。From the results of Experiment 3, it was found that even if the specific surface area of the lithium-containing manganese composite oxide having a spinel structure was reduced, the discharge capacity before the high-temperature treatment was not significantly reduced. In addition, a battery using a lithium-containing manganese composite oxide having a spinel structure having a specific surface area larger than 2.0 m 2 / g has a greatly reduced discharge capacity after high-temperature treatment, but has a specific capacity of 2.0 m 2 / g or less. It was found that in the battery using the specific surface area, the decrease in the discharge capacity after the high temperature treatment was extremely small.
【００３９】以上より、比較例１〜３の各電池はリフロ
ー法等の２００℃を超える高温処理に耐えられない電池
であるが、実施例１〜３の電池はリフロー法等に適用可
能な電池であることがわかった。As described above, the batteries of Comparative Examples 1 to 3 cannot withstand high-temperature treatment exceeding 200 ° C. such as the reflow method, but the batteries of Examples 1 to 3 can be applied to the reflow method and the like. It turned out to be.
【００４０】[0040]
【発明の効果】本発明は、正極活物質であるリチウム含
有金属酸化物の比表面積を規制した点に特徴を有する
が、このような本発明によると、リフロー法等の２００
℃を超えるような高温環境下で表面実装を行っても特に
内部抵抗が大きく上昇せず、良好な電池特性を維持でき
る扁平形リチウム二次電池を提供できる。The present invention is characterized in that the specific surface area of the lithium-containing metal oxide serving as the positive electrode active material is regulated.
Even when surface mounting is performed in a high-temperature environment exceeding ℃, a flat lithium secondary battery which can maintain good battery characteristics without particularly increasing the internal resistance can be provided.
【図１】リチウム含有金属酸化物の粒子形状を模式的に
示す断面図である。FIG. 1 is a cross-sectional view schematically showing a particle shape of a lithium-containing metal oxide.
【図２】本発明の一例である扁平形リチウム二次電池を
模式的に示す断面図である。FIG. 2 is a cross-sectional view schematically showing a flat lithium secondary battery as an example of the present invention.
【図３】二酸化炭素発生量と比表面積との関係を示すグ
ラフ図である。FIG. 3 is a graph showing the relationship between the amount of carbon dioxide generated and the specific surface area.
【図４】内部抵抗と比表面積との関係を示すグラフ図で
ある。FIG. 4 is a graph showing the relationship between internal resistance and specific surface area.
１ 空隙部 ２ 電池外装缶（正極缶） ３ 正極 ４ 負極 ５ セパレータ ６ 電極体 ７ 絶縁ガスケット ８ 電池封口缶（負極キャップ） DESCRIPTION OF SYMBOLS 1 Void part 2 Battery outer can (positive electrode can) 3 Positive electrode 4 Negative electrode 5 Separator 6 Electrode body 7 Insulating gasket 8 Battery sealing can (negative electrode cap)
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田中 章仁 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 藤本 実 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 古橋 利朗 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 Ｆターム(参考） 5H011 AA02 CC06 GG02 HH02 5H029 AJ01 AK03 AL12 AM03 AM04 AM05 AM07 BJ03 DJ02 DJ03 DJ04 DJ17 EJ12 HJ07 HJ14 5H050 AA01 AA05 BA17 CA09 DA18 DA19 FA19 HA07 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akihito Tanaka 2-5-5 Keihanhondori, Moriguchi City, Osaka Prefecture Inside Sanyo Electric Co., Ltd. (72) Minoru Fujimoto 2-5-5 Keihanhondori, Moriguchi City, Osaka Prefecture No. 5 Sanyo Electric Co., Ltd. (72) Inventor Toshiro Furuhashi 2-5-5 Keihanhondori, Moriguchi-shi, Osaka F-term in Sanyo Electric Co., Ltd. 5H011 AA02 CC06 GG02 HH02 5H029 AJ01 AK03 AL12 AM03 AM04 AM05 AM07 BJ03 DJ02 DJ03 DJ04 DJ17 EJ12 HJ07 HJ14 5H050 AA01 AA05 BA17 CA09 DA18 DA19 FA19 HA07
Claims (4)
向させてなる電極体と、非水電解液と、前記電極体と非
水電解液とを収納する電池外装缶と、前記電池外装缶の
開口部を封口する電池封口缶とを有する扁平形リチウム
二次電池において、 前記正極は、ＢＥＴ法により測定した比表面積が２．０
ｍ2 ／ｇ以下のリチウム含有金属酸化物を活物質とす
る、ことを特徴とする扁平形リチウム二次電池。1. An electrode body having a positive electrode and a negative electrode facing each other with a separator interposed therebetween, a non-aqueous electrolyte, a battery outer can containing the electrode body and the non-aqueous electrolyte, and a battery outer can. In a flat lithium secondary battery having a battery sealing can closing an opening, the positive electrode has a specific surface area measured by a BET method of 2.0.
A flat type lithium secondary battery comprising a lithium-containing metal oxide of m 2 / g or less as an active material.
ネル構造を有するリチウム含有マンガン複合酸化物であ
る、請求項１記載の扁平形リチウム二次電池。2. The flat lithium secondary battery according to claim 1, wherein the lithium-containing metal oxide is a lithium-containing manganese composite oxide having a spinel structure.
ともカーボネート系有機溶媒を含むものである、請求項
１または２記載の扁平形リチウム二次電池。3. The flat lithium secondary battery according to claim 1, wherein the non-aqueous electrolyte contains at least a carbonate-based organic solvent as a solvent.
池外装缶の内側縁部に配置された絶縁ガスケットを介し
てかしめ固定されており、かつ、 前記セパレータと前記絶縁ガスケットとが耐熱樹脂から
なり、前記非水電解液が、溶媒として少なくとも高沸点
有機溶媒を含むとともに、溶質としてＬｉＣＦ 3 Ｓ
Ｏ3、ＬｉＮ（ＣＦ3 ＳＯ2 ）2、ＬｉＮ（Ｃ2 Ｆ5 ＳＯ
2 ）2からなる群から選択される少なくとも１種のリチ
ウム塩を含むものである、請求項１〜３のいずれか１項
に記載の扁平形リチウム二次電池。4. The battery outer can and the battery sealing can are
Through an insulating gasket located on the inner edge of the pond outer can
And the separator and the insulating gasket are made of heat-resistant resin.
Wherein the non-aqueous electrolyte has at least a high boiling point as a solvent.
Including organic solvent, LiCF as solute ThreeS
OThree, LiN (CFThreeSOTwo)Two, LiN (CTwoFFiveSO
Two)TwoAt least one species selected from the group consisting of
The composition according to any one of claims 1 to 3, wherein the composition contains a sodium salt.
4. The flat lithium secondary battery according to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000306657A JP4245267B2 (en) | 2000-10-05 | 2000-10-05 | Flat lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000306657A JP4245267B2 (en) | 2000-10-05 | 2000-10-05 | Flat lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002117896A true JP2002117896A (en) | 2002-04-19 |
| JP4245267B2 JP4245267B2 (en) | 2009-03-25 |
Family
ID=18787308
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|---|---|---|---|
| JP2000306657A Expired - Fee Related JP4245267B2 (en) | 2000-10-05 | 2000-10-05 | Flat lithium secondary battery |
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004127545A (en) * | 2002-09-30 | 2004-04-22 | Sanyo Electric Co Ltd | Lithium battery |
| US7588860B2 (en) | 2004-09-03 | 2009-09-15 | Panasonic Corporation | Lithium primary battery |
| KR101073165B1 (en) * | 2002-09-30 | 2011-10-12 | 산요덴키가부시키가이샤 | Heat-Resistant Lithium Battery |
| JP5928591B2 (en) * | 2012-07-26 | 2016-06-01 | Tdk株式会社 | Lithium ion secondary battery |
-
2000
- 2000-10-05 JP JP2000306657A patent/JP4245267B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004127545A (en) * | 2002-09-30 | 2004-04-22 | Sanyo Electric Co Ltd | Lithium battery |
| KR101073165B1 (en) * | 2002-09-30 | 2011-10-12 | 산요덴키가부시키가이샤 | Heat-Resistant Lithium Battery |
| US7588860B2 (en) | 2004-09-03 | 2009-09-15 | Panasonic Corporation | Lithium primary battery |
| JP5928591B2 (en) * | 2012-07-26 | 2016-06-01 | Tdk株式会社 | Lithium ion secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4245267B2 (en) | 2009-03-25 |
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