JP2001266948A - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JP2001266948A JP2001266948A JP2000074231A JP2000074231A JP2001266948A JP 2001266948 A JP2001266948 A JP 2001266948A JP 2000074231 A JP2000074231 A JP 2000074231A JP 2000074231 A JP2000074231 A JP 2000074231A JP 2001266948 A JP2001266948 A JP 2001266948A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- battery
- composite film
- resin composite
- reductant
- 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
-
- 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、非水電解質二次電
池に関し、特に外装体が金属樹脂複合フィルムである密
閉式非水電解質二次電池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a sealed non-aqueous electrolyte secondary battery having an outer package made of a metal resin composite film.
【０００２】[0002]
【従来の技術】小型二次電池は、携帯用端末器用電源に
多く用いられ、更なる高容量化、薄型化が要求されてい
る。特に、リチウムイオン電池は高いエネルギー密度を
有することから、研究が盛んに行われている。2. Description of the Related Art Small secondary batteries are widely used as power supplies for portable terminals, and are required to have higher capacity and thinner. In particular, lithium ion batteries have been actively studied because of their high energy density.
【０００３】前記小型二次電池の構成としては、捲回し
た極群を円筒型のケースに収納した円筒型電池や、平板
状の極板を積層して平角形ケースに収納した角形電池等
がある。より安価で軽量な小型二次電池を提供する手段
として、例えば実開昭６０−１６２３６２号公報、特開
昭６１−２５６１５７号公報では、発電要素を金属樹脂
複合フィルムの袋に収納し、熱溶着により封口したもの
が提案されている。As the configuration of the small secondary battery, there are a cylindrical battery in which wound electrode groups are housed in a cylindrical case, and a rectangular battery in which flat electrode plates are stacked and housed in a rectangular case. is there. As means for providing a cheaper and lighter small secondary battery, for example, Japanese Utility Model Application Laid-Open No. 60-162362 and Japanese Patent Application Laid-Open No. 61-256157 disclose a method in which a power generation element is housed in a metal resin composite film bag, Has been proposed.
【０００４】現在多く用いられている金属樹脂複合フィ
ルムは、金属箔の表裏に外装樹脂及び内装樹脂をそれぞ
れ配したラミネート構造体であり、前記金属箔は例えば
アルミニウムであり、外装樹脂はポリエチレンテレフタ
レート（PET）やポリアミド等であり、内層樹脂は例え
ばポリエチレン（PE）やポリプロピレン（PP）等であ
る。[0004] A metal resin composite film which is widely used at present is a laminated structure in which an exterior resin and an interior resin are respectively disposed on the front and back of a metal foil. The metal foil is, for example, aluminum, and the exterior resin is polyethylene terephthalate ( PET) or polyamide, and the inner layer resin is, for example, polyethylene (PE) or polypropylene (PP).
【０００５】[0005]
【発明が解決しようとする課題】金属樹脂複合フィルム
を外装体に用いた非水電解質電池において、特に電解質
に六フッ化燐酸リチウム等の塩を用いた場合、前記金属
樹脂複合フィルムの樹脂と金属箔との界面に剥離が生じ
やすく、また端子部においては封止強度が低下しやすい
といった問題があった。その結果、外部から水分が侵入
しやすくなり、電池性能の劣化や漏液を引き起こし、電
池の耐久性と安全性の点で問題が生じることがあった。SUMMARY OF THE INVENTION In a non-aqueous electrolyte battery using a metal resin composite film for an outer package, particularly when a salt such as lithium hexafluorophosphate is used for the electrolyte, the resin and the metal of the metal resin composite film are used. There has been a problem that peeling is likely to occur at the interface with the foil and that the sealing strength tends to decrease at the terminal portion. As a result, moisture easily enters from the outside, causing deterioration of battery performance and liquid leakage, which may cause problems in terms of battery durability and safety.
【０００６】これは、電池内部で発生するフッ化水素等
の遊離酸によって前記金属樹脂複合フィルムの金属箔が
腐食されることが原因であると考えられている。前記遊
離酸は、LiPF6等の塩と微量水分が反応することによっ
て発生しやすい。従って、前記反応は前記金属樹脂複合
フィルムの樹脂層を通して外気から水分や酸素が侵入
し、かつ塩を含んだ電解液が接触している部位から優先
的に起こりやすい。具体的には、端子封口部、注液部、
最終封口部である。It is considered that this is caused by corrosion of the metal foil of the metal-resin composite film by a free acid such as hydrogen fluoride generated inside the battery. The free acid is easily generated by a reaction between a salt such as LiPF 6 and a trace amount of water. Therefore, the reaction is likely to occur preferentially from a portion where moisture and oxygen enter from the outside air through the resin layer of the metal-resin composite film and are in contact with the electrolyte containing salt. Specifically, the terminal sealing part, the liquid injection part,
This is the final closure.
【０００７】即ち、端子封口部は、前記金属樹脂複合フ
ィルムの金属箔−樹脂界面が電解液に直接曝されやす
い。また、注液部は、外装体に発電要素を挿入した後電
解液を注入し、注液口を封口する際、電解液が残留しや
すい。また、最終封口部は、特に外装体に液溜部を設
け、過剰量の電解液を注液し、初期充放電をした後、発
生した気体と過剰の電解液を絞り出し、電池部と液溜部
の間を最終封口した後液溜部を切除するといった製造方
法によって作製された場合、電解液が残留しやすい。That is, in the terminal sealing portion, the metal foil-resin interface of the metal-resin composite film is easily exposed directly to the electrolytic solution. In addition, when the electrolyte is injected into the liquid injection section after the power generation element is inserted into the exterior body and the liquid injection port is closed, the electrolyte is likely to remain. In addition, the final sealing part is provided with a liquid reservoir particularly on the exterior body, injects an excessive amount of electrolyte, performs initial charge and discharge, then squeezes out generated gas and excess electrolyte, and connects the battery part and the liquid reservoir. When manufactured by a manufacturing method in which the liquid reservoir is cut off after the final sealing between the parts, the electrolytic solution tends to remain.
【０００８】本発明は、上記問題を解決し、電池の耐久
性及び安全性を確保することを目的とする。[0008] It is an object of the present invention to solve the above-mentioned problems and to ensure the durability and safety of a battery.
【０００９】[0009]
【課題を解決するための手段】前記課題を解決するた
め、本発明は、金属樹脂複合フィルムが発電要素を内包
している非水電解質電池において、前記非水電解質電池
は還元体を具備し、前記還元体は前記金属樹脂複合フィ
ルムに用いられている金属と電気的に絶縁され、かつ、
前記還元体の電位が、リチウム金属の電位に対して２．
５V以下に保たれていることを特徴とする非水電解質電
池である。また、前記還元体は、金属箔からなることを
特徴としている。また、前記還元体は、金属層が前記金
属樹脂複合フィルムの内装材表面に形成されてなること
を特徴としている。また、前記還元体は、端子封口部、
注液部、最終封口部のうち少なくとも１つ以上の部位に
近接して配置されたことを特徴としている。In order to solve the above-mentioned problems, the present invention provides a non-aqueous electrolyte battery in which a metal-resin composite film includes a power generation element, wherein the non-aqueous electrolyte battery has a reducing body, The reductant is electrically insulated from the metal used for the metal-resin composite film, and
1. The potential of the reductant is 2.
A non-aqueous electrolyte battery, which is maintained at 5 V or less. Further, the reductant is made of a metal foil. The reductant is characterized in that a metal layer is formed on the surface of the interior material of the metal-resin composite film. Further, the reducing body is a terminal sealing portion,
It is characterized by being arranged close to at least one or more of the liquid injection part and the final sealing part.
【００１０】即ち、電池内部で発生した前記遊離酸を還
元体によって分解させることで、前記遊離酸が引き起こ
す外装体の剥離や封止強度の低下を防ぐものである。例
えば、フッ化水素は前記還元体によって水素とフッ化リ
チウムに還元される。前記還元体は、リチウムの金属の
電位に対して2.5Ｖ以下の電位を有している場合、前記
遊離酸を分解する効果がある。That is, the free acid generated inside the battery is decomposed by a reductant, thereby preventing peeling of the outer package and reduction in sealing strength caused by the free acid. For example, hydrogen fluoride is reduced to hydrogen and lithium fluoride by the reductant. When the reductant has a potential of 2.5 V or less with respect to the potential of the lithium metal, it has an effect of decomposing the free acid.
【００１１】前記還元体としては、非水電解液中におい
て2.5Ｖ以下の自然電位を持つ材料を用いることができ
る。また、2.5Ｖより高い自然電位を持つ材料であって
も、該材料を、例えば負極と電気的に接続することによ
って2.5Ｖ以下の電位に保つことができるので、本発明
の還元体として用いることができる。As the reductant, a material having a natural potential of 2.5 V or less in a non-aqueous electrolyte can be used. Further, even if the material has a natural potential higher than 2.5 V, the material can be maintained at a potential of 2.5 V or less by, for example, electrically connecting to a negative electrode. Can be.
【００１２】前記還元体の材質と配置の方法としては、
導電性炭素粉末、金属粉末等をバインダーでペースト状
にし、塗布する方法等が挙げられるが、金属箔を用いる
と、材料入手が容易であり、配置方法が簡略である点で
好ましい。The material and the method of disposition of the reductant include:
A method of forming a conductive carbon powder, a metal powder, or the like into a paste with a binder and applying the paste may be mentioned, but the use of a metal foil is preferable in that the material is easily available and the arrangement method is simple.
【００１３】また、金属箔等の部品を配置する方法に代
えて、金属樹脂複合フィルムの内装材表面を金属層で被
覆する方法を用いてもよい。この方法を採れば、あらか
じめ内装材表面に金属層被覆処理を施した金属樹脂複合
フィルムを大量生産することができるので、材料コスト
をさらに低減できる点で好ましい。前記金属被覆処理の
方法としては、無電解メッキ、真空蒸着、スパッタリン
グ等が挙げられるが、これらに限定されるものではな
い。In place of the method of arranging components such as metal foil, a method of covering the surface of the interior material of the metal-resin composite film with a metal layer may be used. By adopting this method, it is possible to mass-produce a metal-resin composite film in which the interior material surface is subjected to a metal layer coating treatment in advance, which is preferable in that the material cost can be further reduced. Examples of the metal coating method include, but are not limited to, electroless plating, vacuum deposition, and sputtering.
【００１４】前記還元体を配置する部位としては、金属
樹脂複合フィルムの金属箔の腐食が最初に発生しやすい
部位に優先的に配置することが効果的である。具体的に
は、前述の理由から、端子封口部、注液部、最終封口部
が選択される。It is effective to preferentially place the reductant in a portion where corrosion of the metal foil of the metal-resin composite film is likely to occur first. Specifically, for the above-mentioned reason, the terminal sealing portion, the liquid injection portion, and the final sealing portion are selected.
【００１５】前記部位に加え、金属樹脂複合フィルムが
電解液と接する面積の大半を占める極群の最外周に前記
還元体を配置すると、さらに効果的である。この場合の
還元体の配置方法としては、前記金属層被覆処理を施し
た金属樹脂複合フィルムを外装体に用いることが特に好
適である。また、負極のうち、カーボン等の負極材料を
塗工していない部分、即ち負極集電体が露出している部
分を、例えば捲回式極群の最外周面に配置させることに
よってもよい。It is more effective to arrange the reductant on the outermost periphery of the electrode group which occupies most of the area where the metal-resin composite film is in contact with the electrolytic solution in addition to the above-mentioned parts. In this case, as a method for arranging the reductant, it is particularly preferable to use the metal-resin composite film subjected to the metal layer coating treatment for the outer package. Alternatively, of the negative electrode, a portion where the negative electrode material such as carbon is not applied, that is, a portion where the negative electrode current collector is exposed may be disposed on the outermost peripheral surface of the wound electrode group, for example.
【００１６】[0016]
【発明の実施の形態】本発明は、以下の記述により限定
されるものではない。なお、以下の実施例では、単極電
位の測定及び強制放電の目的で参照極を設けたが、実際
の電池においては、前記参照極は必ずしも必要ではな
い。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is not limited by the following description. In the following examples, a reference electrode was provided for the purpose of measuring the unipolar potential and forcibly discharging, but in an actual battery, the reference electrode is not necessarily required.
【００１７】（本発明電池１）正極は、以下のように作
製した。ＬｉＣｏＯ2、アセチレンブラック及びポリフ
ッ化ビニリデンを、９０：５：５の重量比率で混合後、
溶剤としてＮ−メチルピロリドンを加え、正極スラリー
を作製した。前記正極スラリーを、厚さ２０μｍの帯状
アルミニウム箔の両面に塗工し（一部片面にのみ塗布し
た片面塗工部を含む）、乾燥によりＮ−メチルピロリド
ンを除去し、正極板を得た。前記正極板をロールプレス
によりプレスし、正極を得た。(Battery 1 of the Present Invention) A positive electrode was prepared as follows. After mixing LiCoO 2 , acetylene black and polyvinylidene fluoride in a weight ratio of 90: 5: 5,
N-methylpyrrolidone was added as a solvent to prepare a positive electrode slurry. The positive electrode slurry was applied to both sides of a 20-μm-thick strip-shaped aluminum foil (including a single-side coated portion applied only to one side), and N-methylpyrrolidone was removed by drying to obtain a positive electrode plate. The positive electrode plate was pressed by a roll press to obtain a positive electrode.
【００１８】負極は、以下のように作製した。炭素粒子
の表面を非晶質炭素で修飾したグラファイト及びポリフ
ッ化ビニリデンを、９５：５の重量比率で混合後、Ｎ−
メチルピロリドンを用いて上記材料の負極スラリーを製
作した。前記負極スラリーを厚さ１２μｍの帯状電解銅
箔の両面に塗工し（一部片面にのみ塗布した片面塗工部
を含む）、乾燥によりＮ−メチルピロリドンを除去し、
負極板を得た。この負極板をロールプレスによりプレス
し、負極を得た。The negative electrode was manufactured as follows. After mixing graphite and polyvinylidene fluoride in which the surfaces of the carbon particles were modified with amorphous carbon in a weight ratio of 95: 5, N-
A negative electrode slurry of the above material was prepared using methylpyrrolidone. The negative electrode slurry is coated on both sides of a 12 μm-thick strip-shaped electrolytic copper foil (including a single-side coated portion applied only on one side), and N-methylpyrrolidone is removed by drying.
A negative electrode plate was obtained. This negative electrode plate was pressed by a roll press to obtain a negative electrode.
【００１９】電解液は、以下のように作成した。エチレ
ンカーボネート、ジメチルカーボネート及びエチル−メ
チルカーボネートを１：１：１の容量比で混合し、六フ
ッ化燐酸リチウム（LiPF6）を１リットルあたり１モル
の濃度で溶解させた。The electrolyte was prepared as follows. Ethylene carbonate, dimethyl carbonate and ethyl-methyl carbonate were mixed at a volume ratio of 1: 1: 1 and lithium hexafluorophosphate (LiPF 6 ) was dissolved at a concentration of 1 mol per liter.
【００２０】前記正極及び負極にそれぞれ正極端子４及
び負極端子２を取り付け、最外周に負極の片面塗工部の
銅箔が現れるように、扁平渦状に捲回し、捲回式極群５
を得た。なお、下部の注液口近傍に配置する還元体に負
極電位を印加させるため、負極端子２は下部にも突出さ
せた。捲回後、負極端子の上部及び下部に、還元体１２
として銅箔をスポット溶接により取り付けた。正極端子
４と負極端子２の間に、リチウム金属を先端に付けた参
照電極３を配置し、正極、ラミネートフィルム、還元体
及び参照電極がそれぞれ短絡しないように熱可塑性樹脂
１を貼り付け、固定した。捲回式極群５の外観図を図１
に示す。前記捲回式極群５を、図２に示すチューブ状の
金属樹脂複合フィルムからなる外装体８に挿入し、端子
側の辺を熱溶着し、袋状とした後、注液部から過剰量の
電解液を注液し、仮封口電池とした。A positive electrode terminal 4 and a negative electrode terminal 2 are attached to the positive electrode and the negative electrode, respectively, and are wound in a flat spiral shape so that a copper foil of a one-side coated portion of the negative electrode appears on the outermost periphery.
I got In addition, the negative electrode terminal 2 was also protruded to the lower part in order to apply a negative electrode potential to the reductant disposed near the lower liquid inlet. After winding, the reductant 12 is placed above and below the negative electrode terminal.
And a copper foil was attached by spot welding. A reference electrode 3 having a tip of lithium metal is disposed between the positive electrode terminal 4 and the negative electrode terminal 2, and the thermoplastic resin 1 is attached and fixed so that the positive electrode, the laminate film, the reductant, and the reference electrode are not short-circuited. did. FIG. 1 is an external view of a wound electrode group 5.
Shown in The wound type electrode group 5 is inserted into an outer package 8 made of a tube-shaped metal-resin composite film shown in FIG. 2, and the side on the terminal side is heat-welded to form a bag. Was injected to obtain a temporarily sealed battery.
【００２１】前記仮封口電池に対し、１サイクルの充放
電を行った後、注液部の先端を切除し、加圧により過剰
の電解液及び発生した気体を絞り出した。次に、液溜部
を切断し、再び注液部を封口し、図３に示す本発明電池
１を得た。After one cycle of charging and discharging of the temporary sealed battery, the tip of the liquid injection part was cut off, and excess electrolyte and generated gas were squeezed out by pressurization. Next, the liquid reservoir was cut, and the liquid injection part was sealed again to obtain the battery 1 of the present invention shown in FIG.
【００２２】（本発明電池２）正極、負極及び電解液を
本発明電池１と同じ方法で作成した。前記正極及び負極
にそれぞれ正極端子４及び負極端子２を取り付け、扁平
渦状に捲回し、最外周が銅箔になるように捲回式極群５
を作成した。正極端子４と負極端子２の間に、リチウム
金属を先端に付けた参照電極３を配置し、正極、ラミネ
ートフィルム及び参照電極がそれぞれ短絡しないように
熱可塑性樹脂１を貼り付け、固定した。捲回式極群５の
外観図を図４に示す。(Battery 2 of the Present Invention) A positive electrode, a negative electrode and an electrolytic solution were prepared in the same manner as the battery 1 of the present invention. A positive electrode terminal 4 and a negative electrode terminal 2 are attached to the positive electrode and the negative electrode, respectively, and are wound in a flat spiral shape.
It was created. A reference electrode 3 having a tip of lithium metal was disposed between the positive electrode terminal 4 and the negative electrode terminal 2, and the thermoplastic resin 1 was attached and fixed so that the positive electrode, the laminate film, and the reference electrode did not short-circuit, respectively. FIG. 4 shows an external view of the wound electrode group 5.
【００２３】外装体８は、図５のように金属樹脂複合フ
ィルムの片面に銅を１０nmの厚さで真空蒸着したもの
に、絞り加工により深さ２mmの凹部を設け、その外周部
に接着剤として酸修飾ポリプロピレンフィルムからなる
熱可塑性樹脂１を熱溶着により貼り付けた。前記凹部に
前記極群を配置し、端子部を有する辺および側部の２辺
のうちの１辺を熱融着により封口し、残りの１辺から電
解液を注液後、封口し、本発明電池２を作製した。As shown in FIG. 5, the outer package 8 is formed by vacuum-depositing copper to a thickness of 10 nm on one side of a metal-resin composite film, forming a recess having a depth of 2 mm by drawing, and forming an adhesive on the outer periphery. A thermoplastic resin 1 made of an acid-modified polypropylene film was bonded by heat welding. The electrode group is disposed in the recess, one of the two sides having the terminal portion and the side portion is sealed by heat sealing, the electrolyte is injected from the remaining one side, and then sealed. Inventive Battery 2 was produced.
【００２４】（比較電池１）正極、負極及び電解液を本
発明電池１と同じ方法で作成した。前記正極及び負極に
それぞれ正極端子４及び負極端子２を取り付け、扁平渦
状に捲回し、最外周が正極の片面塗工部裏面のアルミニ
ウム箔が現れるように捲回式極群５を作成した。正極端
子４と負極端子２の間に、リチウム金属を先端に付けた
参照電極３を配置し、正極、ラミネートフィルム及び参
照電極がそれぞれ短絡しないように熱可塑性樹脂１を貼
り付け、固定した。捲回式極群５の外観図は図４と同様
に現れる。(Comparative Battery 1) A positive electrode, a negative electrode, and an electrolytic solution were prepared in the same manner as Battery 1 of the present invention. A positive electrode terminal 4 and a negative electrode terminal 2 were attached to the positive electrode and the negative electrode, respectively, and were wound in a flat spiral shape to form a wound electrode group 5 such that the outermost surface appeared an aluminum foil on the back surface of the one-side coated portion of the positive electrode. A reference electrode 3 having a tip of lithium metal was disposed between the positive electrode terminal 4 and the negative electrode terminal 2, and the thermoplastic resin 1 was attached and fixed so that the positive electrode, the laminate film, and the reference electrode did not short-circuit, respectively. The appearance of the wound electrode group 5 appears as in FIG.
【００２５】（本発明電池１による効果の確認）実施例
として、本発明電池１を複数個用意し、充電を行った
後、負極の開路電位が参照極に対して０．１V、１．０V
または２．５Vになるように放電し、それぞれ、電池
Ａ、電池Ｂ、電池Ｃとした。電池Ａ、電池Ｂ及び電池Ｃ
は各３個づつ用意した。比較例として、本発明電池１を
複数個用意し、充電を行った後、負極の開路電位が参照
極に対して３．０V、３．３Vになるように強制放電し、
それぞれ、電池Ｄ、電池Ｅとした。電池Ｄ及び電池Ｅ
は、それぞれ３個づつ用意した。前記強制放電は、参照
極に対する負極の電位をモニターしながら正極−負極間
に強制的に電流を流すことにより行った。(Confirmation of Effect by Battery 1 of the Present Invention) As an example, a plurality of batteries 1 of the present invention were prepared and charged, and then the open circuit potential of the negative electrode was 0.1 V and 1.0 V with respect to the reference electrode.
Alternatively, the battery was discharged to 2.5 V to obtain a battery A, a battery B, and a battery C, respectively. Battery A, Battery B and Battery C
Were prepared for each three. As a comparative example, a plurality of batteries 1 of the present invention were prepared, charged, and then forcibly discharged so that the open-circuit potential of the negative electrode became 3.0 V and 3.3 V with respect to the reference electrode.
Battery D and battery E were used, respectively. Battery D and Battery E
Were prepared three each. The forced discharge was performed by forcibly flowing a current between the positive electrode and the negative electrode while monitoring the potential of the negative electrode with respect to the reference electrode.
【００２６】本発明電池２及び比較電池１は、それぞれ
３個づつ用意し、全ての電池を充電し、充電末の開路電
圧を４．１Vとした。このとき、全ての電池において、
負極電位は参照極に対して０．１Vであった。The battery 2 of the present invention and the comparative battery 1 were prepared three each, and all the batteries were charged. The open circuit voltage at the end of charging was 4.1 V. At this time, for all batteries,
The negative electrode potential was 0.1 V with respect to the reference electrode.
【００２７】電池Ａ、電池Ｂ、電池Ｃ、電池Ｄ、電池
Ｅ、本発明電池２及び比較電池１を、６０℃の恒温槽中
に一ヶ月間放置した。放置後、外装体の熱融着された部
分の中から各部位を５ｍｍの幅に切り出し、引っ張り試
験機を用いたＴ型剥離試験法により、金属−樹脂界面の
引張り強度を測定した。また、６０℃放置をしていない
本発明電池１についても同様に引張り強度を測定し、初
期値とした。各部位で測定された値の平均値を図６に示
す。The battery A, the battery B, the battery C, the battery D, the battery E, the battery 2 of the present invention, and the comparative battery 1 were left in a thermostat at 60 ° C. for one month. After the standing, each portion was cut out to a width of 5 mm from the heat-sealed portion of the exterior body, and the tensile strength at the metal-resin interface was measured by a T-type peel test using a tensile tester. In addition, the tensile strength of the battery 1 of the present invention which was not left at 60 ° C. was measured in the same manner, and was set as an initial value. The average of the values measured at each site is shown in FIG.
【００２８】６０℃で一ヶ月放置した、電池Ａ、電池
Ｂ、電池Ｃ及び本発明電池２では、金属−樹脂界面の引
張り強度は300g/5mm以上であり、若干の劣化が見られる
が、初期値がほぼ保たれている。一方、印加電位がリチ
ウム金属の電位に対して２．５Vより貴である電池Ｄ、
電池Ｅや、還元体を配置していない比較電池１では、金
属−樹脂界面の引張り強度が100g/5mm以下の箇所が現
れ、比較電池１の測定サンプルの一部には、完全に剥離
してしまっている箇所もみられた。In the battery A, the battery B, the battery C, and the battery 2 of the present invention left at 60 ° C. for one month, the tensile strength at the metal-resin interface is 300 g / 5 mm or more, and a slight deterioration is observed. The value is almost kept. On the other hand, a battery D whose applied potential is more noble than 2.5 V with respect to the potential of lithium metal,
In the battery E and the comparative battery 1 in which no reductant is disposed, a portion where the tensile strength at the metal-resin interface is 100 g / 5 mm or less appears, and a part of the measurement sample of the comparative battery 1 is completely peeled off. Some spots were found.
【００２９】[0029]
【発明の効果】以上の説明からも明らかなように、本発
明は、外装体に金属樹脂複合フィルムを用いた電池にお
いて、リチウム金属の電位に対して２．５V以下に保た
れた還元体を配置させることにより、金属樹脂複合フィ
ルムを遊離酸から保護し、その耐久性と安全性を確保さ
せたので、その工業的価値は大である。As is apparent from the above description, the present invention relates to a battery using a metal-resin composite film as an outer package, and a reductant maintained at 2.5 V or less with respect to the potential of lithium metal. By arranging the metal resin composite film, the metal resin composite film is protected from free acid, and its durability and safety are ensured. Therefore, its industrial value is great.
【図１】本発明電池の極群の外観図である。FIG. 1 is an external view of a pole group of a battery of the present invention.
【図２】チューブ状に成形した金属樹脂複合フィルムの
外観図である。FIG. 2 is an external view of a metal-resin composite film formed into a tube.
【図３】本発明電池の外観図である。FIG. 3 is an external view of the battery of the present invention.
【図４】比較電池の極群の外観図である。FIG. 4 is an external view of a pole group of a comparative battery.
【図５】本発明電池の外観図である。FIG. 5 is an external view of a battery of the present invention.
【図６】金属−樹脂界面の引張り強度の測定結果を示す
グラフである。FIG. 6 is a graph showing measurement results of tensile strength at a metal-resin interface.
５ 巻回式極板群 ８ 金属樹脂複合フィルム １１、１２ 還元体 5 Wound electrode group 8 Metal-resin composite film 11, 12 Reductant
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１２年４月１２日（２０００．４．１
２）[Submission date] April 12, 2000 (2004.1.
2)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００３[Correction target item name] 0003
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００３】前記小型二次電池の構成としては、捲回し
た極群を円筒型のケースに収納した円筒型電池や、平板
状の極板を積層して平角形ケースに収納した角形電池等
がある。より安価で軽量な小型二次電池を提供する手段
として、例えば実開昭６０−１６２３６２号公報、特開
昭６１−２０６１５７号公報では、発電要素を金属樹脂
複合フィルムの袋に収納し、熱溶着により封口したもの
が提案されている。As the configuration of the small secondary battery, there are a cylindrical battery in which wound electrode groups are housed in a cylindrical case, and a rectangular battery in which flat electrode plates are stacked and housed in a rectangular case. is there. As means for providing a cheaper and lighter small secondary battery, for example, Japanese Utility Model Laid-Open No. 60-162362,
Japanese Patent Application Laid-Open No. 61-206157 proposes a power generation element that is housed in a bag made of a metal-resin composite film and sealed by heat welding.
Claims (4)
している非水電解質電池において、前記非水電解質電池
は還元体を具備し、前記還元体は前記金属樹脂複合フィ
ルムに用いられている金属と電気的に絶縁され、かつ、
前記還元体の電位が、リチウム金属の電位に対して２．
５V以下に保たれていることを特徴とする非水電解質電
池。1. A non-aqueous electrolyte battery in which a metal-resin composite film includes a power generation element, wherein the non-aqueous electrolyte battery includes a reductant, and the reductant is a metal used for the metal-resin composite film. Electrically insulated from the
1. The potential of the reductant is 2.
A non-aqueous electrolyte battery maintained at 5 V or less.
徴とする請求項１記載の非水電解質二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the reductant is made of a metal foil.
合フィルムの内装材表面に形成されてなることを特徴と
する請求項１記載の非水電解質電池。3. The non-aqueous electrolyte battery according to claim 1, wherein the reductant has a metal layer formed on the surface of the interior material of the metal-resin composite film.
終封口部のうち少なくとも１つ以上の部位に近接して配
置されたことを特徴とする請求項１〜３のいずれかに記
載の非水電解質電池。4. The method according to claim 1, wherein the reductant is disposed in proximity to at least one of a terminal sealing portion, a liquid injection portion, and a final sealing portion. The nonaqueous electrolyte battery according to any one of the preceding claims.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000074231A JP2001266948A (en) | 2000-03-16 | 2000-03-16 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000074231A JP2001266948A (en) | 2000-03-16 | 2000-03-16 | Non-aqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001266948A true JP2001266948A (en) | 2001-09-28 |
Family
ID=18592318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000074231A Pending JP2001266948A (en) | 2000-03-16 | 2000-03-16 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001266948A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017021889A (en) * | 2015-07-07 | 2017-01-26 | オートモーティブエナジーサプライ株式会社 | Method and apparatus for producing secondary battery |
-
2000
- 2000-03-16 JP JP2000074231A patent/JP2001266948A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017021889A (en) * | 2015-07-07 | 2017-01-26 | オートモーティブエナジーサプライ株式会社 | Method and apparatus for producing secondary battery |
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