JP3850155B2

JP3850155B2 - Electrolytic copper foil, copper foil for current collector of secondary battery and secondary battery

Info

Publication number: JP3850155B2
Application number: JP35321398A
Authority: JP
Inventors: 浩一張ヶ谷; 英男野口; 勝己小林; 和義阿曽
Original assignee: Nippon Denkai Co Ltd
Current assignee: Nippon Denkai Co Ltd
Priority date: 1998-12-11
Filing date: 1998-12-11
Publication date: 2006-11-29
Anticipated expiration: 2018-12-11
Also published as: JP2000182623A

Description

【０００１】
【発明の属する技術分野】
本発明は引張り強さ、伸び率に優れた電解銅箔、この銅箔からなる二次電池の集電体用銅箔及びこの銅箔を用いた二次電池に関する。
【０００２】
【従来の技術】
近年、携帯電子機器の進展は著しく、例えば、電話、ノート型パソコン、カメラ一体型ＶＴＲ、電子スチルカメラなどが普及し、その電源として、ニッケル・カドミウム電池、ニッケル・水素電池、リチウムイオン電池などの二次電池が広く使用されるようになってきた。
【０００３】
とりわけ、リチウムイオン電池は、エネルギー密度、作動電圧が大きく、充放電を伴うサイクル寿命特性に優れていることが注目されている。このリチウムイオン電池の構造は、一般に、正極集電体、例えば２０μｍ程度の厚さを持つアルミニウム箔の両面に、正極活物質、例えば、ＬｉＣｏＯ₂の粉末をバインダーと非水溶媒で混練し、ペースト状にしたものを塗布し、乾燥、圧着一体化させた正極と、負極集電体、例えば１０μｍ程度の厚さを持つ銅箔を使用して、負極活物質、例えば炭素粉末を正極と同様にバインダーと非水溶媒で混練してペースト状にしたものを塗布し、乾燥、圧着一体化させた負極とからなり、この正極と負極との両極の間に絶縁性を有する多孔質セパレータを介して、順次重ね合わせ、円筒形に巻き上げられている。更にこの両極が円筒缶に収納され、非水電解液が注入され、スイッチ素子、安全弁、端子などの部材を設けて二次電池として組み立てられている。
【０００４】
前記するように負極集電体には、導電性に優れる金属箔、例えば、銅箔が多用されている。銅箔には製法の異なる圧延銅箔、電解銅箔が知られている。電解銅箔は、圧延銅箔に比べて量産性に優れ、比較的製造コストも安価である利点から、圧延銅箔と同様に二次電池の負極集電体材料として使用されるようになってきた。
【０００５】
電解銅箔は、一般に、硫酸−硫酸銅水溶液を電解液として用い、一定速度で回転する円筒型陰極と、これと対向配置させて設けた陽極との間に前記電解液を供給し、通電しながら回転する陰極面に銅を析出させ、所定厚みとなった銅箔を陰極面上から剥がしとり製造される。
【０００６】
この電解銅箔の機械的、物理的特性は、当然のことながら、電解液の組成、必要に応じて加えられる各種の薬剤（添加剤）、また、電流密度、電解液供給量などの電解条件に依存し、添加剤を適量添加することにより、引張り強さ、伸び率が制御できることは知られている。
【０００７】
ところで、二次電池に強く要請される特性の一つとして、安全性の点から過充電が行われる際、集電体（銅箔）が経時的に劣化し、亀裂を生じたりあるいは破断するなどの不具合が生じないことが必要である。しかしながら、従来の電解銅箔では、過充電後の集電体（銅箔）の破断状態を表す過充電試験特性を十分に満足させることはできなかった。
【０００８】
【発明が解決しようとする課題】
本発明の目的は、二次電池用の集電体として好適に用いられる常温及び加熱後の引張り強さに優れ、かつ常温及び加熱後の伸び率に優れた電解銅箔を提供することにある。
【０００９】
本発明の他の目的は、二次電池の集電体として用いた場合、過充電試験特性に優れた二次電池が得られる二次電池の集電体用銅箔を提供することにある。
【００１０】
本発明の他の目的は、過充電試験特性に優れた二次電池を提供することにある。
【００１１】
【課題を解決するための手段】
すなわち、本発明は、銅箔中の炭素含有量が５ｐｐｍ以下、硫黄含有量が３ｐｐｍ以下、酸素含有量が５ｐｐｍ以下、窒素含有量が０．５ｐｐｍ以下であり、かつ炭素、硫黄、酸素、窒素及び水素の合計含有量が１５ｐｐｍ以下であることを特徴とする電解銅箔に関する。
【００１２】
本発明はまた、上記の電解銅箔からなることを特徴とするリチウムイオン二次電池の集電体用銅箔に関する。
【００１３】
本発明はまた、平面状集電体の表面に電極構成物質層が形成されてなる正極及び負極を備えるリチウムイオン二次電池において、負極の平面状集電体が上記の電解銅箔であることを特徴とするリチウムイオン二次電池に関する。
【００１４】
【発明の実施の形態】
本発明の電解銅箔は、銅箔中の炭素含有量が５ｐｐｍ以下であり、かつ硫黄含有量が３ｐｐｍ以下であることを特徴とする。このように銅箔中の炭素含有量及び硫黄含有量を制御することにより、常温及び加熱後の引張り強さに優れ、かつ常温及び加熱後の伸び率に優れた電解銅箔が得られる。銅箔中の炭素含有量が５ｐｐｍを超えると加熱後における伸び率が低下する。また、硫黄含有量が３ｐｐｍを超えると加熱後の伸び率が低下する。炭素含有量の好ましい範囲は０．１〜４ｐｐｍであり、硫黄含有量の好ましい範囲は０．１〜２ｐｐｍである。
【００１５】
さらに、本発明の電解銅箔は、銅箔中の酸素含有量が５ｐｐｍ以下であり、かつ窒素含有量が０．５ｐｐｍ以下であることが好ましい。銅箔中の酸素含有量が５ｐｐｍを超えると加熱後の伸び率が低下する傾向にあり、窒素含有量が０．５ｐｐｍを超えると加熱後の伸び率が低下する傾向がある。酸素含有量のより好ましい範囲は０．１〜４ｐｐｍであり、窒素含有量のより好ましい範囲は０．１〜０．４ｐｐｍである。
【００１６】
さらに、本発明の電解銅箔は、銅箔中の炭素、硫黄、酸素、窒素及び水素の合計含有量が１５ｐｐｍ以下であることが好ましい。この不純物の合計量が１５ｐｐｍを超えると常温における引張り強さ及び加熱後の伸び率が低下する傾向がある。炭素、硫黄、酸素、窒素及び水素の合計含有量は１０ｐｐｍ以下であることが更に好ましい。
【００１７】
本発明において、炭素、硫黄、酸素、窒素及び水素の測定は元素分析装置により行われる。炭素及び硫黄の含有量の測定は、堀場製作所製ＥＭＩＡ−８２０により行なうことができ、酸素及び窒素の含有量の測定は、堀場製作所製ＥＭＧＡ−６２０により行なうことができ、水素の含有量の測定は、堀場製作所製ＥＭＧＡ−５２１により行なうことができる。
【００１８】
上記のように不純物含有量が制御された本発明の銅箔は、例えば、電解銅箔製造に用いられる電解液として有機系不純物を高度に除去したものを用いて電解処理することにより得られる。
【００１９】
電解液中の不純物を高度に除去する方法としては、電解液製造に用いられる原料である銅線を６００〜９００℃で３０〜６０分間焼成して用いる方法、硫酸などを用いて銅線を洗浄する方法、高純度の銅線材、硫酸銅、硫酸を用いる方法、電解液中に通常使用される各種添加剤、例えばチオ尿素、アラビアゴム、ゼラチン、膠などを使用しない方法、使用する水として蒸留水又は純水を使用する方法など、あるいはこれらを適宜組み合わせる方法等が挙げられる。
【００２０】
その他に、電解液を活性炭ろ過装置により処理したり、オゾン発生装置により液中に存在する有機物を酸化分解したりして、電解液中の不純物を除去する方法等が挙げられる。
【００２１】
上記の方法により得られた不純物が高度に除去された電解液を用いて電解銅箔を製造することにより、所定の元素含有量の電解銅箔が得られる。
【００２２】
本発明の電解銅箔は、銅箔中の炭素含有量及び硫黄含有量が前記範囲内にあり、常温及び加熱後の引張り強さに優れ、かつ常温及び加熱後の伸び率に優れ、二次電池の集電体として好適に用いられる。
【００２３】
本発明の電解銅箔の表面には必要に応じて、粗面化処理層や、防錆のためにクロメート処理層などの防錆層が設けられていてもよい。
【００２４】
本発明の二次電池は、平面状集電体の表面に電極構成物質層が形成されてなる正極及び負極を備えたものであり、本発明の電解銅箔を正極及び負極の集電体の少なくとも一方、好ましくは負極集電体として使用している。このように、本発明の電解銅箔を集電体として用いることにより、過充電試験特性に優れた二次電池が得られる。その理由は、本発明の電解銅箔は、従来の電解銅箔と比べて、加熱後の銅箔の強度を表す引き裂き伝播時間が長く、二次電池の過充電試験の箔破れが起こりにくくなるからである。
【００２５】
本発明の二次電池の負極の電極構成物質としては、熱分解炭素類、コークス類、グラファイト類、金属リチウム、リチウム合金、ポリアセチレン、ポリピロールなどを使用することができる。
【００２６】
本発明の二次電池の正極の電極構成物質としては、特に制限はなく、ＬｉＮｉＯ₂、ＬｉＣｏＯ₂、ＬｉＭｎ₂Ｏ₄等を単独、又は混合して使用することができる。
【００２７】
電解液としては、ＬｉＣｌＯ₄、ＬｉＰＦ₆等のリチウム塩を、例えば炭酸エチレン、炭酸ジメチルなどの非水系溶剤に溶解したいわゆる有機系電解液をポリフッ化ビニリデン等の高分子固体電解質に含ませた電解液などを使用することができる。
【００２８】
セパレータとしては、例えばポリエチレン、ポリプロピレン等のポリオレフィンを主成分とした不織布、クロス、微孔フィルム又はこれらを組み合わせたものを使用することができる。
【００２９】
なお、円筒型リチウムイオン電池の一例の一部断面正面図を図１に示す。
【００３０】
【実施例】
以下、本発明の実施例及びその比較例によって本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００３１】
実施例１
（１）電解銅箔の製造
銅原料である市販の銅線を７００℃で１時間焼成し、更に１００ｇ／ｌ硫酸水溶液を用いて２０分間酸洗処理し、銅線に付着する不純物を除去した。次いでこの焼成処理及び酸洗処理された銅線を硫酸に溶解し、硫酸銅溶液を得た。この硫酸銅溶液を活性炭を用いたろ過装置によりろ過して下記組成の電解液を得た。なお、硫酸としては精製硫酸を使用した。
硫酸銅（ＣｕＳＯ₄・５Ｈ₂Ｏ）２８０ｇ／ｌ
硫酸（Ｈ₂ＳＯ₄）８０ｇ／ｌ
この電解液を用いて、貴金属酸化物被覆チタンを陽極、チタン製回転ドラムを陰極として、電流密度５０Ａ／ｄｍ²、液温５０℃の条件で電解することによって、厚さ１０μｍの電解銅箔を製造した。得られた銅箔をサンプルとして銅箔中の不純物量の測定及び下記の特性試験を行い、その結果を表１に示す。
（ａ）引張り強さ
常温（２３℃）及び１３０℃で１５時間加熱後の引張り強さをＪＩＳＣ６５１１に基づいて測定した。
（ｂ）伸び率
常温（２３℃）及び１３０℃で１５時間加熱後の伸び率をＪＩＳＣ６５１１に基づいて測定した。
（ｃ）引き裂き伝播時間
１３０℃で１５時間加熱後の引張り強さ試験（クロスヘッドスピード２．０ｍｍ／分、チャートスピード２００ｍｍ／分）における箔の亀裂開始から破断完了までの時間（秒）を測定した。
【００３２】
（２）リチウムイオン電池の製造
図１は、円筒形リチウムイオン電池の一部断面正面図を示し、１は正極、２は負極、３はセパレータ、４は正極リード、５は負極リード、６は正極蓋、７は電池缶及び８はガスケットである。
【００３３】
図１に示すリチウムイオン電池は以下のようにして作製した。正極活物質としては、ＬｉＣｏＯ₂を９０重量部、導電助剤として平均粒径が１μｍの黒鉛を５重量部、及び結着剤としてポリフッ化ビニリデン（ＰＶＤＦ）を５重量部添加して、これにＮ−メチル−２−ピロリドンを５重量部加え正極用合剤ペーストを調製した。同様に負極活物質としてピッチ系炭素繊維９０重量部及び結着剤としてＰＶＤＦを１０重量部添加して、これにＮ−メチル−２−ピロリドンを１０重量部混合して負極用合剤ペーストを得た。
【００３４】
次に正極用合剤ペーストを厚みが２０μｍのアルミニウム箔の両面に塗布し、１２０℃で１０分間予備乾燥し、ローラープレスによって電極を加圧成形した後１３０℃で１５時間真空乾燥し、厚みを１６０μｍとした。単位面積当たりの正極合剤（ペーストから溶剤を除いたもの）塗布量は、２５ｍｇ／ｃｍ²であり、幅が５４ｍｍで長さが４３７ｍｍの大きさに切り出して正極１を作製した。但し正極１の両端の長さ１０ｍｍは、正極用合剤が塗布されておらず、アルミニウム箔が露出されており、この一方に正極リード４を、超音波接合によって圧着した。
【００３５】
一方負極用合剤ペーストを、厚みが１０μｍの実施例１で得た銅箔の両面に塗布し、その後１２０℃で１０分間予備乾燥し、ローラープレスによって電極を加圧成形した後１３０℃で１５時間真空乾燥し、厚みを２００μｍとした。単位面積当たりの負極用合剤（ペーストから溶剤を除いたもの）の塗布量は、１３ｍｇ／ｃｍ²であり、幅が５６ｍｍで長さが４８０ｍｍの大きさに切り出して、負極２を作製した。これを正極１と同様に、負極２の長さ１０ｍｍの部分は、負極用合剤が塗布されておらず、銅箔が露出しており、この一方に負極リード５を超音波接合により圧着した。
【００３６】
セパレータ３は、厚みが２５μｍ、幅が５８ｍｍのポリエチレン製の微孔膜を用いた。次いで図１に示すように正極１、セパレータ３、負極２及びセパレータ３の順で重ね合わせ、これを捲回して電極群とした。これを電池缶に挿入して、負極リード５を缶底に溶接し、正極蓋６を加締るための絞り部を設けた。この後体積比で１：１の炭酸エチレンと炭酸ジメチルの混合溶媒に六フッ化リン酸リチウムを１モル／リットルで溶解させた電解液を電池缶７に注入した後、正極リード４を正極蓋６に溶接した後、正極蓋６をとりつけてリチウムイオン電池を得た。
【００３７】
過充電試験
得られたリチウムイオン電池を用いて、直流２Ａで４０分間及び直流３Ａで３０分間の過充電後、それぞれ電池を解体し、負極銅箔の巻き終わり箇所（５ｃｍ×５ｃｍ、２５ｃｍ²）を目視観察し銅箔破れの有無を調べその個数を測定した。その結果を表１に示す。
【００３８】
実施例２
電解銅箔の製造において、硫酸銅溶液（電解液）を作製するにあたり、銅線の焼成処理を行わなかった以外は、実施例１と同様にして電解銅箔を製造した。この銅箔を用いて、実施例１と同様に銅箔中の不純物量の測定及び（ａ）引張り強さ、（ｂ）伸び率、（ｃ）引き裂き伝播時間の各特性試験を行い、その結果を表１に示した。また、この銅箔を用いて実施例１と同様にしてリチウムイオン電池を製造し、実施例１と同様に過充電試験を行いその結果を表１に示した。
【００３９】
実施例３
電解銅箔の製造において、硫酸銅溶液（電解液）を作製するにあたり、銅線の酸洗処理を行わなかった以外は、実施例１と同様にして電解銅箔を製造した。この銅箔を用いて、実施例１と同様に銅箔中の不純物量の測定及び（ａ）引張り強さ、（ｂ）伸び率、（ｃ）引き裂き伝播時間の各特性試験を行い、その結果を表１に示した。また、この銅箔を用いて実施例１と同様にしてリチウムイオン電池を製造し、実施例１と同様に過充電試験を行いその結果を表１に示した。
【００４０】
比較例１
電解銅箔の製造において、硫酸銅溶液（電解液）を作製するにあたり、銅線に焼成処理及び酸洗処理を行わなかったこと、及び電解液にゼラチンを０．５ｐｐｍ含有させたこと以外は、実施例１と同様にして電解銅箔を製造した。この銅箔を用いて、実施例１と同様に銅箔中の不純物量の測定及び（ａ）引張り強さ、（ｂ）伸び率、（ｃ）引き裂き伝播時間の各特性試験を行い、その結果を表１に示した。また、この銅箔を用いて実施例１と同様にしてリチウムイオン電池を製造し、実施例１と同様に過充電試験を行いその結果を表１に示した。
【００４１】
比較例２
電解銅箔の製造において、硫酸銅溶液（電解液）を作製するにあたり、電解液にゼラチンを３ｐｐｍ、塩素イオンを２０ｐｐｍ含有させたこと以外は、実施例１と同様にして電解銅箔を製造した。この銅箔を用いて、実施例１と同様に銅箔中の不純物量の測定及び（ａ）引張り強さ、（ｂ）伸び率、（ｃ）引き裂き伝播時間の各特性試験を行い、その結果を表１に示した。また、この銅箔を用いて実施例１と同様にしてリチウムイオン電池を製造し、実施例１と同様に過充電試験を行いその結果を表１に示した。
【００４２】
比較例３
電解銅箔の製造において、硫酸銅溶液（電解液）を作製するにあたり、電解液にゼラチンを１０ｐｐｍ含有させたこと以外は、実施例１と同様にして電解銅箔を製造した。この銅箔を用いて、実施例１と同様に銅箔中の不純物量の測定及び（ａ）引張り強さ、（ｂ）伸び率、（ｃ）引き裂き伝播時間の各特性試験を行い、その結果を表１に示した。また、この銅箔を用いて実施例１と同様にしてリチウムイオン電池を製造し、実施例１と同様に過充電試験を行いその結果を表１に示した。
【００４３】
比較例４
市販の厚さ１０μｍの圧延銅箔［Ｃ１１００（ＪＩＳＨ３１１０、タフピッチ銅）、Ｃｕ９９．９０％以上］を用いて実施例１と同様にしてリチウムイオン電池を製造し、実施例１と同様に評価試験を行いその結果を表１に示した。
【００４４】
【表１】

実施例１〜３において、本発明の電解銅箔は銅箔中の不純物の合計量が１５ｐｐｍ以下に低減されているので、銅箔特性の引張り強さ、伸び率を同時に高めている。特に常温引張り強さが５５ｋｇｆ／ｍｍ²以上、加熱後伸び率が２５％以上を保持している。また、引き裂き伝播時間が長く、かつ電池の過充電試験において破断防止に優れている。
【００４５】
一方、比較例１〜３においては、銅箔中の不純物の合計量が１５ｐｐｍを超えていることから常温及び加熱後における引張り強さ、伸び率を本発明のように高められず、二次電池としての過充電試験から明らかなように、信頼性を欠くものである。また、比較例４（圧延銅箔）では、特に加熱後の引張り強さ及び常温伸び率が本発明の銅箔に比べて低い傾向を示し、過充電試験の評価では本発明の銅箔を使用したものより若干劣っていることが判った。
【００４６】
【発明の効果】
本発明の電解銅箔は、常温及び加熱後の引張り強さに優れ、かつ常温及び加熱後の伸び率に優れ、二次電池用の集電体銅箔として好適に用いられる。
【００４７】
また、本発明の二次電池用の集電体銅箔を用いると、過充電試験特性に優れた二次電池を得ることができる。
【００４８】
また、本発明の二次電池は、過充電試験特性特性に優れたものである。
【図面の簡単な説明】
【図１】円筒形リチウムイオン電池の一部断面正面図である。
【符号の説明】
１正極
２負極
３セパレータ
４正極リード
５負極リード
６正極蓋
７電池缶
８ガスケット[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrolytic copper foil excellent in tensile strength and elongation, a copper foil for a current collector of a secondary battery comprising the copper foil, and a secondary battery using the copper foil.
[0002]
[Prior art]
In recent years, the progress of portable electronic devices has been remarkable. For example, telephones, notebook computers, camera-integrated VTRs, electronic still cameras, and the like have become widespread. Secondary batteries have been widely used.
[0003]
In particular, lithium ion batteries have attracted attention because of their high energy density and operating voltage, and excellent cycle life characteristics that accompany charging and discharging. In general, the lithium ion battery has a structure in which a positive electrode active material, for example, LiCoO ₂ powder is kneaded with a binder and a non-aqueous solvent on both sides of a positive electrode current collector, for example, an aluminum foil having a thickness of about 20 μm, and paste Using a positive electrode that has been formed into a shape, dried and pressure-integrated, and a negative electrode current collector, for example, a copper foil having a thickness of about 10 μm, a negative electrode active material, such as carbon powder, is applied in the same manner as the positive electrode. It consists of a negative electrode that has been kneaded with a binder and a non-aqueous solvent, applied in a paste form, dried, and pressure-integrated, and an insulating porous separator is provided between the positive electrode and the negative electrode. , One after another, rolled up into a cylindrical shape. Further, these two electrodes are housed in a cylindrical can, a nonaqueous electrolyte is injected, and members such as a switch element, a safety valve, and a terminal are provided and assembled as a secondary battery.
[0004]
As described above, metal foils having excellent conductivity, such as copper foils, are frequently used for the negative electrode current collector. As the copper foil, a rolled copper foil and an electrolytic copper foil having different manufacturing methods are known. Electrolytic copper foil has been used as a negative electrode current collector material for secondary batteries in the same way as rolled copper foil because of its advantages in mass productivity and relatively low manufacturing cost compared to rolled copper foil. It was.
[0005]
In general, an electrolytic copper foil uses a sulfuric acid-copper sulfate aqueous solution as an electrolytic solution, and supplies the electrolytic solution between a cylindrical cathode that rotates at a constant speed and an anode that is provided so as to face the cylindrical cathode. However, copper is deposited on the rotating cathode surface, and the copper foil having a predetermined thickness is peeled off from the cathode surface to be manufactured.
[0006]
The mechanical and physical characteristics of this electrolytic copper foil are, of course, the electrolytic composition such as the composition of the electrolytic solution, various chemicals (additives) added as necessary, and the current conditions, electrolytic solution supply amount, etc. It is known that the tensile strength and elongation can be controlled by adding an appropriate amount of additives depending on the above.
[0007]
By the way, as one of the characteristics strongly demanded for the secondary battery, when overcharging is performed from the viewpoint of safety, the current collector (copper foil) deteriorates with time, and cracks or breaks. It is necessary that no problems occur. However, in the conventional electrolytic copper foil, the overcharge test characteristic showing the fracture state of the collector (copper foil) after overcharge could not be fully satisfied.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide an electrolytic copper foil that is excellent in tensile strength after normal temperature and heating, and excellent in elongation after normal temperature and heating, which is suitably used as a current collector for a secondary battery. .
[0009]
Another object of the present invention is to provide a copper foil for a current collector of a secondary battery that provides a secondary battery excellent in overcharge test characteristics when used as a current collector of a secondary battery.
[0010]
Another object of the present invention is to provide a secondary battery excellent in overcharge test characteristics.
[0011]
[Means for Solving the Problems]
That is, the present invention has a carbon content in copper foil of 5 ppm or less , a sulfur content of 3 ppm or less , an oxygen content of 5 ppm or less, and a nitrogen content of 0.5 ppm or less, and carbon, sulfur, oxygen, nitrogen. And the total content of hydrogen is 15 ppm or less , It is related with the electrolytic copper foil characterized by the above-mentioned.
[0012]
The present invention also relates to a copper foil for a current collector of a lithium ion secondary battery, characterized by comprising the above-described electrolytic copper foil.
[0013]
The present invention also provides a lithium ion secondary battery comprising a positive electrode and a negative electrode in which an electrode constituent material layer is formed on the surface of the planar current collector, wherein the planar current collector of the negative electrode is the electrolytic copper foil. The present invention relates to a lithium ion secondary battery.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The electrolytic copper foil of the present invention is characterized in that the carbon content in the copper foil is 5 ppm or less and the sulfur content is 3 ppm or less. Thus, by controlling the carbon content and sulfur content in the copper foil, an electrolytic copper foil having excellent tensile strength after normal temperature and heating and excellent elongation at normal temperature and after heating is obtained. If the carbon content in the copper foil exceeds 5 ppm, the elongation percentage after heating decreases. Moreover, when sulfur content exceeds 3 ppm, the elongation rate after a heating will fall. A preferable range of the carbon content is 0.1 to 4 ppm, and a preferable range of the sulfur content is 0.1 to 2 ppm.
[0015]
Furthermore, the electrolytic copper foil of the present invention preferably has an oxygen content in the copper foil of 5 ppm or less and a nitrogen content of 0.5 ppm or less. When the oxygen content in the copper foil exceeds 5 ppm, the elongation after heating tends to decrease, and when the nitrogen content exceeds 0.5 ppm, the elongation after heating tends to decrease. A more preferable range of the oxygen content is 0.1 to 4 ppm, and a more preferable range of the nitrogen content is 0.1 to 0.4 ppm.
[0016]
Furthermore, the electrolytic copper foil of the present invention preferably has a total content of carbon, sulfur, oxygen, nitrogen and hydrogen in the copper foil of 15 ppm or less. If the total amount of impurities exceeds 15 ppm, the tensile strength at room temperature and the elongation after heating tend to decrease. The total content of carbon, sulfur, oxygen, nitrogen and hydrogen is more preferably 10 ppm or less.
[0017]
In the present invention, measurement of carbon, sulfur, oxygen, nitrogen and hydrogen is performed by an elemental analyzer. Measurement of carbon and sulfur content can be performed with EMIA-820 manufactured by Horiba, Ltd. Measurement of oxygen and nitrogen content can be performed with EMGA-620 manufactured by Horiba, Ltd. Measurement of hydrogen content Can be performed by EMGA-521 manufactured by Horiba.
[0018]
The copper foil of the present invention in which the impurity content is controlled as described above can be obtained, for example, by subjecting the copper foil to electrolytic treatment using an electrolytic solution obtained by removing organic impurities to a high degree as an electrolytic solution used for producing an electrolytic copper foil.
[0019]
As a method for highly removing impurities in the electrolytic solution, a copper wire, which is a raw material used for producing an electrolytic solution, is baked at 600 to 900 ° C. for 30 to 60 minutes, and the copper wire is washed with sulfuric acid or the like. , High-purity copper wire, copper sulfate, sulfuric acid, various additives usually used in the electrolyte such as thiourea, gum arabic, gelatin, glue, etc., distilled as water to be used Examples thereof include a method using water or pure water, or a method of appropriately combining these.
[0020]
In addition, a method of removing impurities in the electrolytic solution by treating the electrolytic solution with an activated carbon filter or oxidatively decomposing organic substances present in the solution with an ozone generator may be used.
[0021]
An electrolytic copper foil having a predetermined element content can be obtained by producing an electrolytic copper foil using an electrolytic solution from which impurities obtained by the above method are highly removed.
[0022]
The electrolytic copper foil of the present invention has a carbon content and a sulfur content in the copper foil within the above ranges, is excellent in tensile strength after normal temperature and heating, and is excellent in elongation at normal temperature and after heating. It is suitably used as a battery current collector.
[0023]
If necessary, the surface of the electrolytic copper foil of the present invention may be provided with a roughening treatment layer or a rust prevention layer such as a chromate treatment layer for rust prevention.
[0024]
The secondary battery of the present invention is provided with a positive electrode and a negative electrode in which an electrode constituent material layer is formed on the surface of a planar current collector, and the electrolytic copper foil of the present invention is used as a positive and negative current collector. At least one is preferably used as a negative electrode current collector. Thus, the secondary battery excellent in the overcharge test characteristic is obtained by using the electrolytic copper foil of this invention as a collector. The reason is that the electrolytic copper foil of the present invention has a longer tear propagation time representing the strength of the copper foil after heating, and the foil breakage of the secondary battery overcharge test is less likely to occur than the conventional electrolytic copper foil. Because.
[0025]
As the electrode constituent material of the negative electrode of the secondary battery of the present invention, pyrolytic carbons, cokes, graphites, metallic lithium, lithium alloys, polyacetylene, polypyrrole, and the like can be used.
[0026]
As the electrode structure material of the positive electrode of the secondary battery of the present invention is not particularly limited, and may be LiNiO _2, alone LiCoO _2, LiMn ₂ O ₄ or the like, or a mixture thereof used.
[0027]
As an electrolytic solution, an electrolytic solution in which a so-called organic electrolytic solution obtained by dissolving a lithium salt such as LiClO ₄ or LiPF _{6 in} a non-aqueous solvent such as ethylene carbonate or dimethyl carbonate is contained in a polymer solid electrolyte such as polyvinylidene fluoride. A liquid etc. can be used.
[0028]
As the separator, for example, a nonwoven fabric, a cloth, a microporous film, or a combination of these having a polyolefin such as polyethylene or polypropylene as a main component can be used.
[0029]
A partial cross-sectional front view of an example of a cylindrical lithium ion battery is shown in FIG.
[0030]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.
[0031]
Example 1
(1) Production of electrolytic copper foil A commercially available copper wire, which is a copper raw material, was baked at 700 ° C. for 1 hour, and further pickled with a 100 g / l sulfuric acid aqueous solution for 20 minutes to remove impurities adhering to the copper wire. . Next, this fired and pickled copper wire was dissolved in sulfuric acid to obtain a copper sulfate solution. This copper sulfate solution was filtered with a filtration device using activated carbon to obtain an electrolytic solution having the following composition. Note that purified sulfuric acid was used as the sulfuric acid.
Copper sulfate (CuSO ₄ .5H ₂ O) 280 g / l
Sulfuric acid (H ₂ SO ₄ ) 80 g / l
Using this electrolytic solution, electrolytic copper foil having a thickness of 10 μm is obtained by electrolysis under the conditions of current density 50 A / dm ² and liquid temperature 50 ° C. using a noble metal oxide-coated titanium as an anode and a titanium rotating drum as a cathode. Manufactured. Using the obtained copper foil as a sample, the amount of impurities in the copper foil was measured and the following characteristic test was performed. The results are shown in Table 1.
(A) Tensile strength Tensile strength after heating at room temperature (23 ° C.) and 130 ° C. for 15 hours was measured based on JIS C 6511.
(B) Elongation rate Elongation rate after heating at room temperature (23 ° C) and 130 ° C for 15 hours was measured based on JIS C 6511.
(C) Tear propagation time Measured in seconds (seconds) from the start of cracking to the completion of breaking in a tensile strength test (crosshead speed 2.0 mm / min, chart speed 200 mm / min) after heating at 130 ° C. for 15 hours did.
[0032]
(2) Production of Lithium Ion Battery FIG. 1 shows a partial cross-sectional front view of a cylindrical lithium ion battery, where 1 is a positive electrode, 2 is a negative electrode, 3 is a separator, 4 is a positive electrode lead, 5 is a negative electrode lead, A positive electrode lid, 7 is a battery can, and 8 is a gasket.
[0033]
The lithium ion battery shown in FIG. 1 was produced as follows. As a positive electrode active material, 90 parts by weight of LiCoO ₂ , 5 parts by weight of graphite having an average particle diameter of 1 μm as a conductive auxiliary agent, and 5 parts by weight of polyvinylidene fluoride (PVDF) as a binder were added to this, 5 parts by weight of N-methyl-2-pyrrolidone was added to prepare a positive electrode mixture paste. Similarly, 90 parts by weight of pitch-based carbon fiber as a negative electrode active material and 10 parts by weight of PVDF as a binder are added, and 10 parts by weight of N-methyl-2-pyrrolidone is mixed therewith to obtain a negative electrode mixture paste. It was.
[0034]
Next, the positive electrode mixture paste was applied to both sides of an aluminum foil having a thickness of 20 μm, pre-dried at 120 ° C. for 10 minutes, the electrode was pressure-formed by a roller press, and then vacuum-dried at 130 ° C. for 15 hours to obtain a thickness. It was set to 160 μm. The coating amount of the positive electrode mixture (excluding the solvent from the paste) per unit area was 25 mg / cm ² , cut into a size of 54 mm in width and 437 mm in length to produce the positive electrode 1. However, the positive electrode mixture was not applied to the both ends of the positive electrode 1 with a length of 10 mm, and the aluminum foil was exposed. The positive electrode lead 4 was pressure bonded to this one by ultrasonic bonding.
[0035]
On the other hand, the negative electrode mixture paste was applied on both sides of the copper foil obtained in Example 1 having a thickness of 10 μm, and then pre-dried at 120 ° C. for 10 minutes. Vacuum drying was performed for a time, and the thickness was 200 μm. The coating amount of the negative electrode mixture (one obtained by removing the solvent from the paste) per unit area was 13 mg / cm ² , cut into a size of 56 mm in width and 480 mm in length to produce the negative electrode 2. Similarly to the positive electrode 1, the negative electrode mixture was not applied to the portion of the negative electrode 2 having a length of 10 mm, and the copper foil was exposed, and the negative electrode lead 5 was pressure bonded to this one by ultrasonic bonding. .
[0036]
As the separator 3, a polyethylene microporous film having a thickness of 25 μm and a width of 58 mm was used. Next, as shown in FIG. 1, the positive electrode 1, the separator 3, the negative electrode 2, and the separator 3 were superposed in this order, and this was wound to form an electrode group. This was inserted into a battery can, the negative electrode lead 5 was welded to the bottom of the can, and a throttle part for crimping the positive electrode lid 6 was provided. After that, an electrolytic solution in which lithium hexafluorophosphate was dissolved at a molar ratio of 1: 1 in a mixed solvent of ethylene carbonate and dimethyl carbonate at 1 mol / liter was poured into the battery can 7, and then the positive electrode lead 4 was connected to the positive electrode lid. After welding to 6, a positive electrode lid 6 was attached to obtain a lithium ion battery.
[0037]
Overcharge test Using the obtained lithium ion battery, the battery was disassembled after overcharging at DC 2A for 40 minutes and DC 3A for 30 minutes, respectively, and the end of winding of the negative electrode copper foil (5cm x 5cm, 25cm ² ) Was visually observed to determine the presence or absence of copper foil breakage, and the number was measured. The results are shown in Table 1.
[0038]
Example 2
In the production of the electrolytic copper foil, an electrolytic copper foil was produced in the same manner as in Example 1 except that the copper sulfate solution (electrolytic solution) was not fired. Using this copper foil, the measurement of the amount of impurities in the copper foil and (a) tensile strength, (b) elongation, and (c) tear propagation time characteristic tests were conducted in the same manner as in Example 1. Is shown in Table 1. Further, a lithium ion battery was produced using this copper foil in the same manner as in Example 1, an overcharge test was conducted in the same manner as in Example 1, and the results are shown in Table 1.
[0039]
Example 3
In the production of the electrolytic copper foil, an electrolytic copper foil was produced in the same manner as in Example 1 except that the pickling treatment of the copper wire was not performed in preparing the copper sulfate solution (electrolytic solution). Using this copper foil, the measurement of the amount of impurities in the copper foil and (a) tensile strength, (b) elongation, and (c) tear propagation time characteristic tests were conducted in the same manner as in Example 1. Is shown in Table 1. Further, a lithium ion battery was produced using this copper foil in the same manner as in Example 1, an overcharge test was conducted in the same manner as in Example 1, and the results are shown in Table 1.
[0040]
Comparative Example 1
In the production of the electrolytic copper foil, in producing a copper sulfate solution (electrolytic solution), except that the copper wire was not subjected to baking treatment and pickling treatment, and the electrolytic solution contained 0.5 ppm of gelatin, An electrolytic copper foil was produced in the same manner as in Example 1. Using this copper foil, the measurement of the amount of impurities in the copper foil and (a) tensile strength, (b) elongation, and (c) tear propagation time characteristic tests were conducted in the same manner as in Example 1. Is shown in Table 1. Further, a lithium ion battery was produced using this copper foil in the same manner as in Example 1, an overcharge test was conducted in the same manner as in Example 1, and the results are shown in Table 1.
[0041]
Comparative Example 2
In the production of an electrolytic copper foil, an electrolytic copper foil was produced in the same manner as in Example 1 except that in preparing a copper sulfate solution (electrolytic solution), 3 ppm of gelatin and 20 ppm of chlorine ions were contained in the electrolytic solution. . Using this copper foil, the measurement of the amount of impurities in the copper foil and (a) tensile strength, (b) elongation, and (c) tear propagation time characteristic tests were conducted in the same manner as in Example 1. Is shown in Table 1. Further, a lithium ion battery was produced using this copper foil in the same manner as in Example 1, an overcharge test was conducted in the same manner as in Example 1, and the results are shown in Table 1.
[0042]
Comparative Example 3
In the production of the electrolytic copper foil, an electrolytic copper foil was produced in the same manner as in Example 1 except that 10 ppm of gelatin was contained in the electrolytic solution in preparing a copper sulfate solution (electrolytic solution). Using this copper foil, the measurement of the amount of impurities in the copper foil and (a) tensile strength, (b) elongation, and (c) tear propagation time characteristic tests were conducted in the same manner as in Example 1. Is shown in Table 1. Further, a lithium ion battery was produced using this copper foil in the same manner as in Example 1, an overcharge test was conducted in the same manner as in Example 1, and the results are shown in Table 1.
[0043]
Comparative Example 4
A lithium ion battery was manufactured in the same manner as in Example 1 using a commercially available rolled copper foil having a thickness of 10 μm [C1100 (JIS H 3110, tough pitch copper), Cu 99.90% or more], and evaluated in the same manner as in Example 1. The test was conducted and the results are shown in Table 1.
[0044]
[Table 1]

In Examples 1 to 3, since the total amount of impurities in the copper foil of the present invention is reduced to 15 ppm or less, the tensile strength and elongation of the copper foil characteristics are simultaneously increased. In particular, the room temperature tensile strength is 55 kgf / mm ² or more and the elongation after heating is 25% or more. In addition, the tear propagation time is long, and it is excellent in preventing breakage in the battery overcharge test.
[0045]
On the other hand, in Comparative Examples 1 to 3, since the total amount of impurities in the copper foil exceeds 15 ppm, the tensile strength and elongation after heating at normal temperature and after heating cannot be increased as in the present invention, and the secondary battery As is clear from the overcharge test, it is unreliable. Further, in Comparative Example 4 (rolled copper foil), the tensile strength after heating and the room temperature elongation tend to be lower than those of the copper foil of the present invention, and the copper foil of the present invention is used in the evaluation of the overcharge test. It was found to be slightly inferior to what was done.
[0046]
【The invention's effect】
The electrolytic copper foil of the present invention has excellent tensile strength after normal temperature and heating, and excellent elongation at normal temperature and after heating, and is suitably used as a current collector copper foil for a secondary battery.
[0047]
Moreover, if the collector copper foil for secondary batteries of this invention is used, the secondary battery excellent in the overcharge test characteristic can be obtained.
[0048]
The secondary battery of the present invention is excellent in overcharge test characteristic characteristics.
[Brief description of the drawings]
FIG. 1 is a partial cross-sectional front view of a cylindrical lithium ion battery.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Positive electrode lead 5 Negative electrode lead 6 Positive electrode lid 7 Battery can 8 Gasket

Claims

The carbon content in the copper foil is 5 ppm or less , the sulfur content is 3 ppm or less , the oxygen content is 5 ppm or less, the nitrogen content is 0.5 ppm or less, and the total content of carbon, sulfur, oxygen, nitrogen and hydrogen Is an electrolytic copper foil characterized by being 15 ppm or less .

Current collector foil of a lithium ion secondary battery, characterized in that it consists of an electrolytic copper foil of claim 1 Symbol placement.

A lithium ion secondary battery comprising a positive electrode and a negative electrode, each having an electrode constituent material layer formed on the surface of the planar current collector, wherein the planar current collector of the negative electrode is the electrolytic copper foil according to claim 1. Lithium ion secondary battery.