JP5652682B2 - 非水電解質二次電池とその製造方法 - Google Patents
非水電解質二次電池とその製造方法 Download PDFInfo
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Description
以下、本発明の一実施形態に係る非水電解質二次電池の製造方法を説明する。特に限定されるものではないが、以下では、リチウム二次電池(リチウムイオン電池)を例として本発明を詳細に説明する。このリチウム二次電池の製造方法は、電池の製造方法の一工程として、塗布工程と、磁場付与工程と、乾燥工程と、圧延工程とを含んでいる。塗布工程は、黒鉛を含む負極合剤を集電体に塗布する工程である。磁場付与工程は、塗布工程において集電体に塗布された負極合剤に対し、負極合剤が塗布された集電体の面と平行な一方向に磁力線が向いた磁場を付与する工程である。乾燥工程は、磁場付与工程において磁場が付与された負極合剤を乾燥させる工程である。圧延工程は、乾燥工程で得られた負極合剤層を圧延する工程である。
続いて、本発明に係る他の実施形態を説明する。この実施形態では、磁場付与工程において、集電体22の幅方向に磁力線が向いた磁場を付与する前に、集電体22の面に直交する方向に磁力線が向いた磁場を付与する点において上述した実施形態とは相違する。
<実施例1>
負極活物質としての天然黒鉛と、結着材としてのSBRと、増粘材としてのCMCとを、それらの材料の質量比が98:1:1となるように水中で混合して負極合剤を調製した。この負極合剤を厚さ10μmの銅箔(負極集電体)に片面当たり塗布量10mg/cm2で塗布し、該塗布された負極合剤に対し、集電体の幅方向に磁力線が向いた磁場を付与した。磁場の付与は、図3に示す磁場付与装置130(磁石132A、132B)を用いて行った。磁石132A、132B間の距離は20cmとし、磁場の強さは0.75Tとし、磁場を作用させる時間は凡そ2.0秒とした。磁場付与後、負極合剤を乾燥させることにより負極集電体の両面に負極合剤層が形成された負極シートを得た。乾燥後、負極合剤層の密度が約1.4g/cm3となるように圧延(プレス)した。
負極合剤層の密度が約1.1g/cm3となるように圧延(プレス)したこと以外は実施例1と同様にして負極シートを作製した。
負極合剤層の密度が約1.7g/cm3となるように圧延(プレス)したこと以外は実施例1と同様にして負極シートを作製した。
集電体に塗布された負極合剤に対し、まず、集電体の面に直交する方向に磁力線が向いた磁場を付与し、その後、集電体の幅方向に磁力線が向いた磁場を付与したこと以外は実施例1と同様にして負極シートを作製した。かかる磁場の付与は、図5に示す磁場付与装置130(磁石132A、132B、134A、134B)を用いて行った。磁石134A、134B間の距離は3.0cmとし、磁場の強さは0.75Tとし、磁場を作用させる時間は凡そ2.0秒とした。磁石132A、132Bについては実施例1と同様の条件である。
負極合剤に対して磁場を付与しなかったこと以外は実施例1と同様にして負極シートを作製した。
負極合剤に対して磁場を付与しなかったこと以外は実施例2と同様にして負極シートを作製した。
負極合剤に対して磁場を付与しなかったこと以外は実施例3と同様にして負極シートを作製した。
正極活物質としてのLiNi1/3Mn1/3Co1/3O2と、導電材としてのアセチレンブラック(AB)と、結着材としてのPVDFとを、それらの材料の質量比が90:8:2となるようにNMP中で混合して正極合剤を調製した。この正極合剤を厚さ15μmのアルミニウム箔(正極集電体)に片面当たり塗布量20mg/cm2塗布し乾燥することにより、正極集電体の両面に正極合剤層が形成された正極シートを得た。乾燥後、正極合剤層の密度が約2.8g/cm3となるように圧延(プレス)した。
上記正極シート及び負極シートを2枚のセパレータシート(厚さ10μmの多孔質ポリプロプレン製の単層構造のものを使用した。)40を介して捲回し、この捲回体を側面方向から押しつぶすことにより扁平状の捲回電極体を作製した。このようにして得られた捲回電極体を非水電解液とともに金属製の箱型の電池ケースに収容し、電池ケースの開口部を気密に封口した。非水電解液としてはエチレンカーボネート(EC)とエチルメチルカーボネート(EMC)とジメチルカーボネート(DMC)とを1:1:1の体積比で含む混合溶媒に支持塩としてのLiPF6を約1mol/リットルの濃度で含有させた非水電解液を使用した。このようにして試験用リチウム二次電池を組み立てた。
以上のように得られた実施例1〜4および比較例1〜3に係る試験用リチウム二次電池のそれぞれを、SOC(充電状態)50%に調整し、25℃の温度条件にて、電流値1Cで電圧4.2Vまで充電した。5分間の休止後、かかる充電後の電池を、25℃において、電流値1Cで電圧2.5Vまで放電した。そして、電流値1Cで電圧4.2Vまで充電し、その後、定電圧方式で電流値が0.1Cに減少するまで充電した。20分間の休止後、かかる充電後の電池を、25℃において、電流値1Cで電圧2.5Vまで放電し、その後、定電圧方式で電流値が0.1Cに減少するまで放電した。このときの放電容量を初期容量として測定した。
また、上記初期容量の測定後、各試験用リチウムイオン電池のそれぞれに対し、高温保存試験を行った。具体的には、試験用リチウム二次電池のそれぞれを50℃で100日間保存した後、上述した初期容量測定と同じ条件で充放電操作を行い、高温保存後の放電容量を測定した。そして、高温保存試験後における放電容量と初期容量とから耐久後容量維持率(「高温保存試験後における放電容量/初期容量」×100)を算出した。結果を表1に示す。
Claims (8)
- 正極および負極を備える非水電解質二次電池の製造方法であって、
黒鉛を含む負極合剤を集電体に塗布する塗布工程と、
前記塗布工程において前記集電体に塗布された前記負極合剤に対し、前記負極合剤が塗布された前記集電体の面と平行な一方向に磁力線が向いた磁場を付与する磁場付与工程と、
前記磁場付与工程において前記磁場が付与された前記負極合剤を乾燥させる乾燥工程と、
前記乾燥工程で得られた負極合剤層を圧延する圧延工程と
を包含し、
前記磁場付与工程では、
(1)前記集電体の面に直交する方向に磁力線が向いた磁場を付与した後、前記集電体の面と平行な一方向に磁力線が向いた磁場を付与する、もしくは、
(2)前記集電体の面と平行な一方向に磁力線が向いた磁場を付与した後、前記集電体の面に直交する方向に磁力線が向いた磁場を付与する、非水電解質二次電池の製造方法。 - 前記磁場付与工程において、まず、前記集電体の面に直交する方向に磁力線が向いた磁場を付与し、その後、前記集電体の面と平行な一方向に磁力線が向いた磁場を付与する、請求項1に記載の非水電解質二次電池の製造方法。
- 前記集電体は、長尺状の集電体であり、
前記磁場付与工程において、前記長尺状の集電体の幅方向に磁力線が向いた磁場を付与する、請求項1または2記載の非水電解質二次電池の製造方法。 - 前記圧延工程後の負極合剤層の密度が1.1g/cm3以上である、請求項1〜3の何れか一つに記載の非水電解質二次電池の製造方法。
- 前記磁場付与工程において前記負極合剤に対し付与される前記磁場の強さが0.5T以上である、請求項1〜4の何れか一つに記載の非水電解質二次電池の製造方法。
- 前記黒鉛は、扁平な鱗片状黒鉛である、請求項1〜5の何れか一つに記載の非水電解質二次電池の製造方法。
- 正極および負極を備える非水電解質二次電池であって、
前記負極は、長尺状の集電体と該集電体の長手方向に形成された少なくとも黒鉛を含む負極合剤層とを有しており、
前記負極合剤層中の黒鉛の少なくとも50質量%は、該黒鉛の(002)面が前記集電体の面に直交し且つ前記集電体の幅方向と平行となるように配置されている、非水電解質二次電池。 - 前記負極合剤層の密度が1.1g/cm3以上である、請求項7に記載の非水電解質二次電池。
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