JP5804712B2 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
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- JP5804712B2 JP5804712B2 JP2011016775A JP2011016775A JP5804712B2 JP 5804712 B2 JP5804712 B2 JP 5804712B2 JP 2011016775 A JP2011016775 A JP 2011016775A JP 2011016775 A JP2011016775 A JP 2011016775A JP 5804712 B2 JP5804712 B2 JP 5804712B2
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- separator
- porous layer
- electrode
- electrolyte secondary
- secondary battery
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- 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
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- 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
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Description
積層して構成された積層微多孔膜を多孔質層(I)としたりする場合には、多孔質層(I)を構成する樹脂(A)中、融点が80℃以上150℃以下の樹脂(例えばPE)が、30質量%以上であることが好ましく、50質量%以上であることがより好ましい。
くするために、例えば、下記のようであることが好ましい。多孔質層(I)の全構成成分
中において主体となる熱可塑性樹脂の体積は、50体積%以上であり、70体積%以上であることがより好ましく、100体積%であってもよい。更に、後記の方法により求められる多孔質層(II)の空孔率が20〜60%であり、かつ熱可塑性樹脂の体積が、多孔質層(II)の空孔体積の50%以上であることが好ましい。
をより有効に発揮させる観点から、6μm以上であることが好ましく、10μm以上であることがより好ましい。ただし、多孔質層(I)が厚すぎると、電池のエネルギー密度の
低下を引き起こす虞があることに加えて、多孔質層(I)が熱収縮しようとする力が大き
くなり、例えば、セパレータA全体の熱収縮を抑える作用が小さくなる虞がある。そのため、多孔質層(I)の厚みは、25μm以下であることが好ましく、20μm以下である
ことがより好ましく、14μm以下であることが更に好ましい。
P={1−m/[(t−tm)×(Σaiρi)+(tm×ρm)]}×100 (1)
ここで、前記式中、ai:成分iの比率、ρi:成分iの密度(g/cm3)、m:セパレータAの単位面積あたりの質量(g/cm2)、t:セパレータAの厚み(cm)、tm:多孔質層(II)の厚み(cm)、ρm:多孔質層(II)を構成する成分の密度(g/cm3)である。
.1、0<x<0.5、0<y<0.5);などを適用することが可能であり、これらの正極活物質に公知の導電助剤(カーボンブラックなどの炭素材料など)やポリフッ化ビニリデン(PVDF)などの結着剤などを適宜添加した正極合剤を、集電体を芯材として成形体(すなわち、正極合剤層)に仕上げたものなどを用いることができる。
SbF6 などの無機リチウム塩;LiCF3SO3、LiCF3CO2、Li2C2F
4(SO3)2、LiN(CF3SO2)2、LiC(CF3SO2)3、LiCnF2n+1SO3(n≧2)、LiN(RfOSO2)2[ここでRfはフルオロアルキル基]などの有機リチウム塩;などを用いることができる。
<正極の作製>
正極活物質であるLiCoO2:85質量部、導電助剤であるアセチレンブラック:10質量部、およびバインダであるPVDF:5質量部を、N−メチル−2−ピロリドン(NMP)を溶剤として均一になるように混合して、正極合剤含有ペーストを調製した。このペーストを、集電体となる厚み15μmのアルミニウム箔の両面に、塗布長が表面320mm、裏面250mmになるように間欠塗布し、乾燥した後、カレンダー処理を行って、全厚が150μmになるように正極合剤層の厚みを調整し、幅43mmになるように切断して、長さ340mm、幅43mmの正極を作製した。更にこの正極のアルミニウム箔の露出部にタブを溶接してリード部を形成した。
また、負極活物質である黒鉛:95質量部と、バインダであるPVDF:5質量部とを、NMPを溶剤として均一になるように混合して負極合剤含有ペーストを調製した。この負極合剤含有ペーストを、銅箔からなる厚み10μmの集電体の両面に間欠塗布し、乾燥した後、カレンダー処理を行って全厚が142μmになるように負極合剤層の厚みを調整し、幅45mmになるように切断して負極を作製した。更にこの負極の銅箔の露出部にタブを溶接してリード部を形成した。
有機バインダであるSBRのエマルジョン(固形分比率40質量%):150gと、水:6000gとを容器に入れ、均一に分散するまで室温で攪拌した。この分散液に耐熱温度が150℃以上のフィラーであるベーマイト粉末(板状、平均粒径1μm、アスペクト比10):2000gを3回に分けて加え、ディスパーにより2800rpmで5時間攪拌して均一なスラリー[多孔質層(II)形成用スラリー、固形分比率49.9質量%]を調製した。湿式二軸延伸法で作製されたPE製微多孔膜[多孔質層(I):厚み12μm、空孔率40%、突き刺し強度400gf、PEの融点135℃]を引き取りつつ、その表面に、前記のスラリーをマイクログラビアコーターによって塗布し、乾燥して、厚みが4.0μmの多孔質層(II)を形成することでセパレータAを作製した。
セパレータBとして、湿式二軸延伸法で作製されたPE製微多孔膜(厚み16μm、空孔率40%)を用意した。
前記の電極巻回体を厚み6mm、高さ50mm、幅34mmのアルミニウム製外装缶に入れ、非水電解液(エチレンカーボネートとエチルメチルカーボネートを1:2の体積比で混合した溶媒に、LiPF6を1.2mol/lの濃度で溶解させた溶液)を注入した後に封止を行って、図3に示す構造で図4に示す外観の非水電解質二次電池を得た。
セパレータBがセパレータAよりも外周側となるようにした以外は、実施例1と同様にして電極巻回体を作製し、この電極巻回体を用いた以外は、実施例1と同様にして非水電解質二次電池を作製した。
乾式一軸延伸法で作製されたPE製微多孔膜[多孔質層(I):厚み12μm、空孔率40%、突き刺し強度250gf、PEの融点135℃]を用いた以外はすべて実施例1と同様にしてセパレータAを作製した。以下、実施例1と同様にして非水電解質二次電池を作製した。
有機バインダであるSBRのエマルジョン(固形分比率40質量%):150gと、水:6000gとを容器に入れ、均一に分散するまで室温で攪拌した。この分散液に耐熱温度が150℃以上のフィラーであるアルミナ粉末(粒状、平均粒径2μm):2600gを3回に分けて加え、ディスパーにより2800rpmで5時間攪拌して均一なスラリー[多孔質層(II)形成用スラリー、固形分比率56.3質量%]を調製した。以下、実施例1と同様にしてセパレータAを作製した。
2枚のセパレータを、いずれも実施例1で使用したものと同じセパレータBとした以外は、実施例1と同様にして電極巻回体を作製し、この電極巻回体を用いた以外は、実施例1と同様にして非水電解質二次電池を作製した。
20、101 正極
30、102 負極
40 セパレータA
50 セパレータB
51 多孔質層(I)
52 多孔質層(II)
Claims (4)
- 正極、負極、並びに前記正極と前記負極との間に介在させる2枚のセパレータAおよびBを重ねて巻回した電極巻回体と、非水電解質とを含む非水電解質二次電池であって、
前記2枚のセパレータのうち、前記セパレータAは、熱可塑性樹脂を主体とする微多孔膜からなる多孔質層(I)と、耐熱温度が150℃以上のフィラーを主体として含む多孔質層(II)とを有する多層構造のセパレータであり、前記セパレータBは、ポリオレフィン製の微多孔膜であり、
前記電極巻回体において、前記正極又は負極は、前記セパレータAと前記セパレータBに隣接し、
前記電極巻回体の両端面において、前記セパレータAと前記セパレータBとが巻回方向に直交する方向に正負極からはみ出していることを特徴とする非水電解質二次電池。 - 前記セパレータAが、前記セパレータBよりも前記電極巻回体のより外周側に配置されている請求項1に記載の非水電解質二次電池。
- 前記多孔質層(I)および前記セパレータBの融点が80℃から150℃の範囲である請求項1または2に記載の非水電解質二次電池。
- 前記多孔質層(II)が前記正極に隣接する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二次電池。
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